The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical Weathering of Granites: The Melechov Massif, Czech Republic

*Václav Procházka, Miroslav Žáček, Petr Sulovský, Tomáš Vaculovič, Lenka Rukavičková and Dobroslav Matějka*

#### **Abstract**

Data of 41 or more elements in superficial as well as drill-core samples of the peraluminous Lipnice and Melechov granites, located several kilometers apart in northern Moldanubian Batholith, are evaluated. Weathering of both granite types proceeded in virtually identical time and environment, but it shows very different patterns. In the weathered Lipnice granite, Al2O3 slightly increased, loss on ignition (LOI) increased strongly, and contents of all other major elements except for Fe are lower (however, reconcentration of K, Mg, and Ti in secondary phases is possible). In the relatively coarse-grained and more acidic Melechov granite, the depleted major elements are Si, Fe, Ti, Mn, and Mg. Strongly increased Al in half of weathered samples is independent on the moderate increase of LOI and relatively small changes of Na, Ca, K, and P contents. These samples are relatively poor in quartz, which is the result of fossil weathering, mechanical mineral separation, and erosion processes. In the Lipnice granite, however, chemical weathering dominated over mechanical fractionation due to a more compact character of the rock (as well as of biotite and plagioclase). Regarding trace elements, enrichment in Ga and loss of U are the only changes documented in both granite types (in different proportions however). The rare-earth element (REE) fractionation is generally weak, but in the Lipnice granite, two processes are proven: (i) dissolution of apatite which has an Mtype lanthanide tetrad effect in the fresh rock and (ii) formation of positive Ce anomaly.

**Keywords:** granite weathering, temperate climate, trace elements, apatite, lanthanide tetrad effect, grain size

#### **1. Introduction**

Knowledge of chemical weathering processes is important for pedology, sedimentology, hydrogeochemistry, environmental chemistry, and petrology. Chemical weathering is most frequently studied in magmatic and high-grade metamorphic

rocks which are, by their nature, thermodynamically unstable in superficial conditions. At the same time, chemical composition of the fresh rock is an important fingerprint of magma origin and differentiation. Several elements relatively conservative at weathering, like Sc, Th, and rare-earth elements (REEs), have been also used to assess the source composition of ancient sediments [1].

Chemical weathering of rocks is a complicated interplay of alteration and decomposition of primary minerals including removal of ions in solution, formation of secondary minerals, and removal of the solid weathering products. Ideal conditions for bedrock decomposition differ from ideal conditions for erosion. Therefore, in geological time, environmental changes may lead to the formation of complex profiles, where fossil weathering can be documented [2].

While the research of weathering crusts in the Bohemian Massif was mainly dedicated to economic clay deposits, fossil weathering and small-scale clay formation have been independently documented in various rocks [3]. Pivec [4] described kaolinization in the Říčany granite which probably took place in a warm and humid climate in the Cretaceous. The study of low-temperature fracture fillings in a 100-m-deep borehole in the Kouty granite of the Melechov Massif (MM) [5, 6] documented an intense downward transport of supergene clay enriched in finegrained resistant accessory minerals prevalently in the lower Cretaceous. In this way, also clay minerals of hydrothermal origin could be concentrated. Štemprok [7] showed that hydrothermal kaolinite in granites and greisens occurs in the whole profile of a 1.5-km-deep borehole at Cínovec.

The Melechov Massif is a good representative of the granite body in highland areas of the Bohemian Massif, with thin soil cover and low rate of recent chemical weathering. However, influence of weathering was documented down to ca. 50 m of depth [6, 8]. In this chapter we will focus on the comparison of chemical weathering of Lipnice and Melechov granites, which proceeds in nearly the same time and space but shows very different patterns due to differences not only in rock and mineral chemistries but also in properties relevant for hydrology, mechanical transport, and mineral separation.

The Lipnice granite is fine-grained, with a grain size mostly below 2–2.5 mm. U-Th-Pb monazite ages of this granite range according to the electron microprobe dating from 308 13 to 315 23 Ma [17]. The major minerals are represented by quartz, oligoclase (locally albitized), K-feldspar (mainly microcline), biotite (with dominant annite or siderophyllite component [18, 19]), and muscovite (less abundant than biotite). K-feldspar partly replaces plagioclase, and domains unusually rich in K-feldspar are common, possibly formed by recrystallization of poikilitic microcline observed in some gneisses nearby. In addition, nodules rich in sillimanite and both micas are also abundant, representing probably restite from a material similar to paragneisses present within the area. The significant accessory minerals are ilmenite, fluorapatite (in the following "apatite" only), monazite (Ce), zircon,

*(a) Situation of the Melechov Massif in the Czech Republic and in the Moldanubian Batholith (delimitation of the batholith from Mísař et al. [15]). (b) Granites of the Melechov Massif [10] with localization of boreholes*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

The delimitation of the Lipnice granite boundary in the south and east is difficult and controversial. Also more acidic intrusive and vein rocks appear frequently in the southwest of the granite body [13, 14]. Nevertheless between Lipnice nad Sázavou and Dolní Město, the granite is remarkably homogeneous [18, 21, 22], regardless of the ubiquitous presence of small restite nodules. Microscopic alterations of biotite (with formation of chlorite, muscovite/illite, TiO2 phase, and Kfeldspar) and of plagioclase, i.e., mainly formation of sericite (illite), together with rock fracturation and porosity were recently investigated in detail in the Mel-5

The Melechov granite to alkali-feldspar granite is relatively coarse-grained (with typical grain size 5 mm) and more fractionated than the Lipnice type. The major minerals are quartz, K-feldspar (prevalently microcline), albite (prevalently in perthite with An < 5, however magmatic albite and oligoclase also occur), muscovite and biotite (siderophyllite; less abundant than muscovite). Abundant apatite is the dominant accessory mineral. Zircon and monazite are less abundant, whereas primary ilmenite and rutile are scarce [20]. Tourmaline (schorl) is distributed

Chemically the differentiation of Melechov granite is manifested by higher content of SiO2 and P2O5 and lower content of elements which are compatible in peraluminous granites (mainly Mg, Ti, Fe, Ca, Zr, LREE, Th). In addition the

rutile/anatase, and locally secondary fluorite or pyrrhotite [19–21].

*and polygons of geochemical mapping. Triangle indicates the top of Melechov (715 m).*

borehole in the Lipnice granite [8].

**Figure 1.**

irregularly; xenotime occurs rarely [19].

**75**

#### **2. Geological setting**

The study area is located in the northwestern part of the Bohemian-Moravian Highlands in the Czech Republic (**Figure 1a**). The granites of MM represent the northernmost surface body of Moldanubian Batholith. The massif was formed during the Variscan orogeny (330–300 Ma) in high-grade metamorphic rocks of Moldanubian Unit (prevalently biotite paragneisses and migmatites). The relatively older granites of Lipnice and Kouty types outcrop in the outer part of MM, prevalently on SE (see **Figure 1b**). The central part is formed by the younger Melechov granite type and its derivative, the Stvořidla type. For additional geological and geochemical information, see [9–14].

Similar to other crystalline units of Bohemian Massif, the area was largely peneplenized during the Mesozoic and then uplifted as late as during Pliocene and Pleistocene [15]. Thus, the rocks may have been affected by supergene alterations more than 100 million years ago (even in warmer and more humid climate), as also indicated by Pb isotope ages of fracture fillings [5, 6]. The present climate is temperate with a mean annual temperature of 7 °C and humid, with maximum rainfall in summer; the annual precipitation is roughly 750 mm. Erosion base represented by rivers Sázava and Želivka is located in altitudes 350–380 m. The region has been little industrialized and belongs to the relatively unpolluted ones within central Europe. However, acidification also influenced the area at the end of the twentieth century [16].

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

#### **Figure 1.**

rocks which are, by their nature, thermodynamically unstable in superficial conditions. At the same time, chemical composition of the fresh rock is an important fingerprint of magma origin and differentiation. Several elements relatively conservative at weathering, like Sc, Th, and rare-earth elements (REEs), have been also

Chemical weathering of rocks is a complicated interplay of alteration and decomposition of primary minerals including removal of ions in solution, formation of secondary minerals, and removal of the solid weathering products. Ideal conditions for bedrock decomposition differ from ideal conditions for erosion. Therefore, in geological time, environmental changes may lead to the formation of complex

While the research of weathering crusts in the Bohemian Massif was mainly dedicated to economic clay deposits, fossil weathering and small-scale clay formation have been independently documented in various rocks [3]. Pivec [4] described kaolinization in the Říčany granite which probably took place in a warm and humid climate in the Cretaceous. The study of low-temperature fracture fillings in a 100-m-deep borehole in the Kouty granite of the Melechov Massif (MM) [5, 6] documented an intense downward transport of supergene clay enriched in finegrained resistant accessory minerals prevalently in the lower Cretaceous. In this way, also clay minerals of hydrothermal origin could be concentrated. Štemprok [7] showed that hydrothermal kaolinite in granites and greisens occurs in the

The Melechov Massif is a good representative of the granite body in highland areas of the Bohemian Massif, with thin soil cover and low rate of recent chemical weathering. However, influence of weathering was documented down to ca. 50 m of depth [6, 8]. In this chapter we will focus on the comparison of chemical weathering of Lipnice and Melechov granites, which proceeds in nearly the same time and space but shows very different patterns due to differences not only in rock and mineral chemistries but also in properties relevant for hydrology, mechanical

The study area is located in the northwestern part of the Bohemian-Moravian Highlands in the Czech Republic (**Figure 1a**). The granites of MM represent the northernmost surface body of Moldanubian Batholith. The massif was formed during the Variscan orogeny (330–300 Ma) in high-grade metamorphic rocks of Moldanubian Unit (prevalently biotite paragneisses and migmatites). The relatively older granites of Lipnice and Kouty types outcrop in the outer part of MM, prevalently on SE (see **Figure 1b**). The central part is formed by the younger Melechov granite type and its derivative, the Stvořidla type. For additional geological and

Similar to other crystalline units of Bohemian Massif, the area was largely peneplenized during the Mesozoic and then uplifted as late as during Pliocene and Pleistocene [15]. Thus, the rocks may have been affected by supergene alterations more than 100 million years ago (even in warmer and more humid climate), as also indicated by Pb isotope ages of fracture fillings [5, 6]. The present climate is temperate with a mean annual temperature of 7 °C and humid, with maximum rainfall in summer; the annual precipitation is roughly 750 mm. Erosion base represented by rivers Sázava and Želivka is located in altitudes 350–380 m. The region has been little industrialized and belongs to the relatively unpolluted ones within central Europe. However, acidification

also influenced the area at the end of the twentieth century [16].

used to assess the source composition of ancient sediments [1].

profiles, where fossil weathering can be documented [2].

whole profile of a 1.5-km-deep borehole at Cínovec.

transport, and mineral separation.

geochemical information, see [9–14].

**2. Geological setting**

*Geochemistry*

**74**

*(a) Situation of the Melechov Massif in the Czech Republic and in the Moldanubian Batholith (delimitation of the batholith from Mísař et al. [15]). (b) Granites of the Melechov Massif [10] with localization of boreholes and polygons of geochemical mapping. Triangle indicates the top of Melechov (715 m).*

The Lipnice granite is fine-grained, with a grain size mostly below 2–2.5 mm. U-Th-Pb monazite ages of this granite range according to the electron microprobe dating from 308 13 to 315 23 Ma [17]. The major minerals are represented by quartz, oligoclase (locally albitized), K-feldspar (mainly microcline), biotite (with dominant annite or siderophyllite component [18, 19]), and muscovite (less abundant than biotite). K-feldspar partly replaces plagioclase, and domains unusually rich in K-feldspar are common, possibly formed by recrystallization of poikilitic microcline observed in some gneisses nearby. In addition, nodules rich in sillimanite and both micas are also abundant, representing probably restite from a material similar to paragneisses present within the area. The significant accessory minerals are ilmenite, fluorapatite (in the following "apatite" only), monazite (Ce), zircon, rutile/anatase, and locally secondary fluorite or pyrrhotite [19–21].

The delimitation of the Lipnice granite boundary in the south and east is difficult and controversial. Also more acidic intrusive and vein rocks appear frequently in the southwest of the granite body [13, 14]. Nevertheless between Lipnice nad Sázavou and Dolní Město, the granite is remarkably homogeneous [18, 21, 22], regardless of the ubiquitous presence of small restite nodules. Microscopic alterations of biotite (with formation of chlorite, muscovite/illite, TiO2 phase, and Kfeldspar) and of plagioclase, i.e., mainly formation of sericite (illite), together with rock fracturation and porosity were recently investigated in detail in the Mel-5 borehole in the Lipnice granite [8].

The Melechov granite to alkali-feldspar granite is relatively coarse-grained (with typical grain size 5 mm) and more fractionated than the Lipnice type. The major minerals are quartz, K-feldspar (prevalently microcline), albite (prevalently in perthite with An < 5, however magmatic albite and oligoclase also occur), muscovite and biotite (siderophyllite; less abundant than muscovite). Abundant apatite is the dominant accessory mineral. Zircon and monazite are less abundant, whereas primary ilmenite and rutile are scarce [20]. Tourmaline (schorl) is distributed irregularly; xenotime occurs rarely [19].

Chemically the differentiation of Melechov granite is manifested by higher content of SiO2 and P2O5 and lower content of elements which are compatible in peraluminous granites (mainly Mg, Ti, Fe, Ca, Zr, LREE, Th). In addition the


Melechov type has significantly lower fluorine content (0.08–0.14 wt.%) than the Lipnice type (usually 0.20–0.25 wt.%) and somewhat lower content of K (see also

*Statistics of elements in boreholes (Mel-1 to Mel-5) and in soil base samples of polygons (P1, P2a).*

**(b) Trace elements and element ratios (average)**

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

**—high Al Element** Sr 109.0 103.8 96.7 92.9 98.0 94.6 Ta 0.81 0.75 0.82 3.5 2.96 3.12 Th 42.9 46.1 43.9 3.9 4.1 4.5 U 9.9 6.6 6.1 13.5 5.0 5.3 V 24 24 30 5.5 4 4 W 1.4 1.9 1.6 48 4.3 4.6 Zr 224.5 213.5 210.6 54 55.6 53.7 Y 15.7 15.5 15.7 11.4 13.1 12.7 La 56.7 52.3 52.6 9.1 9.9 9.7 Gd 5.45 5.03 5.19 2.10 2.22 2.16 Lu 0.17 0.16 0.15 0.09 0.10 0.09 REE total 297 281 271 51.6 53.2 51.9 K/Rb 141 130 127 128 125 123 Ca/Sr 70.1 53.6 50.8 60 51.8 52.1 Al/Ga 3437 3367 3512 3638 3930 4573 Th/U 4.37 7.37 7.21 0.31 0.87 0.88 Zr/Hf 34.4 32.9 33.1 26.6 24.2 24.8 Nb/Ta 11.4 11.8 11.3 4.23 4.5 4.4 Eu/Eu\* 0.247 0.235 0.239 0.43 0.443 0.43 Ce/Ce\* 1.06 1.09 1.09 1.05 0.99 1.00 Pr/Pr\* 1.11 1.01 1.00 1.02 0.97 0.97 Y/Ho 32.6 34.0 33.9 32.8 35.5 34.6 *Primary data are from [13, 21]. Note that borehole samples of "fresh" Melechov granite include also hydrothermally*

**P2a weathered —high Al**

**Lipnice granite Melechov granite**

**Mel-1, Mel-2 fresh**

**P1 weathered —low Al**

**P1 weathered**

In comparison with the Lipnice type, the Melechov granite is generally more affected by subsolidus alterations [13, 14]: chloritization; baueritization with formation of secondary Ti, Fe, and Zn oxides [23]; sericitization of plagioclase (with formation of secondary apatite); probably kaolinization of feldspars; and locally carbonatization. Samples affected by such alteration processes (except for carbonatization) exhibit weaker chemical and mineralogical changes (including

coloration by ferric pigments) during supergene weathering, whose

*altered rock which is relatively common. Weathered samples from boreholes were excluded.*

influence is sometimes difficult to be distinguished from alteration at higher

**Table 1a**; **Figure 2**).

**Table 1.**

*Eu/Eu\* = 2EuN/(SmN + GdN). Ce/Ce\* = 3CeN/(2LaN + NdN). Pr/Pr\* = 3PrN/(2NdN + LaN).*

**Samples Mel-5**

**fresh**

**P2a weathered —low Al**

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

temperature [24].

**77**


*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

*Primary data are from [13, 21]. Note that borehole samples of "fresh" Melechov granite include also hydrothermally altered rock which is relatively common. Weathered samples from boreholes were excluded.*

*Eu/Eu\* = 2EuN/(SmN + GdN).*

*Ce/Ce\* = 3CeN/(2LaN + NdN). Pr/Pr\* = 3PrN/(2NdN + LaN).*

#### **Table 1.**

**(a) Major elements Samples SiO2 TiO2 Al2O3 Fe2O3t. MgO MnO CaO Na2O K2O P2O5 LOI Lipnice granite**

Mean 69.87 0.54 14.93 2.49 0.78 0.044 1.06 2.91 5.46 0.301 1.21

Mean 70.76 0.44 15.15 2.33 0.67 0.027 0.79 2.65 5.09 0.290 1.72

Mean 67.82 0.49 17.36 2.69 0.74 0.028 0.70 2.35 5.06 0.271 2.38

Mean 69.79 0.48 14.99 2.53 0.83 0.039 1.10 2.95 5.43 0.256 1.35

Mean 67.21 0.47 17.14 2.65 0.76 0.034 0.77 2.54 5.12 0.280 2.99

Mean 72.98 0.14 14.66 1.26 0.25 0.045 0.74 3.51 4.54 0.41 1.20

Mean 70.44 0.09 16.49 1.00 0.20 0.032 0.71 4.03 4.68 0.48 1.81

Mean 65.32 0.10 21.51 1.04 0.20 0.030 0.68 3.97 4.62 0.47 1.95

**Lipnice granite Melechov granite**

**Melechov granite**

**(b) Trace elements and element ratios (average)**

**—high Al Element** Ba 528.4 514.4 486.6 168.1 174.7 172.3 Be 3.8 4.2 4.2 3.8 4.3 4.1 Co 3.9 3.6 4.5 1.0 1.0 0.9 Cs 8.0 7.4 8.6 24.5 25.2 24.9 Ga 23.0 23.9 27.1 21.4 22.3 25.1 Hf 6.5 6.5 6.4 2.0 2.3 2.2 Nb 9.1 8.5 9.2 14.6 13.0 13.7 Rb 322.3 327.9 333.4 296.7 313.6 314.6 Sn 5.2 6.4 7.4 19.1 24.1 25.8

**P2a weathered —high Al**

0.24 0.03 0.12 0.05 0.05 0.004 0.12 0.06 0.15 0.017 0.05

0.70 0.05 0.27 0.33 0.12 0.007 0.21 0.22 0.16 0.033 0.49

1.46 0.08 0.52 0.55 0.13 0.006 0.14 0.34 0.26 0.040 0.93

0.41 0.04 0.13 0.12 0.05 0.003 0.07 0.09 0.17 0.010 0.17

2.97 0.08 1.83 0.54 0.15 0.010 0.25 0.48 0.33 0.075 1.38

0.71 0.01 0.43 0.19 0.08 0.011 0.14 0.52 0.26 0.02 0.43

1.16 0.02 0.62 0.14 0.03 0.006 0.12 0.29 0.20 0.08 0.53

1.06 0.02 0.89 0.13 0.03 0.007 0.11 0.30 0.28 0.07 0.52

**Mel-1, Mel-2 fresh**

**P1 weathered —low Al**

**P1 weathered**

Fresh, Mel-5 (16.5–150 m), n = 18

*Geochemistry*

Weathered, P2a low-Al group, n = 20

Weathered, P2a high-Al group, n = 26

Weathered, P1, n = 16

Fresh, Mel-1 (37–199.5 m), Mel-2 (22–193 m), n = 44

Weathered, P1 low-Al group, n = 25

Weathered, P1 high-Al group, n = 29

**Samples Mel-5**

**76**

**fresh**

Fresh, Mel-3 (36.4– 106.5, 175–175.5 m), Mel-4 (22–168.4 m), n = 30

St. dev.

St. dev.

St. dev.

St. dev.

St. dev.

St. dev.

St. dev.

St. dev.

> **P2a weathered —low Al**

*Statistics of elements in boreholes (Mel-1 to Mel-5) and in soil base samples of polygons (P1, P2a).*

Melechov type has significantly lower fluorine content (0.08–0.14 wt.%) than the Lipnice type (usually 0.20–0.25 wt.%) and somewhat lower content of K (see also **Table 1a**; **Figure 2**).

In comparison with the Lipnice type, the Melechov granite is generally more affected by subsolidus alterations [13, 14]: chloritization; baueritization with formation of secondary Ti, Fe, and Zn oxides [23]; sericitization of plagioclase (with formation of secondary apatite); probably kaolinization of feldspars; and locally carbonatization. Samples affected by such alteration processes (except for carbonatization) exhibit weaker chemical and mineralogical changes (including coloration by ferric pigments) during supergene weathering, whose influence is sometimes difficult to be distinguished from alteration at higher temperature [24].

Mel-1 to Mel-4) and P2a (which includes borehole Mel-5) were used. These samples were collected in profile grid making a regular network (interval between profiles is ca. 750–900 m, sampling step on profile 150 m). Samples for chemical analyses were collected from the maximum attainable depth, this varying from 0.6 to 2.8 m (mostly close to 2 m in Lipnice granite and 1.5 m in Melechov granite)—see [21] for details. Analyses of saprolites containing pegmatite or quartz veins were excluded

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

The polygon P1 extends from contact of the Melechov and Stvořidla granites to exocontact of the Lipnice granite with paragneisses (the gneisses/migmatites sampled in this area seem to be chemically very similar to the Lipnice granite [21]). Between the Lipnice and Melechov granites outcrops Kouty granite, compositionally and texturally largely transitional between the Lipnice and Melechov types; this rock, however, is represented by relatively few samples and so is not considered here. The area is dominated by the Melechov hill (715 m) and covered prevalently by a managed spruce forest. The major soil type in the forest is dystric cambisol, locally podzolic [28]. Especially in the southern part of P1 (i.e., mainly on Lipnice

The polygon P2a north of Lipnice nad Sázavou represents Lipnice granite (only locally with acidic vein intrusions) and is dominated by the Holý vrch hill (620 m). Almost all samples were taken in the forest (prevailing spruce) and only few samples in abandoned quarries. The dominant soil type is lithic cambisol, in places

Samples from soil cap were analyzed in the ACME Laboratories for both major and trace elements, the methods applied for the presented trace elements being the same as in case of samples from boreholes. The fact that major elements have not been determined under the same conditions in samples of boreholes and of soil cap implies that subtle differences between fresh and weathered rocks have to be treated carefully; however it plays no role in comparison of behavior of the Lipnice

Regarding the distribution of trace elements in rock-forming minerals of the fresh granite, mainly data from the previous studies [19, 20] are considered. In addition, new trace element analyses of apatite are presented. REE, Y, Sr, Th, and U in apatite have been determined by LA-ICP-MS spot analyses in polished sections of rocks at the Department of Chemistry of Faculty of Science, Masaryk University, Brno. Instrumentation for the LA-ICP-MS consists of a laser ablation system UP 213 (New Wave, USA) and an ICP-MS spectrometer Agilent 7500 CE (Agilent, Japan). A commercial Q-switched Nd:YAG laser ablation device works at the wavelength of 213 nm. Helium was used as the carrier gas. For measurements we used hole drilling mode for the duration of 40 seconds for each spot. Laser ablation was performed

The isotopes were measured with integration time 0.1 s / isotope. Optimization of LA-ICP-MS parameters (gas flow rates, sampling depth, electrostatic lens voltages of the MS) was performed with the glass reference material NIST SRM 612 with

Several interesting facts not related to weathering, especially some vertical com-

positional gradients of fresh rocks, have been also found. Here, we present this

respect to maximum S/N ratio and minimum oxide formation (ThO<sup>+</sup>

, and repetition rate 10 Hz.

/Th<sup>+</sup> count

and Kouty granites), there are also agricultural fields and meadows.

from the data processing in the presented study.

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

also pseudogleys occur [28].

and Melechov granite types.

ratio 0.2%, U+

**4. Results**

**79**

with a spot diameter of 25 μm, laser fluence 4.5 J cm<sup>2</sup>

/Th<sup>+</sup> count ratio 1.1%).

**4.1 Composition of fresh and weathered rocks**

**Figure 2.**

*(a–f) Plots of selected pairs of chemical parameters (major components in wt. %, Sr and Ba in ppm) in Lipnice and Melechov granites from boreholes Mel-5, Mel-1, and Mel-2 (including fresh, altered, and weathered samples) and from soil cap in polygons P2a and P1.*

#### **3. Material and methods**

Since the 1990s, the Melechov Massif has been the subject of intensive investigation, leaded by the Radioactive Waste Repository Authority of the Czech Republic (RAWRA = SÚRAO). The results include numerous whole-rock analyses of granites from cores of boreholes 100–200 m deep and from shallow drill holes. These data are completed in unpublished reports [13, 21] and with respect to weathering partly discussed in [25–27].

The fresh granites are represented by core samples taken in intervals of 5–10 m from boreholes Mel-1 and Mel-2 (Melechov type) and Mel-3 to Mel-5 (Lipnice type). However, due to complicated geology and petrology in boreholes Mel-3 and Mel-4, which were intentionally drilled in inhomogeneous environment [13, 14], we present results from these two boreholes only marginally. Borehole samples displaying visible indices of weathering have been included in graphs (**Figure 2**) but not in the statistical processing (**Table 1**). We also used nine analyses of generally very slightly weathered Lipnice granite from outcrops in polygon P2a, analyzed under the same conditions [22]. The major elements were analyzed in the labs of the Czech Geological Survey (ČGS) in Prague and trace elements in the ACME Laboratories, Vancouver, Canada (by ICP-OES and ICP-MS).

As for weathered granite, analyses of samples taken from the lower part of shallow drill holes (soil cap) in the polygons P1 (which also includes the boreholes

#### *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

Mel-1 to Mel-4) and P2a (which includes borehole Mel-5) were used. These samples were collected in profile grid making a regular network (interval between profiles is ca. 750–900 m, sampling step on profile 150 m). Samples for chemical analyses were collected from the maximum attainable depth, this varying from 0.6 to 2.8 m (mostly close to 2 m in Lipnice granite and 1.5 m in Melechov granite)—see [21] for details. Analyses of saprolites containing pegmatite or quartz veins were excluded from the data processing in the presented study.

The polygon P1 extends from contact of the Melechov and Stvořidla granites to exocontact of the Lipnice granite with paragneisses (the gneisses/migmatites sampled in this area seem to be chemically very similar to the Lipnice granite [21]). Between the Lipnice and Melechov granites outcrops Kouty granite, compositionally and texturally largely transitional between the Lipnice and Melechov types; this rock, however, is represented by relatively few samples and so is not considered here. The area is dominated by the Melechov hill (715 m) and covered prevalently by a managed spruce forest. The major soil type in the forest is dystric cambisol, locally podzolic [28]. Especially in the southern part of P1 (i.e., mainly on Lipnice and Kouty granites), there are also agricultural fields and meadows.

The polygon P2a north of Lipnice nad Sázavou represents Lipnice granite (only locally with acidic vein intrusions) and is dominated by the Holý vrch hill (620 m). Almost all samples were taken in the forest (prevailing spruce) and only few samples in abandoned quarries. The dominant soil type is lithic cambisol, in places also pseudogleys occur [28].

Samples from soil cap were analyzed in the ACME Laboratories for both major and trace elements, the methods applied for the presented trace elements being the same as in case of samples from boreholes. The fact that major elements have not been determined under the same conditions in samples of boreholes and of soil cap implies that subtle differences between fresh and weathered rocks have to be treated carefully; however it plays no role in comparison of behavior of the Lipnice and Melechov granite types.

Regarding the distribution of trace elements in rock-forming minerals of the fresh granite, mainly data from the previous studies [19, 20] are considered. In addition, new trace element analyses of apatite are presented. REE, Y, Sr, Th, and U in apatite have been determined by LA-ICP-MS spot analyses in polished sections of rocks at the Department of Chemistry of Faculty of Science, Masaryk University, Brno.

Instrumentation for the LA-ICP-MS consists of a laser ablation system UP 213 (New Wave, USA) and an ICP-MS spectrometer Agilent 7500 CE (Agilent, Japan). A commercial Q-switched Nd:YAG laser ablation device works at the wavelength of 213 nm. Helium was used as the carrier gas. For measurements we used hole drilling mode for the duration of 40 seconds for each spot. Laser ablation was performed with a spot diameter of 25 μm, laser fluence 4.5 J cm<sup>2</sup> , and repetition rate 10 Hz. The isotopes were measured with integration time 0.1 s / isotope. Optimization of LA-ICP-MS parameters (gas flow rates, sampling depth, electrostatic lens voltages of the MS) was performed with the glass reference material NIST SRM 612 with respect to maximum S/N ratio and minimum oxide formation (ThO<sup>+</sup> /Th<sup>+</sup> count ratio 0.2%, U+ /Th<sup>+</sup> count ratio 1.1%).

#### **4. Results**

#### **4.1 Composition of fresh and weathered rocks**

Several interesting facts not related to weathering, especially some vertical compositional gradients of fresh rocks, have been also found. Here, we present this

**3. Material and methods**

**Figure 2.**

*Geochemistry*

**78**

weathering partly discussed in [25–27].

*samples) and from soil cap in polygons P2a and P1.*

Since the 1990s, the Melechov Massif has been the subject of intensive investigation, leaded by the Radioactive Waste Repository Authority of the Czech Republic (RAWRA = SÚRAO). The results include numerous whole-rock analyses of granites from cores of boreholes 100–200 m deep and from shallow drill holes. These data are completed in unpublished reports [13, 21] and with respect to

*(a–f) Plots of selected pairs of chemical parameters (major components in wt. %, Sr and Ba in ppm) in Lipnice and Melechov granites from boreholes Mel-5, Mel-1, and Mel-2 (including fresh, altered, and weathered*

The fresh granites are represented by core samples taken in intervals of 5–10 m

from boreholes Mel-1 and Mel-2 (Melechov type) and Mel-3 to Mel-5 (Lipnice type). However, due to complicated geology and petrology in boreholes Mel-3 and Mel-4, which were intentionally drilled in inhomogeneous environment [13, 14], we present results from these two boreholes only marginally. Borehole samples displaying visible indices of weathering have been included in graphs (**Figure 2**) but not in the statistical processing (**Table 1**). We also used nine analyses of generally very slightly weathered Lipnice granite from outcrops in polygon P2a, analyzed under the same conditions [22]. The major elements were analyzed in the labs of the Czech Geological Survey (ČGS) in Prague and trace elements in the

ACME Laboratories, Vancouver, Canada (by ICP-OES and ICP-MS).

As for weathered granite, analyses of samples taken from the lower part of shallow drill holes (soil cap) in the polygons P1 (which also includes the boreholes information only to distinguish the influence of weathering processes from original granite inhomogeneity. The chemical contrasts between Lipnice and Melechov granite types (including the ratios of isovalent elements Zr/Hf and Nb/Ta and the Eu/Eu\* ratio) are mostly not significantly affected by weathering; however in case of few elements, they were enhanced (Na, P) or smoothened up to reversed (Si, K, U).

with weathering intensity (**Table 1**; **Figure 2d**). One of the possible explanations is formation of illite. In weathered Melechov granite, no systematic shift of K

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

*Relationships of selected element concentrations and ratios in granites of boreholes and polygons (soil cap) to altitude. (a)–(c) Sn (ppm), W (ppm), and Y/Ho ratio in Lipnice and Melechov granites. (d) Co (ppm), (e)*

it is removed by weathering in both granites (**Table 1**).

Both Ca and Na exhibit very different behaviour in the two granites. In weathered Melechov type, Ca is comparable and Na even higher than in the fresh rock (**Figure 2d** and **e**). In contrast, in the Lipnice type, Ca and Na are strongly depleted during weathering. Mg is slightly depleted in weathered granites of both types; however note that in the Melechov granite, this could be related rather to the original magma inhomogeneity than to the weathering (see **Figure 3d**). As for Mn,

content is observed.

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

**Figure 3.**

**81**

*MgO (wt. %) in Melechov granite.*

#### *4.1.1 Major elements*

Core samples of Lipnice granite from the borehole Mel-5 have very low variability regarding major as well as trace elements (see also **Table 1**), and the results show no relation to rock pigmentation and microscopic alteration patterns (chloritization, sericitization) which were investigated in detail [8] in this borehole (except for the uppermost weathered sample, representing the "brown granite"). In Mel-3 and Mel-4, the situation is more complicated: in addition to the typical Lipnice granite, also magmatic vein rocks and a relatively bright, more acidic variety of Lipnice granite were found [13]. In addition, hydrothermally altered granites occur (in contrast to Mel-5). We excluded such samples from the data processing; however it is obvious that even the "fresh" Lipnice granite from boreholes Mel-3 and Mel-4 is less representative than that from Mel-5.

Similarly, the polygon P1 is very inhomogeneous in comparison with P2a [21], and in addition redistribution and contamination of weathered material have been more intensive there [27]. For these reasons and due to the fact that the Lipnice granite is represented by relatively few samples in P1, we evaluated the weathering of Lipnice granite mainly by comparison of borehole Mel-5 and polygon P2a.

Comparing borehole samples taken from various depths, iron oxidation is observed near the surface [25], which is also supported by several slightly weathered samples taken from outcrops in P2a [22]. However, Fe2O3 and FeO were not determined in samples from soil cap singly, what precludes the application of Fe2O3/FeO ratio as otherwise a powerful indicator of chemical weathering in our study.

The weathered Lipnice as well as Melechov granites are enriched in Al2O3 and H2O (which due to low C and S content represents the majority of loss of ignition), especially at the expense of SiO2. Two distinct groups of weathered granite can be distinguished according to Al content, most notably in the Melechov type: Al2O3 ≤ 17.6% and Al2O3 ≥ 19.8% (**Figure 2a**). As shown by [24, 26, 27], the second group is enriched in small particles, which include secondary minerals, detrite of plagioclase, micas and chlorite, and accessory minerals, and is relatively depleted in quartz (the original overlying quartz-rich eluvia were mostly eroded; nevertheless in places, sandy eluvium was preserved and locally used as a building material). Such mineral fractionation was most effective in the coarse-grained Melechov granite, where plagioclase had been already intensively affected by subsolidus alteration and small particles could be transported through a skeleton formed by quartz and K-feldspar [27].

In the Lipnice granite, two groups with different enrichment in Al can be observed in polygon P2a, but they are not so contrasting (Al2O3 = 14.57–15.82 wt. % and 16.66–19.11 wt. %, respectively; in the first group, SiO2 is not lower than in borehole). The most contrasting single parameter of chemical weathering intensity is hydration (expressed as LOI), reaching higher values than in the Melechov type (**Figure 2c**).

The behavior of K is complicated: its content seems to be slightly decreased in weathered Lipnice granite. However, there is no trend of ongoing K removal *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

with weathering intensity (**Table 1**; **Figure 2d**). One of the possible explanations is formation of illite. In weathered Melechov granite, no systematic shift of K content is observed.

Both Ca and Na exhibit very different behaviour in the two granites. In weathered Melechov type, Ca is comparable and Na even higher than in the fresh rock (**Figure 2d** and **e**). In contrast, in the Lipnice type, Ca and Na are strongly depleted during weathering. Mg is slightly depleted in weathered granites of both types; however note that in the Melechov granite, this could be related rather to the original magma inhomogeneity than to the weathering (see **Figure 3d**). As for Mn, it is removed by weathering in both granites (**Table 1**).

#### **Figure 3.**

*Relationships of selected element concentrations and ratios in granites of boreholes and polygons (soil cap) to altitude. (a)–(c) Sn (ppm), W (ppm), and Y/Ho ratio in Lipnice and Melechov granites. (d) Co (ppm), (e) MgO (wt. %) in Melechov granite.*

information only to distinguish the influence of weathering processes from original granite inhomogeneity. The chemical contrasts between Lipnice and Melechov granite types (including the ratios of isovalent elements Zr/Hf and Nb/Ta and the Eu/Eu\* ratio) are mostly not significantly affected by weathering; however in case of few elements, they were enhanced (Na, P) or smoothened up to reversed

Core samples of Lipnice granite from the borehole Mel-5 have very low variability regarding major as well as trace elements (see also **Table 1**), and the results

(chloritization, sericitization) which were investigated in detail [8] in this borehole (except for the uppermost weathered sample, representing the "brown granite"). In Mel-3 and Mel-4, the situation is more complicated: in addition to the typical Lipnice granite, also magmatic vein rocks and a relatively bright, more acidic variety of Lipnice granite were found [13]. In addition, hydrothermally altered granites occur (in contrast to Mel-5). We excluded such samples from the data processing; however it is obvious that even the "fresh" Lipnice granite from boreholes Mel-3 and Mel-4 is less representative than that from Mel-5.

Similarly, the polygon P1 is very inhomogeneous in comparison with P2a [21], and in addition redistribution and contamination of weathered material have been more intensive there [27]. For these reasons and due to the fact that the Lipnice granite is represented by relatively few samples in P1, we evaluated the weathering of Lipnice granite mainly by comparison of borehole Mel-5 and polygon P2a. Comparing borehole samples taken from various depths, iron oxidation is observed near the surface [25], which is also supported by several slightly weathered samples taken from outcrops in P2a [22]. However, Fe2O3 and FeO were not determined in samples from soil cap singly, what precludes the application of Fe2O3/FeO ratio as otherwise a powerful indicator of chemical weathering in

The weathered Lipnice as well as Melechov granites are enriched in Al2O3 and H2O (which due to low C and S content represents the majority of loss of ignition), especially at the expense of SiO2. Two distinct groups of weathered granite can be

Al2O3 ≤ 17.6% and Al2O3 ≥ 19.8% (**Figure 2a**). As shown by [24, 26, 27], the second group is enriched in small particles, which include secondary minerals, detrite of plagioclase, micas and chlorite, and accessory minerals, and is relatively depleted in quartz (the original overlying quartz-rich eluvia were mostly eroded; nevertheless in places, sandy eluvium was preserved and locally used as a building material). Such mineral fractionation was most effective in the coarse-grained Melechov granite, where plagioclase had been already intensively affected by subsolidus alteration and small particles could be transported through a skeleton formed by

In the Lipnice granite, two groups with different enrichment in Al can be observed in polygon P2a, but they are not so contrasting (Al2O3 = 14.57–15.82 wt. % and 16.66–19.11 wt. %, respectively; in the first group, SiO2 is not lower than in borehole). The most contrasting single parameter of chemical weathering intensity is hydration (expressed as LOI), reaching higher values than in the Melechov type

The behavior of K is complicated: its content seems to be slightly decreased in weathered Lipnice granite. However, there is no trend of ongoing K removal

distinguished according to Al content, most notably in the Melechov type:

show no relation to rock pigmentation and microscopic alteration patterns

(Si, K, U).

*Geochemistry*

our study.

quartz and K-feldspar [27].

(**Figure 2c**).

**80**

*4.1.1 Major elements*

#### *Geochemistry*

Phosphorus, slightly depleted in Lipnice granite in P2a only and possibly enriched in weathered Melechov granite, has in all weathered granites positive correlation with calcium (**Figure 2e**), missing in the fresh rock. This indicates importance of apatite. Negative correlation of P and LOI especially in weathered Lipnice type is an indication for apatite dissolution. Another indirect evidence for apatite dissolution and phosphorus mobility is the common occurrence of P-rich limonite in eluvia and low-temperature fracture fillings ([6] and unpublished data of V. Procházka).

Iron content decreased in the weathered Melechov granite but not in Lipnice granite (**Figure 2b**), where the correlation of Fe and LOI (R = 0.68) indicates the possibility of passive (re)concentration of Fe in weathered rock. Note that Fe content (especially Fe2O3) is also significantly lower in borehole Mel-2 than in Mel-1 [13], perhaps as a result of subsolidus alterations of Melechov granite. The behavior of Ti is similar to that of Fe; however weathered Lipnice granite in polygon P2a is mostly significantly depleted in Ti relatively to the fresh rock (**Figure 2b**).

The total carbon content was not measured in boreholes; in soil cap samples, it is usually smaller than 0.2 wt. %, the peak value being 0.36% in P1 and 0.95% in P2a.

*W*. Of the elements analyzed, W is the most differentiated one by vertical fractionation. Its content increases with altitude in boreholes and even in P1, probably reflecting fluid-dominated upward transport of incompatible elements. After distinguishing this vertical trend, it is obvious that weathered Melechov granite is significantly depleted in W and weathered Lipnice granite possibly too (**Figure 3b**);

*(a) Relation of As and U content (in ppm) in Lipnice and Melechov granites in polygon P1 (samples of Melechov granite divided into groups with lower and higher Al content). (b) Gold and silver in granite eluvia of*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

*U*. In Lipnice granite, the U contents both in the samples from shallow pits and

even from outcrops are significantly lower than in the borehole samples. The removal of U from Melechov granite was yet more intensive than from the Lipnice type. As shown by mineral chemistry data and mass balance calculations [19, 30], the rock-forming accessory minerals (monazite, zircon, apatite; in the Melechov type also xenotime) contain at most 70% of U in the Lipnice granite and < 50% U in Melechov granite (in fresh rocks), the rest being obviously in an unstable phase. One possibility is uraninite which was found scarcely [20]; perhaps more important is uranium bound to Fe-oxyhydroxides (see also [5]) and along grain

In the soil cap, there is correlation of U and As, missing in boreholes and suggesting formation of secondary uranium arsenate, in both granite types in poly-

Unlike U, no systematic shift of Th concentration was observed. Therefore, Th/U ratio increased during weathering of both granites (**Table 1b**). Thorium is concentrated predominantly in monazite whose Th/U ratio is higher than that of

*Au, Ag.* Both elements have been systematically determined only in eluvia of P1 polygon. Nevertheless the high concentrations, especially of Au in Al-rich eluvia, cannot be explained by their high content in the original granite, and probably not only passive concentration during weathering but also supergene contamination was important [27]. In six samples from boreholes Mel-1 and Mel-2, the peak Au content (measured by ET-INAA) is 4.5 ppb (V. Procházka & J. Mizera, unpublished data), i.e., by 1–3 orders of magnitude lower than in eluvia of Melechov granite

*REE, Y.* REEs are generally little affected by weathering. However, the most weathered (high-Al) group of Lipnice granite shows some depletion in total REE, and evaluation of their mutual ratios revealed several trends. The comparison of variability of individual REEs in boreholes and in eluvia shows that the variation coefficient (the mean/standard deviation ratio) in weathered Melechov granite has a distinct minimum at Eu (**Table 2**). It follows that in weathered Melechov granite, the content of feldspars (the major reservoir of Eu2+) in individual samples is more

in both cases, however, mean values are biased by outliers.

gon P1 (**Figure 4a**; in P2a, As was not analyzed).

respective whole rock [19, 20, 30].

boundaries [31].

**Figure 4.**

*Lipnice and Melechov types in P1.*

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

(**Figure 4b**).

**83**

It follows that mainly elements concentrated in plagioclase are depleted in the Lipnice granite whereas elements originally concentrated mainly in biotite (or its alteration products) are depleted in both granite types, except for Fe in Lipnice granite.

#### *4.1.2 Trace elements*

Only elements showing significant fractionation during weathering at least in one granite type are presented here.

*Sr, Ba*. Strontium and barium are significantly depleted in weathered Lipnice granite but not in weathered Melechov granite (**Figure 2f**). Despite the removal of Sr, the mean Ca/Sr ratio of weathered Lipnice granite is significantly lower than that of fresh rock (**Table 1b**).

*Co*. There is no systematic trend of Co content in Lipnice granite. In Melechov type, however, Co has a decreasing trend with altitude (as a compatible element), and it cannot be excluded that weathering leads to enrichment in Co (**Figure 3e**). The Co content in borehole Mel-2 is mostly lower than in Mel-1.

*Ga*. Gallium was passively concentrated in chemically weathered rocks similarly to Al. However, the Al/Ga ratio in weathered Melechov granite is significantly higher than in fresh rock. In weathered Lipnice granite, such a systematic trend is not observed; only the variability of Al/Ga ratio is much higher.

*Sn*. Tin content is at average higher in weathered Melechov granite than in the fresh rock (**Figure 3a**; **Table 1b**). This may reflect vertical differentiation trend only, which however is not apparent in boreholes Mel-1 and Mel-2. Possible explanation is stronger chemical fractionation in apical part of the Melechov granite intrusion (according to [29], the original contact was not far above the present top of Melechov hill). Interestingly, Mg in the Melechov granite exhibits opposite behavior to Sn (**Figure 3d**). In the Lipnice granite, Sn also has an increasing trend with altitude, complicating the evaluation of possible weathering influence (**Figure 3a**).

*V*. In weathered Lipnice granite, V content is higher than in boreholes. The concentration of V by Fe-oxyhydroxides is one of the possible explanations. In Melechov granite, vanadium was mostly below detection limit (<5 ppm), the exception being borehole Mel-1. It follows that weathering led rather to removal of V from the Melechov type; however the effect of older alterations could be similar. *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

**Figure 4.**

Phosphorus, slightly depleted in Lipnice granite in P2a only and possibly enriched in weathered Melechov granite, has in all weathered granites positive correlation with calcium (**Figure 2e**), missing in the fresh rock. This indicates importance of apatite. Negative correlation of P and LOI especially in weathered Lipnice type is an indication for apatite dissolution. Another indirect evidence for apatite dissolution and phosphorus mobility is the common occurrence of P-rich limonite in eluvia and low-temperature fracture fillings ([6] and unpublished data

Iron content decreased in the weathered Melechov granite but not in Lipnice granite (**Figure 2b**), where the correlation of Fe and LOI (R = 0.68) indicates the possibility of passive (re)concentration of Fe in weathered rock. Note that Fe content (especially Fe2O3) is also significantly lower in borehole Mel-2 than in Mel-1 [13], perhaps as a result of subsolidus alterations of Melechov granite. The behavior of Ti is similar to that of Fe; however weathered Lipnice granite in polygon P2a is mostly significantly depleted in Ti relatively to the fresh rock (**Figure 2b**).

The total carbon content was not measured in boreholes; in soil cap samples, it is usually smaller than 0.2 wt. %, the peak value being 0.36% in P1 and 0.95% in P2a. It follows that mainly elements concentrated in plagioclase are depleted in the Lipnice granite whereas elements originally concentrated mainly in biotite (or its alteration products) are depleted in both granite types, except for Fe in Lipnice

Only elements showing significant fractionation during weathering at least in

*Sr, Ba*. Strontium and barium are significantly depleted in weathered Lipnice granite but not in weathered Melechov granite (**Figure 2f**). Despite the removal of Sr, the mean Ca/Sr ratio of weathered Lipnice granite is significantly lower than

*Co*. There is no systematic trend of Co content in Lipnice granite. In Melechov type, however, Co has a decreasing trend with altitude (as a compatible element), and it cannot be excluded that weathering leads to enrichment in Co (**Figure 3e**).

*Ga*. Gallium was passively concentrated in chemically weathered rocks similarly

*Sn*. Tin content is at average higher in weathered Melechov granite than in the fresh rock (**Figure 3a**; **Table 1b**). This may reflect vertical differentiation trend only, which however is not apparent in boreholes Mel-1 and Mel-2. Possible explanation is stronger chemical fractionation in apical part of the Melechov granite intrusion (according to [29], the original contact was not far above the present top of Melechov hill). Interestingly, Mg in the Melechov granite exhibits opposite behavior to Sn (**Figure 3d**). In the Lipnice granite, Sn also has an increasing trend with altitude, complicating the evaluation of possible weathering influence

*V*. In weathered Lipnice granite, V content is higher than in boreholes. The concentration of V by Fe-oxyhydroxides is one of the possible explanations. In Melechov granite, vanadium was mostly below detection limit (<5 ppm), the exception being borehole Mel-1. It follows that weathering led rather to removal of V from the Melechov type; however the effect of older alterations could be similar.

to Al. However, the Al/Ga ratio in weathered Melechov granite is significantly higher than in fresh rock. In weathered Lipnice granite, such a systematic trend is

The Co content in borehole Mel-2 is mostly lower than in Mel-1.

not observed; only the variability of Al/Ga ratio is much higher.

of V. Procházka).

*Geochemistry*

granite.

*4.1.2 Trace elements*

(**Figure 3a**).

**82**

one granite type are presented here.

that of fresh rock (**Table 1b**).

*(a) Relation of As and U content (in ppm) in Lipnice and Melechov granites in polygon P1 (samples of Melechov granite divided into groups with lower and higher Al content). (b) Gold and silver in granite eluvia of Lipnice and Melechov types in P1.*

*W*. Of the elements analyzed, W is the most differentiated one by vertical fractionation. Its content increases with altitude in boreholes and even in P1, probably reflecting fluid-dominated upward transport of incompatible elements. After distinguishing this vertical trend, it is obvious that weathered Melechov granite is significantly depleted in W and weathered Lipnice granite possibly too (**Figure 3b**); in both cases, however, mean values are biased by outliers.

*U*. In Lipnice granite, the U contents both in the samples from shallow pits and even from outcrops are significantly lower than in the borehole samples. The removal of U from Melechov granite was yet more intensive than from the Lipnice type. As shown by mineral chemistry data and mass balance calculations [19, 30], the rock-forming accessory minerals (monazite, zircon, apatite; in the Melechov type also xenotime) contain at most 70% of U in the Lipnice granite and < 50% U in Melechov granite (in fresh rocks), the rest being obviously in an unstable phase. One possibility is uraninite which was found scarcely [20]; perhaps more important is uranium bound to Fe-oxyhydroxides (see also [5]) and along grain boundaries [31].

In the soil cap, there is correlation of U and As, missing in boreholes and suggesting formation of secondary uranium arsenate, in both granite types in polygon P1 (**Figure 4a**; in P2a, As was not analyzed).

Unlike U, no systematic shift of Th concentration was observed. Therefore, Th/U ratio increased during weathering of both granites (**Table 1b**). Thorium is concentrated predominantly in monazite whose Th/U ratio is higher than that of respective whole rock [19, 20, 30].

*Au, Ag.* Both elements have been systematically determined only in eluvia of P1 polygon. Nevertheless the high concentrations, especially of Au in Al-rich eluvia, cannot be explained by their high content in the original granite, and probably not only passive concentration during weathering but also supergene contamination was important [27]. In six samples from boreholes Mel-1 and Mel-2, the peak Au content (measured by ET-INAA) is 4.5 ppb (V. Procházka & J. Mizera, unpublished data), i.e., by 1–3 orders of magnitude lower than in eluvia of Melechov granite (**Figure 4b**).

*REE, Y.* REEs are generally little affected by weathering. However, the most weathered (high-Al) group of Lipnice granite shows some depletion in total REE, and evaluation of their mutual ratios revealed several trends. The comparison of variability of individual REEs in boreholes and in eluvia shows that the variation coefficient (the mean/standard deviation ratio) in weathered Melechov granite has a distinct minimum at Eu (**Table 2**). It follows that in weathered Melechov granite, the content of feldspars (the major reservoir of Eu2+) in individual samples is more

stable than that of the main carriers of trivalent REEs, including Sm and Gd monazite and apatite. The fact that similar situation is not observed in the Lipnice granite could be related to more intense weathering of feldspars and to more homogeneous distribution of monazite in the Lipnice type (in Melechov granite, the most of monazite is bound to large apatite crystals [19]).

In "fresh" Melechov granite of borehole Mel-2, the REE distribution including elevated Eu/Eu\* ratio is very similar to weathered Melechov granite, the weathered granite having only somewhat higher total REE (**Figure 5b**). This shows that the effect of surface weathering on REE distribution of Melechov granite was very similar to the effect of former alteration processes, which were more intensive in Mel-2 than Mel-1. Note that the lower REE content in Melechov granite is associated with relatively greater analytical uncertainty.

To display subtle changes at a relatively low degree of weathering, we normalized REE in weathered samples by the average value of REE in boreholes (**Figure 5**).

The Y/Ho ratios of weathered granites seem to be somewhat elevated, which is however partly masked by vertical fractionation (**Figure 3c**).

In the Lipnice granite of outcrops (in P2a), there are relative minima of Ce and Pr, resembling the W type of tetrad effect. The appearance of only first tetrad can be related to REE distribution in apatite (see Section 4.2.). In more weathered samples (soil cap) of P2a, the minimum at Ce gradually disappears, and rather a positive cerium anomaly is formed. The W-type tetrad effect and positive Ce anomaly partially mask one another. It can be summarized that some portion of REE controlled by apatite (with M-type tetrad effect) was removed from weathered rocks, but Ce was partly immobilized by oxidation to CeIV.

Out of other REEs, the only systematic fractionation in weathered granites is a

*Plot of cerium anomaly and Pr/Pr\* (as a manifestation of the first tetrad) in the Lipnice granite in borehole Mel-5 and polygon P2a (soil cap). Ce/Ce\* = 3CeN/(2LaN + NdN); Pr/Pr\* = 3PrN/(2NdN + LaN). Normalizing*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

Other elements concentrated in monazite (Th), zircon (Zr, Hf), and (Fe-)Ti oxides (Nb, Ta) are not significantly affected by weathering, which is also true for Zr/Hf and Nb/Ta ratios. Therefore, it seems that dissolution of primary accessory minerals except for apatite was not significant for REE behavior during weathering. The locally observed alteration of monazite can be attributed to Ca-rich hydrother-

**(a) Lipnice granite, Kopaniny (standardized to assumed Ca content 38 wt. %)**

Sr 128 153 140 122 121 102 129 118 105 124 151 **127** 15 Y 2101 2755 2477 2182 2040 1979 2124 1959 2031 2470 1171 **2117** 367 La 384 486 473 431 330 378 373 399 405 484 222 **397** 70 Ce 1182 1633 1762 1661 1128 1363 1304 1500 1511 1461 842 **1395** 245 Pr 180 267 287 271 166 226 226 209 221 212 142 **219** 41 Nd 970 1353 1203 1352 815 1039 1132 890 956 1033 743 **1044** 183 Sm 376 475 391 475 318 367 417 350 347 386 233 **376** 63 Eu 9 10 9 10 9 8 10 7 7 9 12 **9** 1,5 Gd 310 525 372 502 368 440 420 316 345 396 262 **387** 74 Tb 48 89 66 65 58 70 63 47 61 58 41 **60** 12 Dy 351 605 516 412 378 475 393 330 422 449 294 **421** 81 Ho 67 98 103 79 73 82 74 64 74 80 61 **78** 12 Er 207 271 272 247 212 213 196 188 197 193 145 **213** 34 Tm 32 36 38 34 32 27 26 29 31 26 28 **31** 3,6 Yb 204 241 216 188 198 172 174 187 184 167 138 **188** 25 Lu 27 38 30 27 27 22 30 26 25 25 21 **27** 4,1 Th 21 16 9 9 23 20 25 10 15 10 19 **16** 5,3

**1 2 3 4 5 8 9 10 14 15 16 Mean St.**

**dev.**

relative maximum of Yb (**Figure 5a** and **b**).

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

mal fluids [20].

**An. no.**

**85**

**Figure 6.**

*values from [32].*

The fact that fractionation of La, Ce, Pr, and Nd does not reflect the original granite inhomogeneity is documented by **Figure 6**.


#### **Table 2.**

*Variation coefficients for individual REE and Y in fresh and weathered granites (bor. = borehole Mel-5 or Mel-1 and Mel-2).*

#### **Figure 5.**

*(a) REE in Lipnice granite of soil base (divided into low-Al and high-Al groups) and small rock outcrops in polygon P2a, normalized by the mean of the borehole Mel-5. (b) REE in various groups of samples of Melechov granite normalized by the mean of fresh Melechov granite from borehole Mel-1.*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

**Figure 6.**

stable than that of the main carriers of trivalent REEs, including Sm and Gd monazite and apatite. The fact that similar situation is not observed in the Lipnice granite could be related to more intense weathering of feldspars and to more homogeneous distribution of monazite in the Lipnice type (in Melechov granite, the

In "fresh" Melechov granite of borehole Mel-2, the REE distribution including elevated Eu/Eu\* ratio is very similar to weathered Melechov granite, the weathered granite having only somewhat higher total REE (**Figure 5b**). This shows that the effect of surface weathering on REE distribution of Melechov granite was very similar to the effect of former alteration processes, which were more intensive in Mel-2 than Mel-1. Note that the lower REE content in Melechov granite is associated

To display subtle changes at a relatively low degree of weathering, we normalized REE in weathered samples by the average value of REE in boreholes (**Figure 5**). The Y/Ho ratios of weathered granites seem to be somewhat elevated, which is

In the Lipnice granite of outcrops (in P2a), there are relative minima of Ce and Pr, resembling the W type of tetrad effect. The appearance of only first tetrad can be related to REE distribution in apatite (see Section 4.2.). In more weathered samples (soil cap) of P2a, the minimum at Ce gradually disappears, and rather a positive cerium anomaly is formed. The W-type tetrad effect and positive Ce anomaly partially mask one another. It can be summarized that some portion of REE controlled by apatite (with M-type tetrad effect) was removed from weathered

The fact that fractionation of La, Ce, Pr, and Nd does not reflect the original

Lip bor. 5 0.05 0.04 0.04 0.05 0.05 0.06 0.07 0.09 0.07 0.06 0.08 0.09 0.13 0.11 0.10 Lip P2a 0.16 0.15 0.15 0.15 0.15 0.14 0.13 0.14 0.13 0.14 0.16 0.17 0.15 0.17 0.17

Mel P1 0.20 0.20 0.20 0.21 0.21 0.14 0.22 0.22 0.22 0.20 0.19 0.19 0.22 0.19 0.22

*Variation coefficients for individual REE and Y in fresh and weathered granites (bor. = borehole Mel-5 or*

*(a) REE in Lipnice granite of soil base (divided into low-Al and high-Al groups) and small rock outcrops in polygon P2a, normalized by the mean of the borehole Mel-5. (b) REE in various groups of samples of Melechov*

*granite normalized by the mean of fresh Melechov granite from borehole Mel-1.*

**La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu**

0.12 0.11 0.10 0.13 0.12 0.10 0.13 0.12 0.13 0.10 0.13 0.12 0.28 0.13 0.20

most of monazite is bound to large apatite crystals [19]).

however partly masked by vertical fractionation (**Figure 3c**).

rocks, but Ce was partly immobilized by oxidation to CeIV.

granite inhomogeneity is documented by **Figure 6**.

Mel bor. 1,2

*Geochemistry*

*Mel-1 and Mel-2).*

**Table 2.**

**Figure 5.**

**84**

with relatively greater analytical uncertainty.

*Plot of cerium anomaly and Pr/Pr\* (as a manifestation of the first tetrad) in the Lipnice granite in borehole Mel-5 and polygon P2a (soil cap). Ce/Ce\* = 3CeN/(2LaN + NdN); Pr/Pr\* = 3PrN/(2NdN + LaN). Normalizing values from [32].*

Out of other REEs, the only systematic fractionation in weathered granites is a relative maximum of Yb (**Figure 5a** and **b**).

Other elements concentrated in monazite (Th), zircon (Zr, Hf), and (Fe-)Ti oxides (Nb, Ta) are not significantly affected by weathering, which is also true for Zr/Hf and Nb/Ta ratios. Therefore, it seems that dissolution of primary accessory minerals except for apatite was not significant for REE behavior during weathering. The locally observed alteration of monazite can be attributed to Ca-rich hydrothermal fluids [20].



**4.2 REE distribution in apatite**

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

**Figure 7.**

**5. Discussion**

**87**

The analyzed trace elements indicate that apatite is a relevant carrier of Y and HREE; however its contribution to whole-rock LREE budget cannot be neglected as well. Results of apatite LA-ICP-MS analyses in polished sections (**Table 3**) are consistent with ICP-MS solution analyses (see [20, 30]). The negative europium anomaly in apatite is deeper than that one in the whole rock. The apatite of Lipnice granite is characterized by strong M-type tetrad effect, forming the first tetrad (whose magnitude is proportional to Pr/Pr\* and, in the absence of cerium anomaly,

*Bulk Earth normalized [32] REE in apatite (minimum, maximum, and median) as determined by LA-ICP-MS in polished sections of rocks: (a) Lipnice granite, Dolní Město—Kopaniny. (b) Melechov granite, Leštinka.*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

In apatite of Melechov granite (as well as of Kouty and Stvořidla granites), the tetrad effect was already documented before [20]. However, the first tetrad from solution analyses is weak and incomparable to that of apatite in Lipnice type. This is partly due to greater portion of altered and secondary apatite, which does not show tetrad effect (e.g., spot 1 in **Table 3b**). The most spot analyses of apatite in Melechov granite (**Table 3b**, **Figure 7b**) show probably the first three tetrads which, however, are weak.

also to Ce/Ce\* values) and probably second tetrad (**Table 3a**, **Figure 7a**).

**5.1 Alteration of primary minerals by chemical weathering**

influence of apatite (and perhaps calcite) is possible as well.

The overall rate of Ca release from the rock is higher than that one of Na, because a large part of the Na budget is relatively better fixed as albite lamellae in perthitic K-feldspar, which is more resistant to weathering than plagioclase; a minor

Strontium is probably—in contrast to calcium—concentrated in K-feldspar too

(see also [33]). This would explain why Ca/Sr ratio decreases at weathering (**Table 1b**). Also note that the Ca/Sr ratio in springwater (130 at Lipnice granite and 200 at Melechov granite; **Table 4a**) is significantly higher than in the rocks. White [34] suggested that at the initial stages of weathering, Ca and Sr are released mainly from accessory calcite. According to [35], both calcite and apatite are important sources of Sr in the very early stages of weathering. The loss of Ba and Na shows

that the simplest explanation—leaching of Ca and Sr from plagioclase and K-

feldspar—is the most likely. Nevertheless the decrease of P2O5 in the most weathered samples suggests that apatite contributes to the release of Ca, too. The Sr abundance in apatite is in the range ca. 100–250 ppm (**Table 3**), and so the Ca/Sr ratio of apatite

*\*\*Analyzed spot influenced by monazite (not included in the statistics).*

*Eu/Eu\* = 2EuN/(SmN + GdN).*

*Ce/Ce\* = 3CeN/(2LaN + NdN).*

*Pr/Pr\* = 3PrN/(2NdN + LaN).*

*Normalizing bulk Earth values from [32].*

#### **Table 3.** *LA-ICP-MS spot analyses of apatite (elements in ppm).*

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

**Figure 7.**

**(a) Lipnice granite, Kopaniny (standardized to assumed Ca content 38 wt. %)**

U 39 63 72 79 54 52 41 43 64 54 34 **54** 13

**1 2 3 4 5 8 9 10 14 15 16 Mean St.**

2974 2489 2707 3117 3143 3720 2936 3220 3628 3055 2514 **3046** 361

0.083 0.061 0.070 0.065 0.079 0.057 0.070 0.063 0.058 0.073 0.150 **0.075** 0.024

1.08 1.08 1.13 1.14 1.15 1.10 1.06 1.24 1.20 1.09 1.11 **1.12** 0.05

1.26 1.38 1.43 1.44 1.26 1.44 1.48 1.24 1.30 1.20 1.48 **1.36** 0.10

31.1 28.0 24.0 27.6 28.1 24.2 28.9 30.8 27.6 30.8 19.2 **27** 3

**(b) Melechov granite, Leštinka (standardized to assumed Ca content 35 wt. %) An. no. 1 2 3 4 5 6 7\*\* 8 9 Mean St. dev.** Sr 186 257 257 153 116 98 143 134 212 **177** 58 Y 252 202 207 1573 946 1740 1686 1876 747 **943** 662 La 201 345 271 242 236 220 536 195 283 **249** 46 Ce 385 766 594 655 603 738 1597 616 730 **636** 113 Pr 46 87 78 86 79 109 205 103 94 **85** 18 Nd 138 247 271 370 302 406 863 469 334 **317** 96 Sm 32 46 54 170 91 154 247 195 95 **105** 58 Eu 12.0 13.7 10.4 12.0 7.3 7.2 6.7 6.6 15.7 **11** 3.1 Gd 28 62 60 178 134 249 361 334 100 **143** 98 Tb 11 9 10 33 40 74 77 73 24 **34** 25 Dy 52 42 49 238 204 409 422 422 152 **196** 144 Ho 7 6 8 43 33 59 69 70 28 **32** 23 Er 13 16 13 94 81 143 142 131 62 **69** 49 Tm 1.7 2.5 1.5 13.4 11.1 17.3 15.6 14.3 7.4 **9** 5.8 Yb 16 19 6 68 65 119 104 82 51 **53** 36 Lu 1.2 0.6 1.2 9.7 7.2 11.4 12.6 8.7 6.2 **6** 4.0 Th 6.8 0.7 2.2 4.3 2.3 4.1 201 25.6 7.6 **7** 7.5 U 19 26 26 205 138 236 333 148 105 **113** 79 Ca/Sr 1881 1363 1363 2290 3020 3571 2447 2620 1648 **2220** 753 Eu/Eu\* 1.208 0.786 0.553 0.211 0.202 0.113 0.068 0.079 0.492 **0.455** 0.366 Ce/Ce\* 0.92 1.03 0.97 1.09 1.06 1.14 1.16 1.03 1.07 **1.04** 0.06 Pr/Pr\* 1.03 1.10 1.07 1.05 1.10 1.30 1.09 1.16 1.14 **1.12** 0.08 Y/Ho 34.1 33.5 25.7 36.9 28.7 29.4 24.5 26.8 27.1 **30.3** 3.8

*\*\*Analyzed spot influenced by monazite (not included in the statistics).*

*LA-ICP-MS spot analyses of apatite (elements in ppm).*

*Eu/Eu\* = 2EuN/(SmN + GdN). Ce/Ce\* = 3CeN/(2LaN + NdN). Pr/Pr\* = 3PrN/(2NdN + LaN). Normalizing bulk Earth values from [32].*

**Table 3.**

**86**

**dev.**

**An. no.**

*Geochemistry*

Ca/ Sr

Eu/ Eu\*

Ce/ Ce\*

Pr/ Pr\*

Y/ Ho

*Bulk Earth normalized [32] REE in apatite (minimum, maximum, and median) as determined by LA-ICP-MS in polished sections of rocks: (a) Lipnice granite, Dolní Město—Kopaniny. (b) Melechov granite, Leštinka.*

#### **4.2 REE distribution in apatite**

The analyzed trace elements indicate that apatite is a relevant carrier of Y and HREE; however its contribution to whole-rock LREE budget cannot be neglected as well. Results of apatite LA-ICP-MS analyses in polished sections (**Table 3**) are consistent with ICP-MS solution analyses (see [20, 30]). The negative europium anomaly in apatite is deeper than that one in the whole rock. The apatite of Lipnice granite is characterized by strong M-type tetrad effect, forming the first tetrad (whose magnitude is proportional to Pr/Pr\* and, in the absence of cerium anomaly, also to Ce/Ce\* values) and probably second tetrad (**Table 3a**, **Figure 7a**).

In apatite of Melechov granite (as well as of Kouty and Stvořidla granites), the tetrad effect was already documented before [20]. However, the first tetrad from solution analyses is weak and incomparable to that of apatite in Lipnice type. This is partly due to greater portion of altered and secondary apatite, which does not show tetrad effect (e.g., spot 1 in **Table 3b**). The most spot analyses of apatite in Melechov granite (**Table 3b**, **Figure 7b**) show probably the first three tetrads which, however, are weak.

#### **5. Discussion**

#### **5.1 Alteration of primary minerals by chemical weathering**

The overall rate of Ca release from the rock is higher than that one of Na, because a large part of the Na budget is relatively better fixed as albite lamellae in perthitic K-feldspar, which is more resistant to weathering than plagioclase; a minor influence of apatite (and perhaps calcite) is possible as well.

Strontium is probably—in contrast to calcium—concentrated in K-feldspar too (see also [33]). This would explain why Ca/Sr ratio decreases at weathering (**Table 1b**). Also note that the Ca/Sr ratio in springwater (130 at Lipnice granite and 200 at Melechov granite; **Table 4a**) is significantly higher than in the rocks. White [34] suggested that at the initial stages of weathering, Ca and Sr are released mainly from accessory calcite. According to [35], both calcite and apatite are important sources of Sr in the very early stages of weathering. The loss of Ba and Na shows that the simplest explanation—leaching of Ca and Sr from plagioclase and Kfeldspar—is the most likely. Nevertheless the decrease of P2O5 in the most weathered samples suggests that apatite contributes to the release of Ca, too. The Sr abundance in apatite is in the range ca. 100–250 ppm (**Table 3**), and so the Ca/Sr ratio of apatite


**(b) Chemistry of springs (all** 

**89**

**Object, date**

Springs on Lipnice granite (n = 5) 27.5. / 22.6.2004

Springs on Melechov granite (n = 24) 27.5. / 22.6.2004

**components**

 **in mg/l) sampled by L.** 

**catchment**

 **Loukov [16, 44]; values in italics represent 1/2 of detection limit**

**Na+**

**Method**

Mean

Median

 Mean Median

Catchment

Catchment discharge

*FAAS, flame atomic absorption spectrometry;*

**Table 4.** *Springs on Melechov and Lipnice granites sampled within the frame of the (a)* 

 discharge 1.6.2004

X.1994–X.2014

 (weighed average, monthly sampling)

 *PMT, photometry;*

 *HPLC,* 

*high-performance*

 *liquid*  *PADAMOT*

 *project and (b) RAWRA project.*

*chromatography;*

 *ISE, ion-selective*

 *electrode.*

 8.4 9.8

 8.9

 3.2

 0.36

 0.82

 13.1

 0.29

 0.21

 59.4

 2.1

 21.1

 5.06

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

 3.2

 0.24

 0.5

 13.9

*0.15*

0.26

 62.7

 2.0

 2.9

 0.27

 1.4

 14.3

 2.3

 0.21

 57.9

 2.3

 18.1

 5.86 5.11

 8.1

 2.8

 0.42

 1.6

 14.0

 3.4

 0.25

 56.7

 2.7

 17.9

 5.43

 9.7

 4.3

 0.20

 1.7

 18.0

 21.0

 0.15

 40.6

 6.6

 19.4

 6.2

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

 10.0

 4.5

 0.20

 1.8

 17.0

 23.2

 0.18

 48.6

 7.1

 19.3

 6.3

 **FAAS**

 **FAAS**

 **FAAS**

 **FAAS**

 **FAAS**

 **HPLC**

 **ISE**

 **HPLC**

 **HPLC**

 **FAAS**

 **ISE**

**Mg2+**

**Al**

 **K+**

**Ca2+**

**(NO3)**

**F**

**(SO4)2**

**Cl**

**SiO2**

**pH**

**Rukavičková**

 **and co-workers**

 **in 2004 within the frame of the RAWRA project; for comparison**

 **the discharge of**

*Geochemistry*


**Table 4.** *SpringsonMelechovandLipnicegranitessampledwithinthe frameofthe(a)PADAMOTprojectand(b)RAWRAproject.*

#### *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical … DOI: http://dx.doi.org/10.5772/intechopen.91383*

**(a) Statistics of major ions and pH in springs on Melechov and Lipnice granites sampled within the frame of the** 

**88**

**represented**

**Substrate rock type**

**Unit** mg/l mg/l mg/l mg/l mg/l μg/l μg/l μg/l mg/l mg/l mg/l mg/l

Na+ Mg2+

Al K+ Ca2+ Mn2+

Zn2+

Sr (NO3)

F (SO4)2

Cl pH Ca/Sr

 **less than half of analyses, they were replaced by 1/2 detection limit**

**Melechov in the forest (n = 17)**

**Mean**

8.86 2.97 0.22 1.39 14.9 89.3 41.3 77.8 5.68 0.28 57.6 2.43 5.32 192

186

212

193

129

128

6.08

6.98

7.04

7.04

7.14

2.21

13

12.5

6.39

4.74

57.4

47.6

49.8

21.5

22.7

0.19

0.1

0.08

0.08

0.08

2.04

24.8

22.9

20

11.3

72.4

117.7

134.6

92.3

81.2

35

18.5

17

9

10

25

34.8

9.5

4.4

5

13.5

24.9

26

11.9

10.4

1.38

11.24

5.72

1.63

1.55

0.2

0.04

0.1

0.1

0.1

2.87

4.44

4.81

3.15

2.87

9.16

11.41

10.57

8.01

7.67

**Median**

**Mean**

**Median**

**Mean**

**Median**

**Melechov others (n = 8)**

**Lipnice (n = 4)**

*Geochemistry*

**PADAMOT**

 **project [36]; if values below detection limit**

is by 2–3 orders of magnitude higher than that of the whole rock. Thus, apatite weathering can contribute to the lower Ca/Sr ratio in the eluvium as well.

The slight depletion of Lipnice granite in K also indicates some weathering of Kfeldspar, because Rb and Cs, concentrated in micas relatively stronger than K (see also analyses of separated micas [37]), are not depleted. However the possibility of selective Rb and Cs concentration (including adsorption) by secondary phases like vermiculite has to be also kept in mind [38–40]. Note that a considerable amount of vermiculite (with minor chlorite) has been proven in concentrates of biotite from eluvia of Lipnice granite [25].

composition [26, 27]. The Al-rich and Si-poor eluvia represent original lower horizon or domains, relatively depleted in quartz due to enrichment in small grains of weathered and secondary minerals. As indicated by Pb isotope evolution of fracture fillings in granite from borehole PDM-1 (close to Mel-3 and Mel-4), as early as in the Early Cretaceous, there was significant supergene redistribution of U and/or Pb [5, 6]. This event corresponds to the erosion of rocks immediately overlying the

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

Solid-phase physical separation may also explain the question why elements contained in the most chemically resistant minerals (Zr, Hf, Nb, Ta, Th, partly REE; see also [45]) were not passively concentrated in weathered rocks (in case of Nb and Ta even slight depletion cannot be excluded). Also Zr/Hf and Nb/Ta ratios are unaffected. Observations of the relevant accessory minerals (zircon, monazite, rutile, ilmenite) in heavy-mineral concentrates from eluvia showed very weak influence of chemical weathering [21, 25]. However, a significant portion of these minerals in the rock forms very small grains—down to a few μm (zircon and monazite in Melechov type). These very small grains, unless included in other minerals, were easily transported by gravity and water flow away and partly to

The lanthanide tetrad effect in granites and other felsic melts, including experimental ones, has been documented and discussed in numerous publications (e.g., [46–48]). Regarding the tetrad effect in apatite, one possibility is fractionation of monazite ( xenotime), which would produce a pattern similar to M-type tetrad effect in the coexisting melt [49, 50]; see also [51]. In monazite within granites of Melechov massif, no fractionation similar to tetrad effect is apparent in EMP data [17, 19]. Nevertheless if monazite crystallized close to apatite, which is true especially in the Melechov granite but partly in the Lipnice granite as well [19], the light REE in apatite would be modified even in the case of only weak tetrad effect in monazite. The difference between apatite composition of Lipnice and Melechov types can be related to the several times higher abundance of monazite in the Lipnice granite. As documented by [48, 52], another important factor can be fluo-

REE fractionation seems to support a hypothesis of formation of P-rich domains in the melt, where monazite and apatite could have influenced one another much more than the remaining melt. Formation of such domains is also supported by

As shown by [49], the tetrad effect-like pattern of trivalent REE produced by monazite and xenotime fractionation is more complex. Another important feature is the peak of Yb in the residual melt. Similar Yb peak is observed in weathered Lipnice and Melechov granites (and in altered Melechov granite), when normalized

Despite the fact that many details of REE fractionation are unanswered, we can sum up that magmatic crystallization of phosphates, possibly with an important role of fluorine, produced complicated REE fractionation among rock-forming minerals, which can be insignificant in whole-rock chondrite-normalized patterns, but it can

Dissolution of apatite whose Y/Ho ratio (**Table 3**) is generally slightly lower than that of whole rock (**Table 1b**) could also lead to slightly elevated Y/Ho ratios of

granites of Melechov Massif.

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

open fractures deeper in the granite [5, 6].

rine content, which is higher in the Lipnice granite as well.

**5.4 Origin of the REE fractionation**

conclusions of [19].

**91**

by fresh rocks (**Figure 5**).

be enhanced by weathering processes.

weathered granites (see **Figure 3c**).

Weathering of feldspars and biotite could also explain the Al/Ga fractionation. It seems that Ga was preferentially removed (in comparison with Al), as documented in the literature [41, 42], but in some places especially in Lipnice granite, it reconcentrated in the eluvium. Ga can be scavenged by Fe-oxyhydroxides [43], as indicated by positive correlation with Fe in P2a.

#### **5.2 Stream water chemistry**

Chemical composition of surface water has been systematically monitored in a small catchment Loukov starting with hydrological year 1995. This catchment drains Melechov granite at the eastern slope of Melechov hill. More than 95% is covered by spruce forest [44]. It has been shown [26] that recent mass balance of the catchment explains very poorly the chemical differences between fresh and weathered Melechov granites (especially the behavior of sodium, which is significantly removed in the discharge but not depleted in weathered rock).

Occasionally springs were analyzed at various granite types. The data show that differences between waters draining Lipnice and Melechov granite types are mainly in anions (usually higher sulfate and lower nitrate and chloride in springs on Melechov type), and they can be largely explained by different land use. Sampled springs on Lipnice granite are prevalently in agricultural area, whereas Melechov granite is largely covered by forest, which also enhances atmospheric deposition of sulfur (peaking in the last quarter of the twentieth century). The surface water draining Melechov granite is usually more acidic, and from that reason (as evidenced by negative correlation with pH), it has higher content of Mn, Al, and Zn than springs on Lipnice granite. Obviously the differences in water chemistry cannot explain the different behavior of Ca, Na, and Sr during weathering of Lipnice and Melechov granites because in such case, the content of these cations should be higher in water draining the Lipnice granite. Similarly, concentration of SiO2 which is depleted mainly in weathered Melechov granite is comparable in discharge from both granite types. On the other hand, the water chemistry data indicate that removal of elements in discharge could explain quite well the observed weathering of Lipnice granite.

Recent accumulation of P and K in the catchment was documented [16]. While some enrichment of the weathered Melechov granite in P is possible (see **Table 1**, **Figure 2**), we should keep in mind that strong retention of both elements can be a short-time phenomenon caused by deposition of dust from agricultural areas and by accumulation of nutrients in biomass (see also [26]) whose volume was increasing during the monitoring period (F. Oulehle, pers.commun.).

For a representative composition of surface water, see **Table 4a** and **b**.

#### **5.3 Erosion and mechanical transport**

It was concluded that erosion of a quartz-rich skeleton in the upper part of the weathering profile influenced significantly the present mineral and chemical

#### *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

composition [26, 27]. The Al-rich and Si-poor eluvia represent original lower horizon or domains, relatively depleted in quartz due to enrichment in small grains of weathered and secondary minerals. As indicated by Pb isotope evolution of fracture fillings in granite from borehole PDM-1 (close to Mel-3 and Mel-4), as early as in the Early Cretaceous, there was significant supergene redistribution of U and/or Pb [5, 6]. This event corresponds to the erosion of rocks immediately overlying the granites of Melechov Massif.

Solid-phase physical separation may also explain the question why elements contained in the most chemically resistant minerals (Zr, Hf, Nb, Ta, Th, partly REE; see also [45]) were not passively concentrated in weathered rocks (in case of Nb and Ta even slight depletion cannot be excluded). Also Zr/Hf and Nb/Ta ratios are unaffected. Observations of the relevant accessory minerals (zircon, monazite, rutile, ilmenite) in heavy-mineral concentrates from eluvia showed very weak influence of chemical weathering [21, 25]. However, a significant portion of these minerals in the rock forms very small grains—down to a few μm (zircon and monazite in Melechov type). These very small grains, unless included in other minerals, were easily transported by gravity and water flow away and partly to open fractures deeper in the granite [5, 6].

#### **5.4 Origin of the REE fractionation**

is by 2–3 orders of magnitude higher than that of the whole rock. Thus, apatite weathering can contribute to the lower Ca/Sr ratio in the eluvium as well.

eluvia of Lipnice granite [25].

*Geochemistry*

**5.2 Stream water chemistry**

indicated by positive correlation with Fe in P2a.

The slight depletion of Lipnice granite in K also indicates some weathering of Kfeldspar, because Rb and Cs, concentrated in micas relatively stronger than K (see also analyses of separated micas [37]), are not depleted. However the possibility of selective Rb and Cs concentration (including adsorption) by secondary phases like vermiculite has to be also kept in mind [38–40]. Note that a considerable amount of vermiculite (with minor chlorite) has been proven in concentrates of biotite from

Weathering of feldspars and biotite could also explain the Al/Ga fractionation. It seems that Ga was preferentially removed (in comparison with Al), as documented

Chemical composition of surface water has been systematically monitored in a small catchment Loukov starting with hydrological year 1995. This catchment drains Melechov granite at the eastern slope of Melechov hill. More than 95% is covered by spruce forest [44]. It has been shown [26] that recent mass balance of the catchment explains very poorly the chemical differences between fresh and weathered Melechov granites (especially the behavior of sodium, which is signifi-

Occasionally springs were analyzed at various granite types. The data show that differences between waters draining Lipnice and Melechov granite types are mainly in anions (usually higher sulfate and lower nitrate and chloride in springs on Melechov type), and they can be largely explained by different land use. Sampled springs on Lipnice granite are prevalently in agricultural area, whereas Melechov granite is largely covered by forest, which also enhances atmospheric deposition of sulfur (peaking in the last quarter of the twentieth century). The surface water draining Melechov granite is usually more acidic, and from that reason (as evidenced by negative correlation with pH), it has higher content of Mn, Al, and Zn than springs on Lipnice granite. Obviously the differences in water chemistry cannot explain the different behavior of Ca, Na, and Sr during weathering of Lipnice and Melechov granites because in such case, the content of these cations should be higher in water draining the Lipnice granite. Similarly, concentration of SiO2 which is depleted mainly in weathered Melechov granite is comparable in discharge from both granite types. On the other hand, the water chemistry data indicate that removal of elements in discharge could explain quite well the observed weathering of Lipnice granite. Recent accumulation of P and K in the catchment was documented [16]. While some enrichment of the weathered Melechov granite in P is possible (see **Table 1**, **Figure 2**), we should keep in mind that strong retention of both elements can be a short-time phenomenon caused by deposition of dust from agricultural areas and by accumulation of nutrients in biomass (see also [26]) whose volume was increasing

in the literature [41, 42], but in some places especially in Lipnice granite, it reconcentrated in the eluvium. Ga can be scavenged by Fe-oxyhydroxides [43], as

cantly removed in the discharge but not depleted in weathered rock).

during the monitoring period (F. Oulehle, pers.commun.).

**5.3 Erosion and mechanical transport**

**90**

For a representative composition of surface water, see **Table 4a** and **b**.

weathering profile influenced significantly the present mineral and chemical

It was concluded that erosion of a quartz-rich skeleton in the upper part of the

The lanthanide tetrad effect in granites and other felsic melts, including experimental ones, has been documented and discussed in numerous publications (e.g., [46–48]). Regarding the tetrad effect in apatite, one possibility is fractionation of monazite ( xenotime), which would produce a pattern similar to M-type tetrad effect in the coexisting melt [49, 50]; see also [51]. In monazite within granites of Melechov massif, no fractionation similar to tetrad effect is apparent in EMP data [17, 19]. Nevertheless if monazite crystallized close to apatite, which is true especially in the Melechov granite but partly in the Lipnice granite as well [19], the light REE in apatite would be modified even in the case of only weak tetrad effect in monazite. The difference between apatite composition of Lipnice and Melechov types can be related to the several times higher abundance of monazite in the Lipnice granite. As documented by [48, 52], another important factor can be fluorine content, which is higher in the Lipnice granite as well.

REE fractionation seems to support a hypothesis of formation of P-rich domains in the melt, where monazite and apatite could have influenced one another much more than the remaining melt. Formation of such domains is also supported by conclusions of [19].

As shown by [49], the tetrad effect-like pattern of trivalent REE produced by monazite and xenotime fractionation is more complex. Another important feature is the peak of Yb in the residual melt. Similar Yb peak is observed in weathered Lipnice and Melechov granites (and in altered Melechov granite), when normalized by fresh rocks (**Figure 5**).

Despite the fact that many details of REE fractionation are unanswered, we can sum up that magmatic crystallization of phosphates, possibly with an important role of fluorine, produced complicated REE fractionation among rock-forming minerals, which can be insignificant in whole-rock chondrite-normalized patterns, but it can be enhanced by weathering processes.

Dissolution of apatite whose Y/Ho ratio (**Table 3**) is generally slightly lower than that of whole rock (**Table 1b**) could also lead to slightly elevated Y/Ho ratios of weathered granites (see **Figure 3c**).

#### **6. Conclusions**

A unique dataset from the Lipnice and Melechov granites showed that wholerock analyses of the fresh rock and eluvium combined with the knowledge of element's abundance in primary minerals are a very effective tool for the reconstruction of granite weathering. Combination with borehole data helps to interpret large medium- to small-scale inhomogeneity of weathering processes.

Both granites are depleted in several elements concentrated mainly in biotite: Mg, Ti, Mn (mainly the Lipnice type), and the Melechov type in Fe and V, too. Content of elements concentrated in plagioclase, apatite, and partly K-feldspar (Ca, Na, Sr, P, Ba) decreased in weathered Lipnice granite, but not in Melechov granite. The main factor causing these differences is that superficial chemical weathering of the relatively coarse-grained and permeable Melechov granite was weaker than in Lipnice granite. In addition, the influence of chemical weathering (e.g., on Fe content and REE distribution) could be similar to subsolidus alterations, which had been more intense in the Melechov type. However, in some cases, like carbonatization or U enrichment, the effect of subsolidus alteration is opposite to weathering. In the Lipnice type, especially in the homogeneous P2a polygon (with borehole Mel-5), we were also able to distinguish formation of positive cerium anomaly at weathering and trace the role of secondary phases (Fe-oxyhydroxides, vermiculite) in retention of some elements (Ga). The first stage of Lipnice granite weathering in P2a is characterized mainly by alteration of biotite, not lowering SiO2 content.

The natural solid-phase separation led to relative depletion of the sampled eluvia in quartz (especially in the Melechov granite) and prevented the most resistant accessory minerals (e.g., zircon) to be passively concentrated in the eluvia. The petrologically important Zr/Hf and Nb/Ta ratios are not significantly affected. Contamination of eluvia by material from quartz veins and other sources led to their enrichment in Au and Ag. A thorough examination of mutual ratios of REE and Y revealed also some influence of apatite dissolution.

**Author details**

Václav Procházka<sup>1</sup>

Czech Republic

**93**

\*, Miroslav Žáček2

4 CEITEC, Masaryk University, Brno, Czech Republic

\*Address all correspondence to: vprochaska@seznam.cz

5 Czech Geological Survey, Praha, Czech Republic

Lenka Rukavičková<sup>5</sup> and Dobroslav Matějka<sup>6</sup>

1 Česká Geologie, Praha, Czech Republic

*DOI: http://dx.doi.org/10.5772/intechopen.91383*

2 GEOMIN Ltd., Jihlava, Czech Republic

University, Praha, Czech Republic

provided the original work is properly cited.

, Petr Sulovský<sup>3</sup>

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical…*

3 Department of Geology, Faculty of Science of the Palacký University, Olomouc,

6 Department of Geochemistry, Mineralogy and Mineral Resources, Charles

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

, Tomáš Vaculovič<sup>4</sup>

,

The loss of U was significant in both granite types, but more intense in the Melechov type where larger portion of U was allocated to unstable phases or only adsorbed. Gallium was passively concentrated in eluvia of both granites, however stronger in the Lipnice type, possibly thanks to better retention of Feoxyhydroxides.

Assessment of weathering behavior of several elements (W, Sn, Co, partly Mg) is complicated by their spatial inhomogeneity in the intrusions, indicated by vertical differentiation in boreholes. In case of strongly incompatible W, we are able to distinguish this vertical trend from obvious removal of W by weathering of the Melechov granite.

#### **Acknowledgements**

We thank to Dr. František Woller and Dr. Jiří Slovák from the RAWRA for their help in facilitating the usage of archived data, obtained during the second phase of Melechov test locality project (2004–2006). The work was also supported by the research plan MSM 0021620855 of the Ministry of Education, Youth and Sports of the Czech Republic.

*The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

### **Author details**

**6. Conclusions**

*Geochemistry*

content.

oxyhydroxides.

Melechov granite.

**Acknowledgements**

the Czech Republic.

**92**

A unique dataset from the Lipnice and Melechov granites showed that wholerock analyses of the fresh rock and eluvium combined with the knowledge of element's abundance in primary minerals are a very effective tool for the reconstruction of granite weathering. Combination with borehole data helps to interpret

Both granites are depleted in several elements concentrated mainly in biotite: Mg, Ti, Mn (mainly the Lipnice type), and the Melechov type in Fe and V, too. Content of elements concentrated in plagioclase, apatite, and partly K-feldspar (Ca, Na, Sr, P, Ba) decreased in weathered Lipnice granite, but not in Melechov granite. The main factor causing these differences is that superficial chemical weathering of the relatively coarse-grained and permeable Melechov granite was weaker than in Lipnice granite. In addition, the influence of chemical weathering (e.g., on Fe content and REE distribution) could be similar to subsolidus alterations, which had

large medium- to small-scale inhomogeneity of weathering processes.

been more intense in the Melechov type. However, in some cases, like

carbonatization or U enrichment, the effect of subsolidus alteration is opposite to weathering. In the Lipnice type, especially in the homogeneous P2a polygon (with borehole Mel-5), we were also able to distinguish formation of positive cerium anomaly at weathering and trace the role of secondary phases (Fe-oxyhydroxides, vermiculite) in retention of some elements (Ga). The first stage of Lipnice granite weathering in P2a is characterized mainly by alteration of biotite, not lowering SiO2

The natural solid-phase separation led to relative depletion of the sampled eluvia

in quartz (especially in the Melechov granite) and prevented the most resistant accessory minerals (e.g., zircon) to be passively concentrated in the eluvia. The petrologically important Zr/Hf and Nb/Ta ratios are not significantly affected. Contamination of eluvia by material from quartz veins and other sources led to their enrichment in Au and Ag. A thorough examination of mutual ratios of REE and Y

The loss of U was significant in both granite types, but more intense in the Melechov type where larger portion of U was allocated to unstable phases or only adsorbed. Gallium was passively concentrated in eluvia of both granites, however

Assessment of weathering behavior of several elements (W, Sn, Co, partly Mg) is complicated by their spatial inhomogeneity in the intrusions, indicated by vertical differentiation in boreholes. In case of strongly incompatible W, we are able to distinguish this vertical trend from obvious removal of W by weathering of the

We thank to Dr. František Woller and Dr. Jiří Slovák from the RAWRA for their help in facilitating the usage of archived data, obtained during the second phase of Melechov test locality project (2004–2006). The work was also supported by the research plan MSM 0021620855 of the Ministry of Education, Youth and Sports of

stronger in the Lipnice type, possibly thanks to better retention of Fe-

revealed also some influence of apatite dissolution.

Václav Procházka<sup>1</sup> \*, Miroslav Žáček2 , Petr Sulovský<sup>3</sup> , Tomáš Vaculovič<sup>4</sup> , Lenka Rukavičková<sup>5</sup> and Dobroslav Matějka<sup>6</sup>

1 Česká Geologie, Praha, Czech Republic

2 GEOMIN Ltd., Jihlava, Czech Republic

3 Department of Geology, Faculty of Science of the Palacký University, Olomouc, Czech Republic

4 CEITEC, Masaryk University, Brno, Czech Republic

5 Czech Geological Survey, Praha, Czech Republic

6 Department of Geochemistry, Mineralogy and Mineral Resources, Charles University, Praha, Czech Republic

\*Address all correspondence to: vprochaska@seznam.cz

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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[52] Peretyazhko IS, Savina EA. Tetradeffects in REE pattern of granitoid rocks: The result of liquid immiscibility in fluorine-rich silicate melts. Doklady Earth Sciences. 2010;**433**:1042-1047

[43] Hieronymus B, Kotschoubey B, Boulégue J. Gallium behaviour in some contrasting lateritic profiles from Cameroon and Brazil. Journal of Geochemical Exploration. 2001;**72**: 147-163

[44] Fottová D. Hydrochemical budgets in the monitoring network GEOMON. In: Project Report SP/1a6/151/07. Prague: Czech Geological Survey; 2011

[45] Nesbitt HW, Markovics G. Weathering of granodioritic crust, longterm storage of elements in weathering profiles, and petrogenesis of siliciclastic sediments. Geochimica et Cosmochimica Acta. 1997;**61**:1653-1670

[46] Bau M. Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: Evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect. Contributions to Mineralogy and Petrology. 1996;**123**:323-333

[47] Irber W. The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu\*, Sr/ Eu, Y/Ho, and Zr/Hf of evolving peraluminous granite suites. Geochimica et Cosmochimica Acta. 1999;**63**:489-508

[48] Veksler IV, Dorfman AM, Kamenetsky M, Dulski P, Dingwell DB. Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks. Geochimica et Cosmochimica Acta. 2005;**69**:2847-2860

[49] Tin QD, Keppler H. Monazite and xenotime solubility in granitic melts and the origin of the lanthanide tetrad effect. Contributions to Mineralogy and Petrology. 2015;**169**:1-26

[50] Stepanov AS, Hermann J, Rubatto D. Experimental study of *The Importance of Mechanical Transport, Rock Texture, and Mineral Chemistry in Chemical… DOI: http://dx.doi.org/10.5772/intechopen.91383*

monazite/melt partitioning with implications for the REE, Th and U geochemistry of crustal rocks. Chemical Geology. 2012;**300-301**:200-220

petrogenesis. Geochimica et

*Geochemistry*

Cosmochimica Acta. 2005;**69**:1455-1471

aluminum in Californian streams. Geochimica et Cosmochimica Acta.

[43] Hieronymus B, Kotschoubey B, Boulégue J. Gallium behaviour in some contrasting lateritic profiles from Cameroon and Brazil. Journal of Geochemical Exploration. 2001;**72**:

[44] Fottová D. Hydrochemical budgets in the monitoring network GEOMON. In: Project Report SP/1a6/151/07. Prague: Czech Geological Survey; 2011

Weathering of granodioritic crust, longterm storage of elements in weathering profiles, and petrogenesis of siliciclastic

Cosmochimica Acta. 1997;**61**:1653-1670

[46] Bau M. Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: Evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect. Contributions to Mineralogy and

[47] Irber W. The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu\*, Sr/

peraluminous granite suites. Geochimica et Cosmochimica Acta. 1999;**63**:489-508

Kamenetsky M, Dulski P, Dingwell DB. Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in

Cosmochimica Acta. 2005;**69**:2847-2860

[49] Tin QD, Keppler H. Monazite and xenotime solubility in granitic melts and the origin of the lanthanide tetrad effect. Contributions to Mineralogy and

[45] Nesbitt HW, Markovics G.

sediments. Geochimica et

Petrology. 1996;**123**:323-333

Eu, Y/Ho, and Zr/Hf of evolving

[48] Veksler IV, Dorfman AM,

igneous rocks. Geochimica et

Petrology. 2015;**169**:1-26

[50] Stepanov AS, Hermann J, Rubatto D. Experimental study of

1996;**60**:1323-1328

147-163

[35] Erel Y, Blum JD, Roueff E, Ganor J. Lead and strontium isotopes as monitors of experimental granitoid mineral dissolution. Geochimica et

Cosmochimica Acta. 2004;**68**:4649-4663

[36] Milodowski AE, Tullborg E-L, Buil B, Gómez P, Turrero M-J, Haszeldine S, et al. Application of mineralogical, petrological and geochemical tools for evaluating the palaeohydrogeological evolution of the PADAMOT study sites. In: PADAMOT Project Technical Report WP2. Harwell,

[37] Breiter K, Hrubeš M, Mlčoch B, Štěpánek P, Táborský Z. Results of new geologic-petrological studies in the Melechov massif area (in Czech). In: Procházka J, editor. Geological Investigation of the Testing Locality Melechov Massif. Praha: MS RAWRA;

[38] Jeong GY, Cheong CS, Kim J. Rb–Sr and K–Ar systems of biotite in surface environments regulated by weathering processes with implications for isotopic dating and hydrological cycles of Sr isotopes. Geochimica et Cosmochimica

[39] Komarneni S, Roy DM. Shale as a radioactive waste repository: The importance of vermiculite. Journal of Inorganic and Nuclear Chemistry. 1979;

[40] Sawhney BL. Selective sorption and fixation of cations by clay minerals: A review. Clays and Clay Minerals. 1972;

[41] Shiller AM. Enrichment of dissolved gallium relative to aluminium in natural waters. Geochimica et Cosmochimica

Acta. 2006;**70**:4734-4749

Acta. 1988;**52**:1879-1882

[42] Shiller AM, Frilot DM. The geochemistry of gallium relative to

**41**:1793-1796

**20**:93-100

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UK: Nirex Ltd.; 2005

2001

[51] Yurimoto H, Duke EF, Papike JJ, Shearer CK. Are discontinuous chondrite-normalized REE patterns in pegmatitic granite systems the results of monazite fractionation? Geochimica et Cosmochimica Acta. 1990;**54**(7): 2141-2145

[52] Peretyazhko IS, Savina EA. Tetradeffects in REE pattern of granitoid rocks: The result of liquid immiscibility in fluorine-rich silicate melts. Doklady Earth Sciences. 2010;**433**:1042-1047

**99**

types of stone.

**Chapter 6**

**Abstract**

of elements

**1. Introduction**

Changes of Granite Rapakivi

*Oksana A. Rodina, Alexey D. Vlasov* 

on the type of biofilm developing on granite.

noticeable effect on the state of the stone.

*and Katerina V. Sazanova*

under the Biofouling Influence

*Dmitry Yu. Vlasov, Elena G. Panova, Marina S. Zelenskaya,* 

Interdisciplinary study of granite rapakivi biofouling in the natural and anthropogenic environment (St. Petersburg, Vyborg, Southern Finland) was carried out. The biodiversity of microorganisms (cyanobacteria, micromycetes, and organotrophic bacteria) and various types of biofilms are characterized. The influence of external factors on the changes of cyanobacterial biofilms is shown. The features of biofilms localization on the granite surface in an urban environment and in natural outcrops are studied. Differences in the biofilms metabolites composition at the granite quarries and monuments of St. Petersburg are shown. The behavior of chemical elements during the bioweathering of granite is estimated. The role of biofilms in the accumulation of chemical elements on the surface of granite is established. The dynamics of chemical elements leaching from granite may depend

**Keywords:** granite, weathering, biofouling, biogeochemical process, leaching, biodeterioration, microorganisms, environment, model experiments, mobile forms

Granite is one of the most widespread types of a stone in architecture of northern Russian cities such as Saint Petersburg, Vyborg, Priozersk, Primorsk as well as Finish cities such as Helsinki, Lappeenranta, Kotka, Hamina, Kuopio (Finland). The destruction of granite in the northern cities is a result of interrelated physical, chemical, and biological processes [1]. Biogenic weathering is connected with the impact on the rock surface by microorganisms (bacteria, microfungi, and microalgae) as well as lichens and mosses. They form lithobiotic communities which have a

The study of this problem seems to be an interdisciplinary task, the solution of which is possible only on the basis of an integrated scientific approach and the use of modern research methods. Organisms of lithobiotic communities are able to actively influence on the mineral substance chemically and physically. They catalyze the destruction of rocks, contributing to the extraction of minerals from them. Microbial activity in combination with atmospheric pollution is one of the features of urban ecosystems that determine the rate of weathering of granite and other

#### **Chapter 6**

### Changes of Granite Rapakivi under the Biofouling Influence

*Dmitry Yu. Vlasov, Elena G. Panova, Marina S. Zelenskaya, Oksana A. Rodina, Alexey D. Vlasov and Katerina V. Sazanova*

#### **Abstract**

Interdisciplinary study of granite rapakivi biofouling in the natural and anthropogenic environment (St. Petersburg, Vyborg, Southern Finland) was carried out. The biodiversity of microorganisms (cyanobacteria, micromycetes, and organotrophic bacteria) and various types of biofilms are characterized. The influence of external factors on the changes of cyanobacterial biofilms is shown. The features of biofilms localization on the granite surface in an urban environment and in natural outcrops are studied. Differences in the biofilms metabolites composition at the granite quarries and monuments of St. Petersburg are shown. The behavior of chemical elements during the bioweathering of granite is estimated. The role of biofilms in the accumulation of chemical elements on the surface of granite is established. The dynamics of chemical elements leaching from granite may depend on the type of biofilm developing on granite.

**Keywords:** granite, weathering, biofouling, biogeochemical process, leaching, biodeterioration, microorganisms, environment, model experiments, mobile forms of elements

#### **1. Introduction**

Granite is one of the most widespread types of a stone in architecture of northern Russian cities such as Saint Petersburg, Vyborg, Priozersk, Primorsk as well as Finish cities such as Helsinki, Lappeenranta, Kotka, Hamina, Kuopio (Finland). The destruction of granite in the northern cities is a result of interrelated physical, chemical, and biological processes [1]. Biogenic weathering is connected with the impact on the rock surface by microorganisms (bacteria, microfungi, and microalgae) as well as lichens and mosses. They form lithobiotic communities which have a noticeable effect on the state of the stone.

The study of this problem seems to be an interdisciplinary task, the solution of which is possible only on the basis of an integrated scientific approach and the use of modern research methods. Organisms of lithobiotic communities are able to actively influence on the mineral substance chemically and physically. They catalyze the destruction of rocks, contributing to the extraction of minerals from them. Microbial activity in combination with atmospheric pollution is one of the features of urban ecosystems that determine the rate of weathering of granite and other types of stone.

Most microorganisms on stone surface exist in the form of biofilms, which are composed of microbial cells and metabolites. Primary biofilms on granite most often consist of cyanobacteria and green algae. Aerophilic green algae are less resistant to adverse conditions than cyanobacteria and need more moisture. Green biofilm usually can be indicator of increased periodic or constant moisture of a stone [2, 3]. As organic matter accumulates on the surface of the stone, the participation of heterotrophic bacteria and fungi in the microbial community increases [4]. The close cooperation in microbial communities contributes to the successful growth and development of biofilms on stony substrates including granite. Biofilms can penetrate into cracks and pores. As a result, the absorption and retention of water in the rock mass increases, the intensity of diffusion and evaporation of water changes, and the processes of dissolution of the stone take place. The growth of biofilms causes pressure on the structural elements of the rock, acts on individual crystals and grains of stone.

Biochemical activity of microbial communities has a strong influence on mineral substance due to producing chemically active compounds such as polysaccharides, lipopolysaccharides, proteins, glycoproteins, lipids, glycolipids, fatty acids, and enzymes [5, 6]. Biomineral interaction leads to the leaching, formation of secondary minerals, primary soil formation, and thus, prepares the conditions for the further biological colonization of the stone.

The state of the stone surface has a particular importance for the biological colonization. A rough (uneven) surface is colonized much better than a smooth one [7]. Rough surface provides more opportunities for attachment and development of microorganisms (local humidity, microcracking, delay of various contaminants that serve as sources of nutrition for microorganisms, etc.). The biosusceptibility of natural stone may vary depending on the duration and conditions of its exposure in the open air [8].

Thus, natural stone together with biofouling is a peculiar and very complex lithobiotic system, the development of which depends on the properties of the stone, the composition of biological community, and environmental conditions. The aim of our investigation is the analysis of granite biological colonization peculiarities in different environment as well as the estimation of granite changes under the biofouling influence.

#### **2. Materials and methods**

#### **2.1 Materials**

The objects of research were selected in urban environment as well as in natural outcrops. Peter and Paul Fortress and monuments of the Museum Necropolises were studied in Saint Petersburg. Vyborg castle, fountain, tunnels, and outcrops in the Monrepos park were observed in Vyborg.

Granite outcrops were examined in the natural park Ristijärvi and on the Owl Mountain (Karelia). Also, four old quarries in the south part of Finland were examined: quarry I – (N 60° 34.207′ E 027° 43.835′); quarry II (N 60° 31.855′ E 027° 39.698′); quarry III (N 60° 32.101′ E 027° 39.823′); quarry IV (N 60° 44.413′ E 028° 00.564′). Granite mining at these quarries has long been discontinued. Currently, they undergo a process of natural overgrowth and are ideal model for studying of natural stone biofouling in low anthropogenic influence. More than 500 samples of destroyed rapakivi granite were investigated from 2013 to 2019. Rapakivi granite, as a rule, had its own unique image: large egg-shaped clusters of feldspar with a

**101**

*Changes of Granite Rapakivi under the Biofouling Influence*

fine-grained matrix of feldspars, quartz, and biotite.

diameter of 3–6 cm, surrounded by an edge of greenish-gray plagioclase, placed in a

Primary attention was paid to the structure of granite, the presence of cracks, holes, and other surface irregularities, which can serve as a shelter for microorganisms. Traditional cultural methods of mycology and microbiology have been applied for isolation and identification of microorganisms in biofilms on the surface of the granite [9]. Also, metagenomic analysis was used to determine a wide range of microorganisms in biofilms. The work was carried out in the resource center of Saint Petersburg State University "Development of cellular and molecular technologies." Diversity of bacteria in biofilms on granite was carried out on the basis of the 16S rRNA genes analysis. Metagenomic study of fungal diversity in biofilms on granite was carried out with primers for site amplification ITS1-5.8S–ITS2. For the identification of cyanobacteria, direct microscopy of the samples was used. Cumulative cultures were also obtained in distilled water and in the Gromov 6 medium (period cultivation from week to month). Verification of species in accordance with the current nomenclature was carried out using the electronic database

For analysis of small organic molecules in several types of biofilms samples were extracted with 15 mL methanol vigorously mixed and centrifuged (10 min, 400 × g) at room temperature. The supernatant was transferred to a new vial and dryed by a

The dried extracts were soluble in pyridine (30 μL) and BSTFA (N,O-bis—3 methyl-silyl-3-F-acetamide) (30 μL), incubated at 100°C for 15 minutes. The derivatized samples were analyzed by gas chromatography-mass spectrometry (GC-MS) by Agilent MSD 597, column HP-5MS, 30m × 0.25 mm. Chromatography was carried out with linear temperature programming from 70 to 320° at a speed of 4°C/min. Data were collected using Agilent ChemStation software. Mass spectrometric information was processed and interpreted using AMDIS program (http://www.amdis.net/index.html), standard NIST2005 library, and the library of standard compounds of BIN RAS. Quantitative interpretation of chromatograms was carried out with hydrocarbon using UniChrom program http://www.unichrom.

Scanning electron microscopy was used in order to study peculiarities of localization of microorganisms in the surface layer of the stone and to characterize the relationship between lithobiotic organisms during colonization of the granite. Samples of the damaged stone (0.5–1.0 cm × 0.5–1.0 cm) were initially examined under binocular loupe. The criterion of selection for SEM analysis was the presence of structures of microorganisms on the stone surface as well as transformation of the granite surface. The material was examined (after fixation) under the scanning electron microscope in the range of magnification from 100× to 10000×. SEM studies were performed on electron microscope ABT-55 (Japan) and TM 3000 (HITACHI, Japan, 2010) with an attachment of an energy-dispersive microanalysis

OXFORD in SPbU Resource Center "Microscopy and Microanalysis."

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

AlgaeBase (http://www.algaebase.org/).

**2.3 Biochemical analysis**

rotary evaporator at 40°C.

com/unichrome.shtml.

**2.4 Scanning electron microscopy**

**2.2 Study of microorganisms**

diameter of 3–6 cm, surrounded by an edge of greenish-gray plagioclase, placed in a fine-grained matrix of feldspars, quartz, and biotite.

#### **2.2 Study of microorganisms**

*Geochemistry*

crystals and grains of stone.

biological colonization of the stone.

of its exposure in the open air [8].

the biofouling influence.

**2.1 Materials**

**2. Materials and methods**

the Monrepos park were observed in Vyborg.

Most microorganisms on stone surface exist in the form of biofilms, which are composed of microbial cells and metabolites. Primary biofilms on granite most often consist of cyanobacteria and green algae. Aerophilic green algae are less resistant to adverse conditions than cyanobacteria and need more moisture. Green biofilm usually can be indicator of increased periodic or constant moisture of a stone [2, 3]. As organic matter accumulates on the surface of the stone, the participation of heterotrophic bacteria and fungi in the microbial community increases [4]. The close cooperation in microbial communities contributes to the successful growth and development of biofilms on stony substrates including granite. Biofilms can penetrate into cracks and pores. As a result, the absorption and retention of water in the rock mass increases, the intensity of diffusion and evaporation of water changes, and the processes of dissolution of the stone take place. The growth of biofilms causes pressure on the structural elements of the rock, acts on individual

Biochemical activity of microbial communities has a strong influence on mineral substance due to producing chemically active compounds such as polysaccharides, lipopolysaccharides, proteins, glycoproteins, lipids, glycolipids, fatty acids, and enzymes [5, 6]. Biomineral interaction leads to the leaching, formation of secondary minerals, primary soil formation, and thus, prepares the conditions for the further

The state of the stone surface has a particular importance for the biological colonization. A rough (uneven) surface is colonized much better than a smooth one [7]. Rough surface provides more opportunities for attachment and development of microorganisms (local humidity, microcracking, delay of various contaminants that serve as sources of nutrition for microorganisms, etc.). The biosusceptibility of natural stone may vary depending on the duration and conditions

Thus, natural stone together with biofouling is a peculiar and very complex lithobiotic system, the development of which depends on the properties of the stone, the composition of biological community, and environmental conditions. The aim of our investigation is the analysis of granite biological colonization peculiarities in different environment as well as the estimation of granite changes under

The objects of research were selected in urban environment as well as in natural outcrops. Peter and Paul Fortress and monuments of the Museum Necropolises were studied in Saint Petersburg. Vyborg castle, fountain, tunnels, and outcrops in

Granite outcrops were examined in the natural park Ristijärvi and on the Owl

Mountain (Karelia). Also, four old quarries in the south part of Finland were examined: quarry I – (N 60° 34.207′ E 027° 43.835′); quarry II (N 60° 31.855′ E 027° 39.698′); quarry III (N 60° 32.101′ E 027° 39.823′); quarry IV (N 60° 44.413′ E 028° 00.564′). Granite mining at these quarries has long been discontinued. Currently, they undergo a process of natural overgrowth and are ideal model for studying of natural stone biofouling in low anthropogenic influence. More than 500 samples of destroyed rapakivi granite were investigated from 2013 to 2019. Rapakivi granite, as a rule, had its own unique image: large egg-shaped clusters of feldspar with a

**100**

Primary attention was paid to the structure of granite, the presence of cracks, holes, and other surface irregularities, which can serve as a shelter for microorganisms. Traditional cultural methods of mycology and microbiology have been applied for isolation and identification of microorganisms in biofilms on the surface of the granite [9]. Also, metagenomic analysis was used to determine a wide range of microorganisms in biofilms. The work was carried out in the resource center of Saint Petersburg State University "Development of cellular and molecular technologies." Diversity of bacteria in biofilms on granite was carried out on the basis of the 16S rRNA genes analysis. Metagenomic study of fungal diversity in biofilms on granite was carried out with primers for site amplification ITS1-5.8S–ITS2. For the identification of cyanobacteria, direct microscopy of the samples was used. Cumulative cultures were also obtained in distilled water and in the Gromov 6 medium (period cultivation from week to month). Verification of species in accordance with the current nomenclature was carried out using the electronic database AlgaeBase (http://www.algaebase.org/).

#### **2.3 Biochemical analysis**

For analysis of small organic molecules in several types of biofilms samples were extracted with 15 mL methanol vigorously mixed and centrifuged (10 min, 400 × g) at room temperature. The supernatant was transferred to a new vial and dryed by a rotary evaporator at 40°C.

The dried extracts were soluble in pyridine (30 μL) and BSTFA (N,O-bis—3 methyl-silyl-3-F-acetamide) (30 μL), incubated at 100°C for 15 minutes. The derivatized samples were analyzed by gas chromatography-mass spectrometry (GC-MS) by Agilent MSD 597, column HP-5MS, 30m × 0.25 mm. Chromatography was carried out with linear temperature programming from 70 to 320° at a speed of 4°C/min. Data were collected using Agilent ChemStation software. Mass spectrometric information was processed and interpreted using AMDIS program (http://www.amdis.net/index.html), standard NIST2005 library, and the library of standard compounds of BIN RAS. Quantitative interpretation of chromatograms was carried out with hydrocarbon using UniChrom program http://www.unichrom. com/unichrome.shtml.

#### **2.4 Scanning electron microscopy**

Scanning electron microscopy was used in order to study peculiarities of localization of microorganisms in the surface layer of the stone and to characterize the relationship between lithobiotic organisms during colonization of the granite. Samples of the damaged stone (0.5–1.0 cm × 0.5–1.0 cm) were initially examined under binocular loupe. The criterion of selection for SEM analysis was the presence of structures of microorganisms on the stone surface as well as transformation of the granite surface. The material was examined (after fixation) under the scanning electron microscope in the range of magnification from 100× to 10000×. SEM studies were performed on electron microscope ABT-55 (Japan) and TM 3000 (HITACHI, Japan, 2010) with an attachment of an energy-dispersive microanalysis OXFORD in SPbU Resource Center "Microscopy and Microanalysis."

#### **2.5 Geochemical study**

The determination of elemental composition in fresh granite and various types of crusts was carried out using inductively coupled plasma (ICP MS, Agilent 7700) in the chemical laboratory of the All-Russian Geological Institute.

For the experiment on the dynamics of granite bioleaching, we took three types of samples from the surface of granite rapakivi from the Monrepos Park (Vyborg): surface layer of granite without biofilms, granite with black (lichens + fungi + cyanobacteria), and with gray (lichens + alga) biofilms. There are no local sources of pollutions in this area. Previously, the samples were powdered. Samples part (2 g) were diluted with 10 mL of bidistilled water each (in a ratio of 1:5) and mounted on a vibration panel for constant mixing of the sample and placed in a thermostat. The experiment lasted about a month. During this period, the temperature in the thermostat was 250 C at normal pressure. Aliquots of the solution were taken from the upper part of the flasks in the following time intervals: 1, 3, 6 hours from the beginning of the experiment; then after 1, 3, 8, 11, 14, 18, 22, 28, 32 days. The solution was analyzed with the following parameters: pH, particle size (HORIBA LA-950 nano-sizer), and composition of elements (ICP-MS, Agilent 7700).

#### **3. Results and discussion**

#### **3.1 Main types of granite biofilms (outward, biodiversity, and metabolism)**

There are different types of granite destruction in St. Petersburg, Vyborg, and quarries in Finland: fissuring, granular disintegration, flaking, exfoliation, loss of color, crusts, biofilms of different composition, ovoid weathering, and macrofouling. Primary biological colonization usually connected with the formation of pigmented biofilms. The color and structure of biofilms usually depends on the dominance of certain groups of microorganisms (cyanobacteria, algae, microscopic fungi, and lichens).

Cyanobacteria typically prevailed in primary biofilms, especially in natural outcrops of granite. They formed the basis of lithobiotic communities in most of the studied habitats. Both mono-species and multi-species communities dominated by cyanobacteria were noted. The dominance of specific species often determined the morphology of the whole biofilm. So, on granite in quarry I, a rich biofilm with a dominance of *Stigonema ocellatum* Thuret ex Bornet & Flahault (Dillw.) was formed in the place of natural water seepage (**Figure 1**). This species forms the interwoven filaments, which are clearly visible in the SEM image. The upper part of the biofilm has a greenish-olive color and is represented by *Stigonema ocellatum*. In the lower part of the biofilm, a change in color to brown-red can be seen due to the change of the dominant species by *Gloeocapsopsis magma* (Brébisson) Komarék et Anagnostidis. Other representatives of cyanobacteria also appear in the lower part of the biofilm: *Lyngbya* sp., *Leptolyngbya foveolarum* (Rabenhorst ex Gomont) Anagnostidis et Komarek, *Synechocystis salina* Wislouch.

Lighting also plays an important role in the formation of biofilms on the granite surface. Thus, it was shown by comparative studies of the species composition of cyanobacteria in the Vyborg granite tunnels (with scarce of light) and open areas of granite near tunnels. Under natural lighting, six species of cyanobacteria were identified (for 1 sample): *Gloeocapsopsis magma*, *Nostoc commune* Vaucher ex Bornet et Flahault f. Commune, *Calothrix parietina* (Nägeli) Thuret ex Bornet et Flahault f. *parietina*, *Scytonema hofmannii* C. Agardh ex Bornet & Flahault, *Aphanocapsa* sp. 1, *Aphanocapsa* cf. *fusco-lutea*. In the same time, no more than three species of

**103**

*Changes of Granite Rapakivi under the Biofouling Influence*

cyanobacteria were detected in each of the studied samples which were collected inside the tunnels. Moreover, the diversity of biofilms types inside tunnels was much lower than in the open air. In total, only three types of biofilms with the

a.Dark green to black biofilm is represented by the dominant species *Chroococcus*

b.Green algae predominate in the green biofilm; cyanobacteria *Chroococcus* sp. 1

c.White deposits represent a mineral layer and contain neither cyanobacteria nor

d.Cyanobacteria *Gloeocapsopsis magma* dominates in the reddish-brown biofilm.

In total, 78 cyanobacteria taxa belonging to 5 orders, 18 families, and 29 genera were identified in the studied habitats. Quarry IV was the richest in the number of

The most common in the studied areas are *Calothrix parietina* Thur. ex born. & Flah., *Gloeocapsopsis magma* (Brébisson) Komarék et Anagnostidis, *Leptolyngbya foveolarum* (Rabenhorst ex Gomont) Anagnostidis et Komarek, *Gloeocapsa atrata*

The largest number of families (4), genera (8), and species (29) was noted for the order Synechococcales, followed by the order Chroococcales (25 species). The most diverse is the genus *Leptolyngbya* (**Figure 7**). It occurs most often.

Cosmopolitan species predominated among the identified cyanobacteria.

It is interesting to note that only five taxa were found in Monrepos Park (Vyborg). This is due to the super dominance of certain species of cyanobacteria in

dominance of cyanobacteria were found in the tunnels (**Figure 2**).

Stigonema ocellatum *dominated biofilm on the surface of granite rapakivi in the quarry I.*

sp. 1 with the participation of *Aphanocapsa* sp.;

and *Aphanocapsa* sp. also found;

biofilms on the surface of granite (**Figures 3–5**).

microalgae;

**Figure 1.**

species (**Figure 6**).

Kützing, nom. illeg. (**Figure 8**).

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

*Changes of Granite Rapakivi under the Biofouling Influence DOI: http://dx.doi.org/10.5772/intechopen.92324*

*Geochemistry*

**2.5 Geochemical study**

thermostat was 250

fungi, and lichens).

**3. Results and discussion**

The determination of elemental composition in fresh granite and various types of crusts was carried out using inductively coupled plasma (ICP MS, Agilent 7700)

For the experiment on the dynamics of granite bioleaching, we took three types of samples from the surface of granite rapakivi from the Monrepos Park (Vyborg): surface layer of granite without biofilms, granite with black (lichens + fungi + cyanobacteria), and with gray (lichens + alga) biofilms. There are no local sources of pollutions in this area. Previously, the samples were powdered. Samples part (2 g) were diluted with 10 mL of bidistilled water each (in a ratio of 1:5) and mounted on a vibration panel for constant mixing of the sample and placed in a thermostat. The experiment lasted about a month. During this period, the temperature in the

the upper part of the flasks in the following time intervals: 1, 3, 6 hours from the beginning of the experiment; then after 1, 3, 8, 11, 14, 18, 22, 28, 32 days. The solution was analyzed with the following parameters: pH, particle size (HORIBA LA-950 nano-sizer), and composition of elements (ICP-MS, Agilent 7700).

**3.1 Main types of granite biofilms (outward, biodiversity, and metabolism)**

There are different types of granite destruction in St. Petersburg, Vyborg, and quarries in Finland: fissuring, granular disintegration, flaking, exfoliation, loss of color, crusts, biofilms of different composition, ovoid weathering, and macrofouling. Primary biological colonization usually connected with the formation of pigmented biofilms. The color and structure of biofilms usually depends on the dominance of certain groups of microorganisms (cyanobacteria, algae, microscopic

Cyanobacteria typically prevailed in primary biofilms, especially in natural outcrops of granite. They formed the basis of lithobiotic communities in most of the studied habitats. Both mono-species and multi-species communities dominated by cyanobacteria were noted. The dominance of specific species often determined the morphology of the whole biofilm. So, on granite in quarry I, a rich biofilm with a dominance of *Stigonema ocellatum* Thuret ex Bornet & Flahault (Dillw.) was formed in the place of natural water seepage (**Figure 1**). This species forms the interwoven filaments, which are clearly visible in the SEM image. The upper part of the biofilm has a greenish-olive color and is represented by *Stigonema ocellatum*. In the lower part of the biofilm, a change in color to brown-red can be seen due to the change of the dominant species by *Gloeocapsopsis magma* (Brébisson) Komarék et Anagnostidis. Other representatives of cyanobacteria also appear in the lower part of the biofilm: *Lyngbya* sp., *Leptolyngbya foveolarum* (Rabenhorst ex Gomont)

Lighting also plays an important role in the formation of biofilms on the granite surface. Thus, it was shown by comparative studies of the species composition of cyanobacteria in the Vyborg granite tunnels (with scarce of light) and open areas of granite near tunnels. Under natural lighting, six species of cyanobacteria were identified (for 1 sample): *Gloeocapsopsis magma*, *Nostoc commune* Vaucher ex Bornet et Flahault f. Commune, *Calothrix parietina* (Nägeli) Thuret ex Bornet et Flahault f. *parietina*, *Scytonema hofmannii* C. Agardh ex Bornet & Flahault, *Aphanocapsa* sp. 1, *Aphanocapsa* cf. *fusco-lutea*. In the same time, no more than three species of

Anagnostidis et Komarek, *Synechocystis salina* Wislouch.

C at normal pressure. Aliquots of the solution were taken from

in the chemical laboratory of the All-Russian Geological Institute.

**102**

**Figure 1.** Stigonema ocellatum *dominated biofilm on the surface of granite rapakivi in the quarry I.*

cyanobacteria were detected in each of the studied samples which were collected inside the tunnels. Moreover, the diversity of biofilms types inside tunnels was much lower than in the open air. In total, only three types of biofilms with the dominance of cyanobacteria were found in the tunnels (**Figure 2**).


It is interesting to note that only five taxa were found in Monrepos Park (Vyborg). This is due to the super dominance of certain species of cyanobacteria in biofilms on the surface of granite (**Figures 3–5**).

In total, 78 cyanobacteria taxa belonging to 5 orders, 18 families, and 29 genera were identified in the studied habitats. Quarry IV was the richest in the number of species (**Figure 6**).

The largest number of families (4), genera (8), and species (29) was noted for the order Synechococcales, followed by the order Chroococcales (25 species). The most diverse is the genus *Leptolyngbya* (**Figure 7**). It occurs most often. Cosmopolitan species predominated among the identified cyanobacteria.

The most common in the studied areas are *Calothrix parietina* Thur. ex born. & Flah., *Gloeocapsopsis magma* (Brébisson) Komarék et Anagnostidis, *Leptolyngbya foveolarum* (Rabenhorst ex Gomont) Anagnostidis et Komarek, *Gloeocapsa atrata* Kützing, nom. illeg. (**Figure 8**).

**Figure 2.** *Different types of biofilms and deposits in the Vyborg tunnels.*

#### **Figure 3.**

*Biofilm formed by the cyanobacteria* Microcoleus vaginatus *Gomont ex Gomont on the granite wall of the Vyborg castle (Vyborg).*

Organotrophic bacteria were also characterized by significant diversity at various granite sites in the city of Vyborg, including Monrepos Park. Their number reached 107 cells per 1 gram of material. A similar picture was observed in St. Petersburg (on the granite monuments of Museum Necropolises). The results of

**105**

**Figure 5.**

*Monrepos Park (Vyborg).*

**Figure 4.**

*Monrepos Park (Vyborg).*

from black biofilms (**Table 1**).

*Changes of Granite Rapakivi under the Biofouling Influence*

metagenomic analysis show that two main bacterial phyla dominate in biofilms on the granite rapakivi in city environment: Bacteroidetes and Proteobacteria. The Bacteroidetes phyla were characterized by a large presence in black biofilms. A significant part of the lithobiotic communities in all samples of granite was represented by actinomycetes. Acidobacteria were also isolated in a significant amount

*Biofilm formed by the cyanobacteria from the genera* Lyngbya *and* Synechococcus *on a granite wall in* 

*Biofilm formed by the cyanobacteria* Lyngbya martensiana *Meneghini ex Gomont on a granite block in* 

In the heterotrophic block of biofilms on the surface of granite, a significant diversity of micromycetes was noted. In total, 64 species of micromycetes were isolated and identified (47 – St. Petersburg, 42 – granite outcrops, and 25 – common species). The domination of dark-colored fungi in biofilms on the granite

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

#### **Figure 4.**

*Geochemistry*

**104**

reached 107

*Vyborg castle (Vyborg).*

**Figure 3.**

**Figure 2.**

*Different types of biofilms and deposits in the Vyborg tunnels.*

Organotrophic bacteria were also characterized by significant diversity at various granite sites in the city of Vyborg, including Monrepos Park. Their number

*Biofilm formed by the cyanobacteria* Microcoleus vaginatus *Gomont ex Gomont on the granite wall of the* 

Petersburg (on the granite monuments of Museum Necropolises). The results of

cells per 1 gram of material. A similar picture was observed in St.

*Biofilm formed by the cyanobacteria* Lyngbya martensiana *Meneghini ex Gomont on a granite block in Monrepos Park (Vyborg).*

#### **Figure 5.**

*Biofilm formed by the cyanobacteria from the genera* Lyngbya *and* Synechococcus *on a granite wall in Monrepos Park (Vyborg).*

metagenomic analysis show that two main bacterial phyla dominate in biofilms on the granite rapakivi in city environment: Bacteroidetes and Proteobacteria. The Bacteroidetes phyla were characterized by a large presence in black biofilms. A significant part of the lithobiotic communities in all samples of granite was represented by actinomycetes. Acidobacteria were also isolated in a significant amount from black biofilms (**Table 1**).

In the heterotrophic block of biofilms on the surface of granite, a significant diversity of micromycetes was noted. In total, 64 species of micromycetes were isolated and identified (47 – St. Petersburg, 42 – granite outcrops, and 25 – common species). The domination of dark-colored fungi in biofilms on the granite

**Figure 6.** *The number of cyanobacterial taxa revealed on the granite in study areas.*

**Figure 7.** *Number of species in the richest genera.*

surface was typical for the urban environment. It is interesting to note that some microfungi were superdominants in biofilms on granite in an urban environment (*Cladosporium, Alternaria, Aureobasidium*, and also black yeast-like fungi). Species of ascomycetes prevailed in the taxonomic relationship, which was shown using metagenomic analysis. Microcolonies and hyphae of microscopic fungi were typical for damaged granite surface (**Figures 9–11**). According to scanning electron microscopy study (SEM-analysis), microcolonies can be considered as the dominant form of the fungal existence on granite. Small compact clusters and chains of thickwalled cells (short hyphae) were noted in the granite surface in natural outcrops as well as in urban environment. Fungi are able to penetrate through microcracks into the rock substrate while causing weakening of the surface layer of granite. Fungal microcolonies were formed usually on feldspar and mica. Long hyphae were usually connected with the microrelief of K-feldspar. They were more typical for granite rapakivi in Saint Petersburg (**Figure 11**).

**107**

isms in biofilms.

**Figure 8.**

**Table 1.**

*Changes of Granite Rapakivi under the Biofouling Influence*

As a result of biochemical studies, more than 200 different compounds were found in biofilms samples from granite quarries. Among them were identified: mono, di, and trisaccharides, aliphatic carboxylic acids, amino acids, sugar alcohols, phenolic compounds, diterpenes, sterols, ethanolamine, phosphate, glycerol-3-P, and urea. In samples of biofilms taken in an urban environment only about 100 different low molecular weight organic compounds were identified. In general, the biofilm samples from granite in urban environment had a significantly lower molecular diversity of metabolites than the samples taken in the quarries in Finland. At the same time, the quantitative content of some compounds, primarily sugar alcohols, was significantly higher in biofilms in the urban environment. Most likely, the revealed differences are associated with the species composition of microorgan-

*The dominant groups of organotrophic bacteria in biofilms on granite at the monuments of the Museum* 

*Necropolises in St. Petersburg (share according to the results of metagenomic analysis).*

*The presence of common taxa of cyanobacteria in biofilms on granites in the studied places.*

**Bacteria phyla Green biofilm Black biofilm** *Acidobacteria* 0.2 6.6 *Actinobacteria* 15.2 7.5 *Bacteroidetes* 13.3 40.5 *Firmicutes* 2.7 0.0 *Proteobacteria* 48.7 33.4

The general patterns of the distribution of small organic molecules depending on the type of biofilms were similar for samples taken in the quarries and in Museum Necropolises (Saint Petersburg). In biofilms with a predominance of algae and cyanobacteria, the amount of mono- and disaccharides, amino acids and organic acids in free form was significantly higher in comparison with other types of biofilms. In samples dominated by fungi, the amount of free-form organic acids

Sugar alcohols and phenolic compounds predominated in the fouling formed by lichens. In samples of primary soil with a moss cover, the greatest variety of low molecular weight metabolites was observed; however, their quantitative content was lower than in other samples. The data obtained show the possibility

was lower and concentration of polyols was higher compared to algae.

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

#### *Changes of Granite Rapakivi under the Biofouling Influence DOI: http://dx.doi.org/10.5772/intechopen.92324*

#### **Figure 8.**

*Geochemistry*

**Figure 6.**

**Figure 7.**

*Number of species in the richest genera.*

*The number of cyanobacterial taxa revealed on the granite in study areas.*

**106**

rapakivi in Saint Petersburg (**Figure 11**).

surface was typical for the urban environment. It is interesting to note that some microfungi were superdominants in biofilms on granite in an urban environment (*Cladosporium, Alternaria, Aureobasidium*, and also black yeast-like fungi). Species of ascomycetes prevailed in the taxonomic relationship, which was shown using metagenomic analysis. Microcolonies and hyphae of microscopic fungi were typical for damaged granite surface (**Figures 9–11**). According to scanning electron microscopy study (SEM-analysis), microcolonies can be considered as the dominant form of the fungal existence on granite. Small compact clusters and chains of thickwalled cells (short hyphae) were noted in the granite surface in natural outcrops as well as in urban environment. Fungi are able to penetrate through microcracks into the rock substrate while causing weakening of the surface layer of granite. Fungal microcolonies were formed usually on feldspar and mica. Long hyphae were usually connected with the microrelief of K-feldspar. They were more typical for granite

*The presence of common taxa of cyanobacteria in biofilms on granites in the studied places.*


#### **Table 1.**

*The dominant groups of organotrophic bacteria in biofilms on granite at the monuments of the Museum Necropolises in St. Petersburg (share according to the results of metagenomic analysis).*

As a result of biochemical studies, more than 200 different compounds were found in biofilms samples from granite quarries. Among them were identified: mono, di, and trisaccharides, aliphatic carboxylic acids, amino acids, sugar alcohols, phenolic compounds, diterpenes, sterols, ethanolamine, phosphate, glycerol-3-P, and urea. In samples of biofilms taken in an urban environment only about 100 different low molecular weight organic compounds were identified. In general, the biofilm samples from granite in urban environment had a significantly lower molecular diversity of metabolites than the samples taken in the quarries in Finland. At the same time, the quantitative content of some compounds, primarily sugar alcohols, was significantly higher in biofilms in the urban environment. Most likely, the revealed differences are associated with the species composition of microorganisms in biofilms.

The general patterns of the distribution of small organic molecules depending on the type of biofilms were similar for samples taken in the quarries and in Museum Necropolises (Saint Petersburg). In biofilms with a predominance of algae and cyanobacteria, the amount of mono- and disaccharides, amino acids and organic acids in free form was significantly higher in comparison with other types of biofilms. In samples dominated by fungi, the amount of free-form organic acids was lower and concentration of polyols was higher compared to algae.

Sugar alcohols and phenolic compounds predominated in the fouling formed by lichens. In samples of primary soil with a moss cover, the greatest variety of low molecular weight metabolites was observed; however, their quantitative content was lower than in other samples. The data obtained show the possibility

**Figure 9.** *Fungal microcolonies on the border of mica (Quarry I).*

#### **Figure 10.**

*Fungal microcolonies and short hyphae located on the K-feldspar (Quarry I).*

of applying the metabolomic approach to the study of lithobiotic communities in different environment.

#### **3.2 Geochemical peculiarities of granite bioweathering**

To assess the effect of biofouling on the behavior of chemical elements during granite weathering, samples of granite rapakivi were taken in natural outcrops

**109**

**Figure 11.**

**Figure 12.**

*Changes of Granite Rapakivi under the Biofouling Influence*

(granite wall) in Monrepos Park (Vyborg neighborhood) where the influence of the urban environment on natural ecosystem is insignificant. This type of granite is commonly called Wiborgite. Wiborgite is a porphyritic, coarse-grained granite with a typical rapakivi texture composed of round 1–3 cm potassium feldspar ovoids with a plagioclase mantle. The color of this rock can be brown, brownish red, red or green. The essential minerals are potassium feldspar, quartz, plagioclase, biotite,

*Thin skin of rapakivi granite: (a) plagioclase, microcline and biotite with pyrite and zircon; (b) quartz,* 

*Fungal hyphae in the granite surface of Stasov monument (Museum Necropolis of Saint Petersburg).*

Three types of samples were taken for comparative study: fresh granite, crust without biofilm (3 mm) and crust with biofilm (3 mm). The results of the analysis

It is shown that the content of almost all petrogenic oxides (except SiO2), decreases in the crust without a biofilm (**Table 3**). This fact can be explained by the destruction of the granite structure and leaching of the most mobile chemical elements and particles of minerals under the influence of rain and wind. The crust is

and hornblende (**Figure 12a** and **b**, **Table 2**).

are presented in **Tables 3** and **4**.

*plagioclase and microcline. XPL (a), PPL (b).*

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

**Figure 11.**

*Geochemistry*

**Figure 9.**

*Fungal microcolonies on the border of mica (Quarry I).*

**108**

**Figure 10.**

different environment.

of applying the metabolomic approach to the study of lithobiotic communities in

To assess the effect of biofouling on the behavior of chemical elements during granite weathering, samples of granite rapakivi were taken in natural outcrops

**3.2 Geochemical peculiarities of granite bioweathering**

*Fungal microcolonies and short hyphae located on the K-feldspar (Quarry I).*

*Fungal hyphae in the granite surface of Stasov monument (Museum Necropolis of Saint Petersburg).*

**Figure 12.**

(granite wall) in Monrepos Park (Vyborg neighborhood) where the influence of the urban environment on natural ecosystem is insignificant. This type of granite is commonly called Wiborgite. Wiborgite is a porphyritic, coarse-grained granite with a typical rapakivi texture composed of round 1–3 cm potassium feldspar ovoids with a plagioclase mantle. The color of this rock can be brown, brownish red, red or green. The essential minerals are potassium feldspar, quartz, plagioclase, biotite, and hornblende (**Figure 12a** and **b**, **Table 2**).

Three types of samples were taken for comparative study: fresh granite, crust without biofilm (3 mm) and crust with biofilm (3 mm). The results of the analysis are presented in **Tables 3** and **4**.

It is shown that the content of almost all petrogenic oxides (except SiO2), decreases in the crust without a biofilm (**Table 3**). This fact can be explained by the destruction of the granite structure and leaching of the most mobile chemical elements and particles of minerals under the influence of rain and wind. The crust is


#### **Table 2.**

*Mineral composition of rapakivi granite (Wiborgite).*


#### **Table 3.**

*Content of pertogenic oxides in fresh granite and two types of crust (mass%).*


#### **Table 4.**

*Content of trace elements in fresh granite and two types of crust (ppm) and coefficient concentration (CC).*

relatively enriched with the most stable mineral quartz. The organic matter content LOI (loss on ignition) increases slightly in comparison with fresh granite. In the crust with biofilm the situation is different. Particles of weathered granite can be

**111**

**Figure 13.**

*Changes of Granite Rapakivi under the Biofouling Influence*

accumulated in a biofilm. This probably explains the fact that the content of almost all basic elements in the crust with biofilm is close to the composition of unaltered granite. The organic matter content in the crust with biofilm is naturally the highest

A similar situation is observed in the behavior of trace elements. It is shown using the concentration coefficient (CC) calculated as the ratio of the content of the element in the crust to its content in not weathered granite. In the weathered crust, in comparison with fresh granite, the removal of most chemical elements is observed (**Table 4**). The concentration coefficient in this case is less than 1. At the same time, trace elements (Se, Mo, U, Cu, Ni, Zn, and Sr) are accumulated in the

It is well known that the main environment of migration of chemical elements in the nature is water. Migration of elements in the liquid phase occurs in the form of ions, molecules, and colloidal particles. The chemical composition of water in the hypergenesis zone is formed primarily due to the dissolution of solid phases interacting with water. Granite biofouling may affect this process. For the experiment on the dynamics of granite bioleaching, we took three types of samples from the surface of granite rapakivi from the Monrepos Park (Vyborg): surface layer of granite without biofilms, with black (lichens + fungi + cyanobacteria), and with

As a result, it was shown that the particle size changes over time that reflects the periods of their dissolution and coagulation. On the first day no changes are observed. Further until the 22nd day changes in particles size are observed and then alignment occurs (about 380 nm in size). The curves for the studied variants differ markedly. Largest particle size during the experiment is observed for granite with

A comparison of the graphs of pH changes (**Figure 14**) shows that at the beginning of the experiment, the pH of solutions for the granite without biofilms and granite with biofilms is different. Amplitude of the pH values changes varies from 6.3 to 7.6 and does not connect with the changes in particles size. Correlation analysis confirmed the absence of any linear dependence of the change in the size of

*Particles size changes in time for granite, granite with black, and gray biofilms (nm). h – hours; d – days.*

crust with the biofilm (concentration coefficient is more than 1).

black biofilm a compared to granite with gray biofilm (**Figure 13**).

nanoparticle in solution on the pH of the solutions.

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

in comparison with other variants.

gray (lichens + alga) biofilms.

*Geochemistry*

Granite (n = 7)

*Mineral composition of rapakivi granite (Wiborgite).*

**Table 2.**

Granite crust (n = 7)

Granite crust with biofilm (n = 7)

**Elements Granite** 

**(n = 7)**

**Table 3.**

**110**

**Table 4.**

relatively enriched with the most stable mineral quartz. The organic matter content LOI (loss on ignition) increases slightly in comparison with fresh granite. In the crust with biofilm the situation is different. Particles of weathered granite can be

*Content of trace elements in fresh granite and two types of crust (ppm) and coefficient concentration (CC).*

**Samples SiO2 Al2O3 Fe2O3 K2O Na2O CaO MgO TiO2 P2O5 MnO LOI**

**Crust with biofilm (n = 7)**

Ba 119 126 121 1.06 1.02 Sr 12.8 8.1 15.8 0.63 1.18 Li 38.3 34 40.2 0.89 1.05 Sc 4.88 4.36 5.1 0.89 1.05 U 7.37 2.37 12.4 0.32 1.68 Se 3.19 1.89 6.45 0.59 2.02 Mo 1.66 0.22 2.83 0.13 1.70 Cd 0.24 0.11 0.25 0.46 1.08 Sb 0.09 0.05 0.09 0.56 1.00 Ni 12.6 14.6 15.5 1.16 1.23 Co 3.3 3.09 3.79 0.94 1.15 Cu 6.28 6.1 7.98 0.97 1.27 Zn 65.3 72.2 79.1 1.11 1.21 As 11.7 10.3 11.1 0.88 0.95

**Mineral Mass % Mineral Mass % Mineral Mass %** Quartz 24–42% Muscovite 0–0.1% Ilmenite 0–0.5% K-feldspar 28–42% Allanite 0–0.2% Rutile 0–0.1% Albite 7–13.7% Tourmaline 0–0.2% Apatite 0–0.3% Andesine 3–27% Zircon 0.1–0.2% Pyrite 0.0 Amphibole 0.2–11% Kaolinite 0–0.1% Calcite 0.0 Chlorite 0.0–0.2% Thorite 0-0.1% Bastnasite 0–0.9% Biotite 2.9–7.5% Magnetite 0–0.1% Fluorite 0.2–1.9%

*Content of pertogenic oxides in fresh granite and two types of crust (mass%).*

**Crust (n = 7)**

70.78 13.51 3.38 5.57 3.39 2.32 0.22 0.33 0.07 0.04 0.38

72.19 13.05 3.19 5.29 3.11 2.06 0.20 0.34 0.08 0.04 0.46

69.51 14.50 3.54 5.41 3.34 2.29 0.23 0.36 0.06 0.03 0.76

**CC1 = crust / granite**

**CC2 = crust with biofilm/granite**

accumulated in a biofilm. This probably explains the fact that the content of almost all basic elements in the crust with biofilm is close to the composition of unaltered granite. The organic matter content in the crust with biofilm is naturally the highest in comparison with other variants.

A similar situation is observed in the behavior of trace elements. It is shown using the concentration coefficient (CC) calculated as the ratio of the content of the element in the crust to its content in not weathered granite. In the weathered crust, in comparison with fresh granite, the removal of most chemical elements is observed (**Table 4**). The concentration coefficient in this case is less than 1. At the same time, trace elements (Se, Mo, U, Cu, Ni, Zn, and Sr) are accumulated in the crust with the biofilm (concentration coefficient is more than 1).

It is well known that the main environment of migration of chemical elements in the nature is water. Migration of elements in the liquid phase occurs in the form of ions, molecules, and colloidal particles. The chemical composition of water in the hypergenesis zone is formed primarily due to the dissolution of solid phases interacting with water. Granite biofouling may affect this process. For the experiment on the dynamics of granite bioleaching, we took three types of samples from the surface of granite rapakivi from the Monrepos Park (Vyborg): surface layer of granite without biofilms, with black (lichens + fungi + cyanobacteria), and with gray (lichens + alga) biofilms.

As a result, it was shown that the particle size changes over time that reflects the periods of their dissolution and coagulation. On the first day no changes are observed. Further until the 22nd day changes in particles size are observed and then alignment occurs (about 380 nm in size). The curves for the studied variants differ markedly. Largest particle size during the experiment is observed for granite with black biofilm a compared to granite with gray biofilm (**Figure 13**).

A comparison of the graphs of pH changes (**Figure 14**) shows that at the beginning of the experiment, the pH of solutions for the granite without biofilms and granite with biofilms is different. Amplitude of the pH values changes varies from 6.3 to 7.6 and does not connect with the changes in particles size. Correlation analysis confirmed the absence of any linear dependence of the change in the size of nanoparticle in solution on the pH of the solutions.

**Figure 13.** *Particles size changes in time for granite, granite with black, and gray biofilms (nm). h – hours; d – days.*

#### *Geochemistry*

The results show the periodic variation of the acid-alkaline properties of the solutions. As a whole, the variant with the black biofilm are characterized by a more alkaline medium; the variant with gray biofilm has a relatively more acidic medium.

In selected aliquots of solutions, the content of chemical elements was determined by the ICP MS method. The highest concentrations of elements in the solutions were observed for K, Na, Mg, and Ca (an example for calcium is shown in **Figure 15**). This indicates a fairly rapid leaching of these elements from the minerals of the rock, where they are in water-soluble form. Lower contents are typical for a group of elements: Al, Fe, Ba, and Li. Hundreds of mg per liter were found for: Mn, Rb, Sr, and Cs. Thousands of mg were found for the following elements: Sc, V, Ni, Pb, Cu, Zn, Mo, U, Th, Y, La, and Ce. An increased concentration of various groups of elements is observed on the 8th day (K, Na, Ni, As, Cd, and Mo) that can be associated with an increase in the pH of the solution.

The experimental results demonstrate the different behavior of chemical elements in the absence and presence of biofilms on granite. There is also a different

**Figure 14.**

*pH values changes of solutions (granite, granite with black, and gray biofilms). h – hours; d – days.*

#### **Figure 15.**

*Dynamics of the calcium content changes in solutions (mg/L) during the dissolution of granite, granite with gray and black biofilms. h – hours; d – days.*

**113**

*Changes of Granite Rapakivi under the Biofouling Influence*

behavior of chemical elements in variants with different types of biofilms. The dissolution of granite with a black biofilm is the least intense, which is especially noticeable on the example of Na, Ca, and Mo. The content of these elements in granite with black biofilm practically does not change in solutions over time. Since fungi dominate in the black biofilm, it can be assumed that the migration of elements into the solution may be limited due to the immobilization of elements by fungal biomass. Due to metabolic processes (the release of organic acids and the binding of metals by specific proteins) as well as the physicochemical properties of the cell wall, fungi can efficiently bind metals and significantly reduce their mobil-

Biogenic weathering of granite is connected with the impact on the rock surface by microorganisms of lithobiotic communities (bacteria, microfungi, microalgae, lichens, and mosses). The biological colonization of granite is a multifactorial process. It depends on the composition of the microbiota, the state of the stone, as well as external conditions. The ecological aspect of the problem is determined by the difference between granite biofouling in the anthropogenic (urban) and natural environment. The biofilms on granite are characterized by a wide diversity of cyanobacteria, micromycetes, and organotrophic bacteria. The species composition often determines the features of the appearance of a biofilm, the features of its development on granite, as well as the biochemical composition and degree of impact on granite. Behavior of chemical elements during the bioweathering of granite depends on the type of biofilm in which some elements can be accumulated. This problem seems as an interdisciplinary task and requires the collaboration of biologists and

The work was carried out in the resource centers of Saint Petersburg State University: "Chemical Analysis and Materials Research Center," "Development of cellular and molecular technologies," and "Microscopy and Microanalysis."

Researches are supported by the European Union, Russia, and Finland (KS 1528

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

ity in solution [6].

**4. Conclusion**

geologists.

project).

**Acknowledgements**

**Conflict of interest**

The authors declare no conflict of interest.

*Changes of Granite Rapakivi under the Biofouling Influence DOI: http://dx.doi.org/10.5772/intechopen.92324*

behavior of chemical elements in variants with different types of biofilms. The dissolution of granite with a black biofilm is the least intense, which is especially noticeable on the example of Na, Ca, and Mo. The content of these elements in granite with black biofilm practically does not change in solutions over time. Since fungi dominate in the black biofilm, it can be assumed that the migration of elements into the solution may be limited due to the immobilization of elements by fungal biomass. Due to metabolic processes (the release of organic acids and the binding of metals by specific proteins) as well as the physicochemical properties of the cell wall, fungi can efficiently bind metals and significantly reduce their mobility in solution [6].

#### **4. Conclusion**

*Geochemistry*

**112**

**Figure 15.**

*gray and black biofilms. h – hours; d – days.*

**Figure 14.**

*pH values changes of solutions (granite, granite with black, and gray biofilms). h – hours; d – days.*

*Dynamics of the calcium content changes in solutions (mg/L) during the dissolution of granite, granite with* 

be associated with an increase in the pH of the solution.

The results show the periodic variation of the acid-alkaline properties of the solutions. As a whole, the variant with the black biofilm are characterized by a more alkaline medium; the variant with gray biofilm has a relatively more acidic medium. In selected aliquots of solutions, the content of chemical elements was determined by the ICP MS method. The highest concentrations of elements in the solutions were observed for K, Na, Mg, and Ca (an example for calcium is shown in **Figure 15**). This indicates a fairly rapid leaching of these elements from the minerals of the rock, where they are in water-soluble form. Lower contents are typical for a group of elements: Al, Fe, Ba, and Li. Hundreds of mg per liter were found for: Mn, Rb, Sr, and Cs. Thousands of mg were found for the following elements: Sc, V, Ni, Pb, Cu, Zn, Mo, U, Th, Y, La, and Ce. An increased concentration of various groups of elements is observed on the 8th day (K, Na, Ni, As, Cd, and Mo) that can

The experimental results demonstrate the different behavior of chemical elements in the absence and presence of biofilms on granite. There is also a different

Biogenic weathering of granite is connected with the impact on the rock surface by microorganisms of lithobiotic communities (bacteria, microfungi, microalgae, lichens, and mosses). The biological colonization of granite is a multifactorial process. It depends on the composition of the microbiota, the state of the stone, as well as external conditions. The ecological aspect of the problem is determined by the difference between granite biofouling in the anthropogenic (urban) and natural environment. The biofilms on granite are characterized by a wide diversity of cyanobacteria, micromycetes, and organotrophic bacteria. The species composition often determines the features of the appearance of a biofilm, the features of its development on granite, as well as the biochemical composition and degree of impact on granite. Behavior of chemical elements during the bioweathering of granite depends on the type of biofilm in which some elements can be accumulated. This problem seems as an interdisciplinary task and requires the collaboration of biologists and geologists.

#### **Acknowledgements**

The work was carried out in the resource centers of Saint Petersburg State University: "Chemical Analysis and Materials Research Center," "Development of cellular and molecular technologies," and "Microscopy and Microanalysis."

Researches are supported by the European Union, Russia, and Finland (KS 1528 project).

#### **Conflict of interest**

The authors declare no conflict of interest.

*Geochemistry*

#### **Author details**

Dmitry Yu. Vlasov1,3\*, Elena G. Panova1 , Marina S. Zelenskaya1 , Oksana A. Rodina1 , Alexey D. Vlasov2 and Katerina V. Sazanova2,3

1 Saint Petersburg State University, Saint Petersburg, Russia

2 The Archive of the Russian Academy of Sciences, Saint Petersburg, Russia

3 Komarov Botanical Institute of the Russian Academy of Sciences, Saint Petersburg, Russia

\*Address all correspondence to: dmitry.vlasov@mail.ru

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**115**

*Changes of Granite Rapakivi under the Biofouling Influence*

2012;**426**:1-12. DOI: 10.1016/j.

[9] Vlasov DY, Panova EG, Zelenskaya MS, Vlasov AD,

Metabolism and Interaction with Substrate. In: Processes and Phenomena on the Boundart Between Biogenic and Abiogenic Nature. Springer; 2020. pp. 535-559. DOI: 10.1007/978-3-030-21614-6\_29

Sazanova KV, Rodina OA, et al. Biofilms on Granite Rapakivi in Natural Outcrops and Urban Environment: Biodiversity,

scitotenv.2012.03.026

*DOI: http://dx.doi.org/10.5772/intechopen.92324*

[1] Toreno G, Isola D, Meloni P, Carcangiu G, Selbmann L, Onofri S, et al. Biological colonization on stone monuments: A new low impact cleaning method. Journal of Cultural Heritage. 2018;**30**:100-109. DOI: 10.1016/j.

[2] Grbić ML, Vukojević J, Simić GS, Krizmanić J, Stupar M. Biofilm forming cyanobacteria, algae and fungi on two historic monuments in Belgrade, Serbia. Archives of Biological Sciences. 2010;**62**(3):625-631. DOI: 10.2298/

[3] Ozturk A, Karaca Z, Unsal T. The activity of oxygenic photosynthetic microbial consortia on different granites. Ekoloji. 2014;**23**(90):90-96. DOI: 10.5053/ekoloji.2014.9011

[4] Gorbushina AA. Life on the rocks. Environmental Microbiology.

[6] Gadd MG. Fungi, rocks and minerals. Elements. 2017;**13**:171-176. DOI: 10.2113/gselements.13.3.171

[7] Prieto B, Silva B. Estimation of potential bioreceptivity of granitic rocks from their instrinsic properties. International Biodeterioration and Biodegradation. 2005;**56**:206-215. DOI:

[8] Miller AZ, Sanmartín P, Pereira-Pardo L, Dionísio A, Saiz-Jimenez C, Macedo MF, et al. Bioreceptivity of building stones: A review. The Science of the Total Environment.

10.1016/j.ibiod.2005.08.001

[5] Dakal TC, Cameotra SS. Microbially induced deterioration of architectural heritages: Routes and mechanisms involved. Environmental Sciences Europe. 2012;**24**(1):1-12. DOI: 10.1186/2190-4715-24-36

2007;**9**(7):1613-1631. DOI: 10.1111/j.1462-2920.2007.01301.x

**References**

culher.2017.09.004

ABS1003625L

*Changes of Granite Rapakivi under the Biofouling Influence DOI: http://dx.doi.org/10.5772/intechopen.92324*

#### **References**

*Geochemistry*

**114**

**Author details**

Alexey D. Vlasov2

Saint Petersburg, Russia

Dmitry Yu. Vlasov1,3\*, Elena G. Panova1

and Katerina V. Sazanova2,3

2 The Archive of the Russian Academy of Sciences, Saint Petersburg, Russia

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

3 Komarov Botanical Institute of the Russian Academy of Sciences,

1 Saint Petersburg State University, Saint Petersburg, Russia

\*Address all correspondence to: dmitry.vlasov@mail.ru

provided the original work is properly cited.

, Marina S. Zelenskaya1

, Oksana A. Rodina1

,

[1] Toreno G, Isola D, Meloni P, Carcangiu G, Selbmann L, Onofri S, et al. Biological colonization on stone monuments: A new low impact cleaning method. Journal of Cultural Heritage. 2018;**30**:100-109. DOI: 10.1016/j. culher.2017.09.004

[2] Grbić ML, Vukojević J, Simić GS, Krizmanić J, Stupar M. Biofilm forming cyanobacteria, algae and fungi on two historic monuments in Belgrade, Serbia. Archives of Biological Sciences. 2010;**62**(3):625-631. DOI: 10.2298/ ABS1003625L

[3] Ozturk A, Karaca Z, Unsal T. The activity of oxygenic photosynthetic microbial consortia on different granites. Ekoloji. 2014;**23**(90):90-96. DOI: 10.5053/ekoloji.2014.9011

[4] Gorbushina AA. Life on the rocks. Environmental Microbiology. 2007;**9**(7):1613-1631. DOI: 10.1111/j.1462-2920.2007.01301.x

[5] Dakal TC, Cameotra SS. Microbially induced deterioration of architectural heritages: Routes and mechanisms involved. Environmental Sciences Europe. 2012;**24**(1):1-12. DOI: 10.1186/2190-4715-24-36

[6] Gadd MG. Fungi, rocks and minerals. Elements. 2017;**13**:171-176. DOI: 10.2113/gselements.13.3.171

[7] Prieto B, Silva B. Estimation of potential bioreceptivity of granitic rocks from their instrinsic properties. International Biodeterioration and Biodegradation. 2005;**56**:206-215. DOI: 10.1016/j.ibiod.2005.08.001

[8] Miller AZ, Sanmartín P, Pereira-Pardo L, Dionísio A, Saiz-Jimenez C, Macedo MF, et al. Bioreceptivity of building stones: A review. The Science of the Total Environment.

2012;**426**:1-12. DOI: 10.1016/j. scitotenv.2012.03.026

[9] Vlasov DY, Panova EG, Zelenskaya MS, Vlasov AD, Sazanova KV, Rodina OA, et al. Biofilms on Granite Rapakivi in Natural Outcrops and Urban Environment: Biodiversity, Metabolism and Interaction with Substrate. In: Processes and Phenomena on the Boundart Between Biogenic and Abiogenic Nature. Springer; 2020. pp. 535-559. DOI: 10.1007/978-3-030-21614-6\_29

Section 2

Geochemistry of Isotopes

and Exploration

Geochemistry

**117**

### Section 2
