[77] Balistrieri LS, Shanks WC, Cuhel RL, Aguilar C, Val Klump J. The influence of sublacustrine hydrothermal vent fluids on the geochemistry of Yellowstone Lake. In: Morgan LA, editor. Integrated Geoscience Studies in the Greater Yellowstone Area— Volcanic, Tectonic, and Hydrothermal Processes in the Yellowstone Geoecosystem. Professional Paper 1717 ed. U.S. Geological Survey; 2009. pp. 173-199

[64] Mudelsee M, Raymo ME. Slow dynamics of the northern hemisphere glaciation.

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

[65] Sternai P, Caricchi L, Castelltort S, Champagnac J-D. Deglaciation and glacial erosion: A joint control on magma productivity by continental unloading. Geophysical Research

[66] Ligi M, Cuffaro M, Chierici F, Calafato A. Three-dimensional passive mantle flow beneath midocean ridges: An analytical approach. Geophysical Journal International. 2008;175:783-805

[67] Maclennan J, Jull M, McKenzie D, Slater L, Gronvold K. The link between volcanism and

[68] Roy M, Clark PU, Barendregt RW, Glasmann JR, Enkin RJ. Glacial stratigraphy and paleomagnetism of late Cenozoic deposits of the north-central United States. GSA Bulletin.

[69] Loewen MW, Bindeman IN. Oxygen isotope and trace element evidence for three-stage petrogenesis of the youngest episode (260-79 ka) of Yellowstone rhyolitic volcanism.

[70] Petit JR, Jouzel J, Raynaud D, Barkov NI, Barnola JM, Basile I, Bender M, Chappellaz J, Davis J, Delaygue G, Delmotte M, Kotlyakov VM, Legrand M, Lipenkov V, Lorius C, Pe'pin L, Ritz C, Saltzman E, Stievenard M. Climate and atmospheric history of the past

[71] Christiansen RL. The Quaternary and Pliocene Yellowstone Plateau Volcanic Field of Wyoming, Idaho, and Montana. Professional Paper 729-G Ed. U.S. Geological Survey:

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[73] Wu P. Intraplate earthquakes and postglacial rebound in Eastern Canada and northern Europe. In: Wu P, editor. Dynamics of the Ice Age Earth: A Modern Perspective. Uetikon-

[74] Browne PRL, Lawless JV. Characteristics of hydrothermal eruptions, with examples from

[75] Hedenquist JW, Henley RW. Hydrothermal eruptions in the Waiotapu geothermal system, New Zealand: Their origin, associated breccias and relation to precious metal min-

[76] Simakin AG, Salova TP, Gabitov RI, Isaenko SI. Dry CO2–CO fluid as an important

Zurich, Switzerland: Trans Tech Publications; 1998. pp. 603-628

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potential deep earth solvent. Geofluids. 2016;16:1043-1057

420,000 years from the Vostok ice Core, Antarctica. Nature. 1999;399:429-436

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deglaciation in Iceland. G3. 2002;3:1062. DOI: 10.1029/2001GC000282

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Industry and Their Impact on the Human Health

206

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Reston, Virginia; 2001. 146 p

2009.2459

2004;116(1/2):30-41

**Section 4**

**Application of Volcanoes to Industry**

**Application of Volcanoes to Industry**

**Chapter 10**

**Provisional chapter**

**Volcanic Scoria as Cement Replacement**

**Volcanic Scoria as Cement Replacement**

DOI: 10.5772/intechopen.77970

Numerous volcanic scoria (VS) cones are found in many places of the world. Many of them have not yet been investigated, although few have been used as binders for a very long time. The use of natural pozzolans as cement replacement could be considered as a common practice in the construction industry due to the related economic, ecologic and performance benefits. This chapter highlights the advantages and disadvantages of the use of volcanic scoria as cement replacement in concrete mixes in terms of fresh and hardened concrete properties. The chemical and mineralogical composition of volcanic scoria samples collected from 36 countries is presented in this chapter, with some further analysis. The effects of using volcanic scoria as cement replacement on some paste, mortar and concrete properties, such as the setting times, the heat of hydration, the compressive strength, the water permeability and the chloride penetrability, have been studied. The improvement in resistance against the chemical attack of volcanic scoria-based cement mortar has also been highlighted. Some estimation equations depending on the data available in literature have also been derived from the analyzed data. The modification of

the microstructure of VS-based cement paste has been confirmed, as well.

of concrete per capita [2].

**Keywords:** volcanic scoria, blended cement, compressive strength, concrete durability,

Concrete is the most widely used construction material around the world, because of the economic and widespread availability of its constituents, its versatility, its durability and its adaptability [1]. In the year 2000, more than 1.5 billion tons of cement were produced to make,

> © 2016 The Author(s). Licensee InTech. 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.

© 2018 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.

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.77970

Aref M. al-Swaidani

Aref M. al-Swaidani

**Abstract**

pozzolan

**1. Introduction**

on average, nearly 1 m3

#### **Volcanic Scoria as Cement Replacement Volcanic Scoria as Cement Replacement**

#### Aref M. al-Swaidani Aref M. al-Swaidani

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.77970

#### **Abstract**

Numerous volcanic scoria (VS) cones are found in many places of the world. Many of them have not yet been investigated, although few have been used as binders for a very long time. The use of natural pozzolans as cement replacement could be considered as a common practice in the construction industry due to the related economic, ecologic and performance benefits. This chapter highlights the advantages and disadvantages of the use of volcanic scoria as cement replacement in concrete mixes in terms of fresh and hardened concrete properties. The chemical and mineralogical composition of volcanic scoria samples collected from 36 countries is presented in this chapter, with some further analysis. The effects of using volcanic scoria as cement replacement on some paste, mortar and concrete properties, such as the setting times, the heat of hydration, the compressive strength, the water permeability and the chloride penetrability, have been studied. The improvement in resistance against the chemical attack of volcanic scoria-based cement mortar has also been highlighted. Some estimation equations depending on the data available in literature have also been derived from the analyzed data. The modification of the microstructure of VS-based cement paste has been confirmed, as well.

DOI: 10.5772/intechopen.77970

**Keywords:** volcanic scoria, blended cement, compressive strength, concrete durability, pozzolan

#### **1. Introduction**

Concrete is the most widely used construction material around the world, because of the economic and widespread availability of its constituents, its versatility, its durability and its adaptability [1]. In the year 2000, more than 1.5 billion tons of cement were produced to make, on average, nearly 1 m3 of concrete per capita [2].

© 2016 The Author(s). Licensee InTech. 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. © 2018 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.

Ordinary Portland cement concrete (OPC) is a composite material and its constituents are cement mixed with water, fine-grained aggregate (sand) and coarse-grained aggregate consisting of natural gravel or crushed stones [3]. Cement is a finely pulverized, dry material that by itself is not a binder but develops the binding property as a result of hydration (i.e., from chemical reactions between cement minerals and water) [4]. The considerable amount of carbon dioxide (CO2 ) liberated during the production of Portland cement, the most commonly used hydraulic cement, is of a greater concern. On average, about 1 ton of CO2 is liberated per ton of Portland cement produced [1].

The use of mineral admixtures such as pozzolans (materials containing reactive silica) in concrete is now widespread due to many economic, ecological and performance-related benefits [4, 5]. Pozzolanic material is "a siliceous or siliceous-aluminous material that in itself possesses little or no cementitious value but will, in finely divided form and in the presence of water, chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties" [6]. Pozzolanic supplementary cementitious materials (SCMs) differ from hydraulic SCMs in that hydraulic SCMs can form cementitious products in water, without the presence of calcium hydroxide [6]. The term "pozzolan" comes from the town of Pozzuoli, northeast of Naples in Italy, where red pozzolanic deposits from the volcano Vesuvius were found [7].

Pozzolanic materials can be divided into natural and artificial pozzolans. Natural pozzolans could be considered the first cementing materials used for the production of artificial stones, ancient mortars and concretes, 3000 years ago [8]. For example, according to Jackson et al. [9], the binding pozzolanic mortars of 2000-year-old concretes in the monuments of imperial age Rome contained 40–50 vol. % of scoriaceous volcanic ash. The natural pozzolans may be further divided into two main groups: (1) those derived from volcanic rocks (volcanic scorias, ashes, tuffs, pumices and obsidians) and (2) others derived from rocks and earths, such as the diatomaceous earths (cherts, opaline silica), clays which have been naturally calcined by heat from flowing lava [10].

Volcanic scoria is loose, rubbly, basaltic to andesitic (40–60% SiO2 ) ejecta that accumulates around Strombolian eruptive volcanic vents, eventually building up as a scoria cone, whose height may range from a few tens of meters to 300 m. The scoria clasts range widely in size, from millimeters to centimeters in size, and have a light, frothy texture, being full of vesicles (**Figure 1e**). The vesicular nature of scoria is due to the escape of volcanic gases during eruption. Sometimes these vesicles are refilled with minerals like zeolite, calcite and quartz that form from hot water-rich fluids. The scoria clasts are mainly dark gray in color, although when fresh they may be iridescent, but often the scoria oxidizes by reaction with steam escaping from the vent, when it becomes a deep reddish brown [11–13]. The most economically valuable volcanic scoria deposits are late tertiary or quaternary in age [14]. Most of the scorias are composed of glassy fragments and may contain phenocrysts. The word scoria comes from the Greek *skōria*, rust. An old name for scoria is cinder [15].

Although there are numerous studies on using natural pozzolan as cement replacement, few works on studying volcanic scoria were reported in the literature. The present chapter highlights some characteristics of volcanic scoria and their effects on performance-related properties of paste, mortar and concrete. The importance of this chapter is to encourage countries having ample sources of volcanic scoria cones to further investigate the possibility of using it

**Figure 1.** (a) Map of African and Arabian plate with a clearer map of Harrat al-Shaam in the upper part of the figure, (b) Photo of Syrian volcanic scoria cones, (c) Macrograph of volcanic scoria aggregates, (d) SEM of volcanic scoria particle

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 213

The chemical composition of volcanic scoria varies within wide ranges and depends on its sources. Various scoria cones are abundant in many parts of the world, such as Syria, Turkey,

as cement replacement and thus making a greener concrete.

with clear vesicles, (e) Thin section in a Syrian volcanic scoria sample.

**2. Chemical and mineralogical composition of volcanic scoria**

With respect to pumice, typical scoria has larger and more interconnected vesicles, is characterized by lower silica content and displays a darker, brown, reddish or black color [16]. Volcanic scoria can be utilized, other than as cement replacement, in several industrial applications including the manufacturing of lightweight concrete, as a heat-insulating material, in addition to other uses such as fillers, filter materials, absorbents and other architectural applications [17].

Ordinary Portland cement concrete (OPC) is a composite material and its constituents are cement mixed with water, fine-grained aggregate (sand) and coarse-grained aggregate consisting of natural gravel or crushed stones [3]. Cement is a finely pulverized, dry material that by itself is not a binder but develops the binding property as a result of hydration (i.e., from chemical reactions between cement minerals and water) [4]. The considerable amount of car-

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

The use of mineral admixtures such as pozzolans (materials containing reactive silica) in concrete is now widespread due to many economic, ecological and performance-related benefits [4, 5]. Pozzolanic material is "a siliceous or siliceous-aluminous material that in itself possesses little or no cementitious value but will, in finely divided form and in the presence of water, chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties" [6]. Pozzolanic supplementary cementitious materials (SCMs) differ from hydraulic SCMs in that hydraulic SCMs can form cementitious products in water, without the presence of calcium hydroxide [6]. The term "pozzolan" comes from the town of Pozzuoli, northeast of Naples in Italy, where red pozzolanic deposits from the

Pozzolanic materials can be divided into natural and artificial pozzolans. Natural pozzolans could be considered the first cementing materials used for the production of artificial stones, ancient mortars and concretes, 3000 years ago [8]. For example, according to Jackson et al. [9], the binding pozzolanic mortars of 2000-year-old concretes in the monuments of imperial age Rome contained 40–50 vol. % of scoriaceous volcanic ash. The natural pozzolans may be further divided into two main groups: (1) those derived from volcanic rocks (volcanic scorias, ashes, tuffs, pumices and obsidians) and (2) others derived from rocks and earths, such as the diatomaceous earths (cherts,

around Strombolian eruptive volcanic vents, eventually building up as a scoria cone, whose height may range from a few tens of meters to 300 m. The scoria clasts range widely in size, from millimeters to centimeters in size, and have a light, frothy texture, being full of vesicles (**Figure 1e**). The vesicular nature of scoria is due to the escape of volcanic gases during eruption. Sometimes these vesicles are refilled with minerals like zeolite, calcite and quartz that form from hot water-rich fluids. The scoria clasts are mainly dark gray in color, although when fresh they may be iridescent, but often the scoria oxidizes by reaction with steam escaping from the vent, when it becomes a deep reddish brown [11–13]. The most economically valuable volcanic scoria deposits are late tertiary or quaternary in age [14]. Most of the scorias are composed of glassy fragments and may contain phenocrysts. The word scoria comes from

With respect to pumice, typical scoria has larger and more interconnected vesicles, is characterized by lower silica content and displays a darker, brown, reddish or black color [16]. Volcanic scoria can be utilized, other than as cement replacement, in several industrial applications including the manufacturing of lightweight concrete, as a heat-insulating material, in addition to other uses such as fillers, filter materials, absorbents and other architectural applications [17].

opaline silica), clays which have been naturally calcined by heat from flowing lava [10].

Volcanic scoria is loose, rubbly, basaltic to andesitic (40–60% SiO2

the Greek *skōria*, rust. An old name for scoria is cinder [15].

used hydraulic cement, is of a greater concern. On average, about 1 ton of CO2

) liberated during the production of Portland cement, the most commonly

is liberated per

) ejecta that accumulates

bon dioxide (CO2

212

ton of Portland cement produced [1].

Industry and Their Impact on the Human Health

volcano Vesuvius were found [7].

**Figure 1.** (a) Map of African and Arabian plate with a clearer map of Harrat al-Shaam in the upper part of the figure, (b) Photo of Syrian volcanic scoria cones, (c) Macrograph of volcanic scoria aggregates, (d) SEM of volcanic scoria particle with clear vesicles, (e) Thin section in a Syrian volcanic scoria sample.

Although there are numerous studies on using natural pozzolan as cement replacement, few works on studying volcanic scoria were reported in the literature. The present chapter highlights some characteristics of volcanic scoria and their effects on performance-related properties of paste, mortar and concrete. The importance of this chapter is to encourage countries having ample sources of volcanic scoria cones to further investigate the possibility of using it as cement replacement and thus making a greener concrete.

#### **2. Chemical and mineralogical composition of volcanic scoria**

The chemical composition of volcanic scoria varies within wide ranges and depends on its sources. Various scoria cones are abundant in many parts of the world, such as Syria, Turkey,

**Source** New Zealand

46.3–

11.5–

10.8–

8.4–

9.2–

0.8–1.3 2.9–

2.8

0.6

n.a.

n.a.

58.8–

69.6–

59.9

73.0

47.3

Nicaragua Papua New

47.5

14

3.5

6.5

5

5.0

n.a.

n.a.

1.4

0.02

61.5

65.0

n.a.

Guinea

Peru Philippines

Romania

Russia Saudi Arabia

42.0–

13.1–

11.1–

7.8–

2.5–

0.6–1.5 0.2–

2.1–

0.3–

0.9–

0.02–

58.0–

69.4–

Gl, Pl, Ol, CPy, Py, Qz

[61–65]

46.5

Southern

43.9

10.8

12.6

13.1

12.9

1.5

1.4

3.1

0.5

n.a.

n.a.

54.7

67.3

n.a.

[66]

Pacific Ocean

South Africa

Spain

Syria

44.9–

13.0–

8.6–

9.4–

8.9–9.1

0.8–1.8 2.1–

0.9

n.a.

0.4–

0.01–

59.5–

70.5–

Gl, Ol, Pl, Ca, CPy, Fu

[71, 72]

2.6

0.27

61.9

70.9

2.8

46.5

Tanzania

Taiwan Turkey

USA Yemen

48.5 LOI: Loss On Ignition; n.a.: Not available.

16.5

12.2

8.6

5.7

1.0

3.6

1.9

0.4 Gl: Glass; Pl: Plagioclase; Ol: Olivine; Py: Pyroxene; CPy: Clinopyroxene, Mu: Muscovite; Qz: Quartz; Ma: Managocalcite; An: Anatase; Mc: Microcline, SCAS: Sodium

calcium aluminum silicate; Co: Cordierite; Ac: Analcime; Ax: Axinite; Mn: Magnetite; Ca: Calcite; Hm: Hematite; Il: Illite; Mm: Montmorillonite; Ho: Hornblend; Mg:

Maghemite; Fu: Fujasite; Am: Amphibole; OP: Opaque minerals; Mi: Mica; Kn: Kaolinite; Le: Leucite

Chemical composition of some different scoria samples quarried from 36 countries.

 Chemical composition of some different scoria samples quarried from 36 countries.

Maghemite; Fu: Fujasite; Am: Amphibole; OP: Opaque minerals; Mi: Mica; Kn: Kaolinite; Le: Leucite

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 215 Saudi Arabia, Cameroon, Ethiopia, Jordan, Libya, Algeria, Spain and others [18–79]. Harrat Al-Shaam volcanic field, for example (**Figure 1a**), is a basaltic province, extends widely at the Arabian plate (over 50,000 km<sup>2</sup> ), covers the south of Syria, northeast of Jordan, north of Saudi Arabia and contains hundreds of volcanic scoria cones [80, 81]. The chemical analysis of some volcanic scoria reported for 36 countries [18–79] is presented in **Table 1**.

**Table 1** shows that most of the volcanic scoria samples are relatively rich in silica (40–60%) and alumina (10–20%). The next oxides are iron (5–16%), calcium (5–13%) and magnesium (2–13%) oxides. The alkali content is not high but may vary between 1 and 7%. Loss on ignition is generally low but may reach 10% in some pozzolans. Harker variation diagrams (**Figure 2**),

The mineralogical composition of volcanic scoria also varies depending upon their sources. Owing to their formation process, volcanic scoria consists of crystalline and noncrystalline particles as glassy particles. The most detected minerals are plagioclase, olivine, pyroxene

with a glassy/amorphous structure for reactivity with lime or cement [82]. Reactive silica con-

CH (Portlanite) + S (reactive silica) + H (Water) → C − S − H (Calcium silicate hydrates) (1)

The composition of C-S-H is not very different from that formed in regular hydration, although generally the C/S molar ratio is slightly lower [83]. Analogously to reactive silica, reactive alumina present in volcanic scoria can react with CH to form calcium aluminate hydrates (C-A-H) [83]. This reaction which is frequently called the pozzolanic reaction is slow, portlandite consuming and very efficient in filling up capillary spaces [4]. It depends on several factors, such as the glassy

ASTM designation C618 (2012) [84] requires that for a material to be accepted as a natural

strength activity index should exceed 75% of the control mortar's compressive strength at either 7 or 28 days. The strength activity index (SAI) gives an indication of the reactivity of volcanic scoria by comparing the compressive strength of mortar cubes made with 80 wt.% cement and 20 wt.% volcanic scoria to the compressive strength of the control mortar cubes made with only cement. In addition, EN 197–1(2000) [85] requires a reactive silica content of

An increase in fineness that exposes more surface area of the volcanic scoria may accelerate the early pozzolanic reactivity [86, 87]. The specific surface area of volcanic scoria, which is the area

O3

This reaction forms additional calcium silicate hydrates (C-S-H). The principal reaction is.

) from the knowledge of SiO<sup>2</sup>

and alkalis with increasing SiO<sup>2</sup>

display inverse relationships with SiO2

(sum of SiO2

, Al2 O3

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970

content (**Figure 2**).

) and alumina (Al2

should have a minimum value of 70% and the

S and C2

. However, the

and Fe2

O3

) content

S in cement.

. The

217

O3 )

O3

, MgO, CaO and TiO2

O3

author attempted to derive an equation in order to estimate R<sup>1</sup>

Volcanic scoria as a pozzolanic material has high silica (SiO2

phase content in volcanic scoria and the fineness of volcanic scoria.

and Fe2

more than 25% for volcanic scoria to be accepted as natural pozzolan.

, Al2 O3

tent can react with portlandite (CH) liberated from the hydration of C3

and Fe2

using SiO2, show a general increase of Al2

O3

, Al2 O3

**3. Reactivity of volcanic scoria**

**3.1. Glassy phase in volcanic scoria**

pozzolan, the sum of SiO2

**3.2. Fineness of volcanic scoria**

elements such as Fe2

and clinopyroxene.

(sum of SiO2

and R2

**Figure 2.** Different oxides versus silica content in the volcanic scoria (R<sup>1</sup> : sum of SiO2 and Al2 O3 ; R2 : sum of SiO2 , Al2 O3 and Fe2 O3 ) [18–79].

**Table 1** shows that most of the volcanic scoria samples are relatively rich in silica (40–60%) and alumina (10–20%). The next oxides are iron (5–16%), calcium (5–13%) and magnesium (2–13%) oxides. The alkali content is not high but may vary between 1 and 7%. Loss on ignition is generally low but may reach 10% in some pozzolans. Harker variation diagrams (**Figure 2**), using SiO2, show a general increase of Al2 O3 and alkalis with increasing SiO<sup>2</sup> . However, the elements such as Fe2 O3 , MgO, CaO and TiO2 display inverse relationships with SiO2 . The author attempted to derive an equation in order to estimate R<sup>1</sup> (sum of SiO2 , Al2 O3 and Fe2 O3 ) and R2 (sum of SiO2 , Al2 O3 and Fe2 O3 ) from the knowledge of SiO<sup>2</sup> content (**Figure 2**).

The mineralogical composition of volcanic scoria also varies depending upon their sources. Owing to their formation process, volcanic scoria consists of crystalline and noncrystalline particles as glassy particles. The most detected minerals are plagioclase, olivine, pyroxene and clinopyroxene.

### **3. Reactivity of volcanic scoria**

Saudi Arabia, Cameroon, Ethiopia, Jordan, Libya, Algeria, Spain and others [18–79]. Harrat Al-Shaam volcanic field, for example (**Figure 1a**), is a basaltic province, extends widely at the

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

Arabia and contains hundreds of volcanic scoria cones [80, 81]. The chemical analysis of some

volcanic scoria reported for 36 countries [18–79] is presented in **Table 1**.

**Figure 2.** Different oxides versus silica content in the volcanic scoria (R<sup>1</sup>

and Fe2 O3 ) [18–79]. ), covers the south of Syria, northeast of Jordan, north of Saudi

: sum of SiO2

 and Al2 O3 ; R2

: sum of SiO2

, Al2 O3

Arabian plate (over 50,000 km<sup>2</sup>

216

Industry and Their Impact on the Human Health

Volcanic scoria as a pozzolanic material has high silica (SiO2 ) and alumina (Al2 O3 ) content with a glassy/amorphous structure for reactivity with lime or cement [82]. Reactive silica content can react with portlandite (CH) liberated from the hydration of C3 S and C2 S in cement. This reaction forms additional calcium silicate hydrates (C-S-H). The principal reaction is.

CH (Portlanite) + S (reactive silica) + H (Water) → C − S − H (Calcium silicate hydrates) (1)

The composition of C-S-H is not very different from that formed in regular hydration, although generally the C/S molar ratio is slightly lower [83]. Analogously to reactive silica, reactive alumina present in volcanic scoria can react with CH to form calcium aluminate hydrates (C-A-H) [83]. This reaction which is frequently called the pozzolanic reaction is slow, portlandite consuming and very efficient in filling up capillary spaces [4]. It depends on several factors, such as the glassy phase content in volcanic scoria and the fineness of volcanic scoria.

#### **3.1. Glassy phase in volcanic scoria**

ASTM designation C618 (2012) [84] requires that for a material to be accepted as a natural pozzolan, the sum of SiO2 , Al2 O3 and Fe2 O3 should have a minimum value of 70% and the strength activity index should exceed 75% of the control mortar's compressive strength at either 7 or 28 days. The strength activity index (SAI) gives an indication of the reactivity of volcanic scoria by comparing the compressive strength of mortar cubes made with 80 wt.% cement and 20 wt.% volcanic scoria to the compressive strength of the control mortar cubes made with only cement. In addition, EN 197–1(2000) [85] requires a reactive silica content of more than 25% for volcanic scoria to be accepted as natural pozzolan.

#### **3.2. Fineness of volcanic scoria**

An increase in fineness that exposes more surface area of the volcanic scoria may accelerate the early pozzolanic reactivity [86, 87]. The specific surface area of volcanic scoria, which is the area

**4.2. Heat of hydration**

**4.3. Microstructure**

**Figure 4.** Relationship between initial and final setting times.

**Figure 5.** Influence of different SCMs on the heat of hydration of the mixtures [94].

The hydration of cement paste is accompanied by the liberation of heat that raises the temperature of the concrete mix. Because of the slower pozzolanic reaction, the partial replacement of cement by volcanic action results in a release of heat over a longer period of time enabling the heat to dissipate and the overall concrete temperature to remain lower. This is of great importance in mass concrete where cooling, following a large temperature rise, can lead to cracking. As shown in **Figure 5**, a volcanic scoria from Syria reduced the heat of hydration [94]. Similar results were also reported by Alhozaimy et al. [95] who concluded that the heat of hydration of VS-based cement pastes liberated in the first 72 h was, on average, 85% of the control mix.

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 219

The presence of volcanic scoria leads to the disappearance of portlandite crystals and the appearance of the condensed type of C-S-H crystals, as shown in **Figure 6**. This type of condensed C-S-H results from the interaction of pozzolanic material with portlandite. Condensed

**Figure 3.** Effect of fineness on compressive strength of VS-based cement mortars cured for 2 (a) and 7 (b) days [89].

of a unit mass, is measurable by different techniques. The most common is the Blaine-specific surface area technique, which measures the resistance of compacted particles to an air flow. A laser particle size analyzer can also be used for the determination of the specific surface area of volcanic scoria [88, 89]. Al-Swaidani et al. [89] reported an increase of about 145% in the early compressive strength when the Blaine fineness of 2-day-cured volcanic scoria (VS)-based cement increased from 240 to 510 m2 /kg at replacement levels ranging from 25 to 35% by mass, as shown in **Figure 3**. The authors also concluded that an increase of about 5 MPa can be expected for every 1000 cm2 /g increase in Blaine fineness for VS-based binder mortars at all curing times [89]. Similar results were obtained by other researchers [90, 91]. This reactivity enhancement was explained by the effect of grinding which breaks the vitreous body, decreases the particle size and increases dissolution rate and solubility of volcanic scoria, which will accelerate pozzolanic reaction rate and the strength development of mortar containing volcanic scoria [89, 90, 92].

#### **4. Properties of VS-based cement paste**

#### **4.1. Setting times**

Most of the studied scoria samples showed an increase, ranging from slight to significant, in setting times of the VS-based cement paste with the increase in volcanic scoria content. This can be explained by the reduction of hydration heat on the binder system with the presence of VS [91]. A significant relationship (R<sup>2</sup> ≈ 0.9) between initial and final setting times was obtained by the author depending on data collected from other papers [20, 62, 71, 72, 75, 79, 89, 91], as clearly shown in **Figure 4**. So, knowing initial setting time, the final setting time of the VS-based cement paste can be predicted by using the equation shown in **Figure 4**. It is worth to note that among all the investigated volcanic scoria compiled with the standard requirements in terms of the initial setting time, most of them met the requirements in terms of final setting times (i.e., initial setting time ≥ 45 min and final setting time ≤ 420 min), according to ASTM C595 [93].

#### **4.2. Heat of hydration**

The hydration of cement paste is accompanied by the liberation of heat that raises the temperature of the concrete mix. Because of the slower pozzolanic reaction, the partial replacement of cement by volcanic action results in a release of heat over a longer period of time enabling the heat to dissipate and the overall concrete temperature to remain lower. This is of great importance in mass concrete where cooling, following a large temperature rise, can lead to cracking. As shown in **Figure 5**, a volcanic scoria from Syria reduced the heat of hydration [94]. Similar results were also reported by Alhozaimy et al. [95] who concluded that the heat of hydration of VS-based cement pastes liberated in the first 72 h was, on average, 85% of the control mix.

#### **4.3. Microstructure**

**Figure 3.** Effect of fineness on compressive strength of VS-based cement mortars cured for 2 (a) and 7 (b) days [89].

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

increased from 240 to 510 m2

Industry and Their Impact on the Human Health

218

**4. Properties of VS-based cement paste**

every 1000 cm2

**4.1. Setting times**

of a unit mass, is measurable by different techniques. The most common is the Blaine-specific surface area technique, which measures the resistance of compacted particles to an air flow. A laser particle size analyzer can also be used for the determination of the specific surface area of volcanic scoria [88, 89]. Al-Swaidani et al. [89] reported an increase of about 145% in the early compressive strength when the Blaine fineness of 2-day-cured volcanic scoria (VS)-based cement

in **Figure 3**. The authors also concluded that an increase of about 5 MPa can be expected for

Similar results were obtained by other researchers [90, 91]. This reactivity enhancement was explained by the effect of grinding which breaks the vitreous body, decreases the particle size and increases dissolution rate and solubility of volcanic scoria, which will accelerate pozzolanic reaction rate and the strength development of mortar containing volcanic scoria [89, 90, 92].

Most of the studied scoria samples showed an increase, ranging from slight to significant, in setting times of the VS-based cement paste with the increase in volcanic scoria content. This can be explained by the reduction of hydration heat on the binder system with the presence of VS [91]. A significant relationship (R<sup>2</sup> ≈ 0.9) between initial and final setting times was obtained by the author depending on data collected from other papers [20, 62, 71, 72, 75, 79, 89, 91], as clearly shown in **Figure 4**. So, knowing initial setting time, the final setting time of the VS-based cement paste can be predicted by using the equation shown in **Figure 4**. It is worth to note that among all the investigated volcanic scoria compiled with the standard requirements in terms of the initial setting time, most of them met the requirements in terms of final setting times (i.e., initial setting time ≥ 45 min and final setting time ≤ 420 min), according to ASTM C595 [93].

/kg at replacement levels ranging from 25 to 35% by mass, as shown

/g increase in Blaine fineness for VS-based binder mortars at all curing times [89].

The presence of volcanic scoria leads to the disappearance of portlandite crystals and the appearance of the condensed type of C-S-H crystals, as shown in **Figure 6**. This type of condensed C-S-H results from the interaction of pozzolanic material with portlandite. Condensed

**Figure 4.** Relationship between initial and final setting times.

**Figure 5.** Influence of different SCMs on the heat of hydration of the mixtures [94].

**Figure 6.** SEM of (a) control cement paste; (b) 20% VS-based cement paste [63].

C-S-H fills the micropores, reduces the porosity and consequently improves the impermeability and the compressive strength. The enhancement in the microstructure in the mixtures with volcanic scoria can be attributed to the formation of additional C-S-H, which generally fills in the pores, creates denser hydration products and accordingly reduces the permeability [63]. Similar observations were also reported in the literature [71, 72].

#### **5. Properties of VS-based cement mortar/concrete**

#### **5.1. Compressive and flexural strength**

All the results reported in the literature [18–20, 30, 56, 62, 63, 71, 72, 75, 79, 89, 91, 96, 97] show that the compressive strength of VS-based cement mortars/concretes increases with the curing age and decreases with the replacement level of volcanic scoria content (**Figure 7**). This reduction in the compressive strength is attributed mainly to slower pozzolanic activity at room temperature of volcanic scoria as natural pozzolan [71, 83]. This ascertainment is explained by the interaction between the reactive silica which is in the glassy portion of the addition and the Ca(OH)2 released by the hydration of the cement. It has also been noted that the mortars containing volcanic scorias exhibit compressive strength comparable to those of the control mortar starting from the period of 90 days.

The author attempted to derive an equation in order to reasonably estimate the relative compressive strength of VS-based mortars. This prediction equation could be written as follows:

$$\text{RCS} = \text{(0.176Int - 1.343) VS} + 1.01 \text{ (R2 = 0.81)} \tag{2}$$

curing age and the volcanic scoria content and the compressive strength of the control sample (i.e., without volcanic scoria), the compressive strength of VS-based cement and mortar could

**Figure 8.** Experimental results versus calculated values for relative compressive strength of volcanic scoria cement-based

It is worth to mention that, in contrast to previous literature, studying the effect of total alkali

A similar behavior was observed by many researchers in terms of flexural tensile strength of VS-based cement mortars. An attempt to predict the flexural strength based on the compressive strength, with a reasonable coefficient of determination (R<sup>2</sup> = 0.83), is clearly shown in **Figure 10**.

Drying shrinkage represents the strain caused by the loss of water from the hardened material. The shrinkage is believed to originate in the C-S-H and its associated porosity [83].

O on the compressive strength of VS-based cement mortars

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 221

be reasonably estimated.

**5.2. Drying shrinkage**

O and K2

did not give definite correlations (**Figure 9**).

O) and K2

**Figure 7.** Compressive strength of VS-based cement concrete at different curing times [98].

content (Na2

mortars.

where RCS is the relative compressive strength, t is the curing age (day) and VS is the volcanic scoria content (%). This prediction equation having a relatively high coefficient of determination (R2 = 0.81) was obtained through the regression analysis of literature data (**Figure 8**). The variants in the equation are the curing age and the volcanic scoria content. So, knowing the

**Figure 7.** Compressive strength of VS-based cement concrete at different curing times [98].

**Figure 8.** Experimental results versus calculated values for relative compressive strength of volcanic scoria cement-based mortars.

curing age and the volcanic scoria content and the compressive strength of the control sample (i.e., without volcanic scoria), the compressive strength of VS-based cement and mortar could be reasonably estimated.

It is worth to mention that, in contrast to previous literature, studying the effect of total alkali content (Na2 O and K2 O) and K2 O on the compressive strength of VS-based cement mortars did not give definite correlations (**Figure 9**).

A similar behavior was observed by many researchers in terms of flexural tensile strength of VS-based cement mortars. An attempt to predict the flexural strength based on the compressive strength, with a reasonable coefficient of determination (R<sup>2</sup> = 0.83), is clearly shown in **Figure 10**.

#### **5.2. Drying shrinkage**

C-S-H fills the micropores, reduces the porosity and consequently improves the impermeability and the compressive strength. The enhancement in the microstructure in the mixtures with volcanic scoria can be attributed to the formation of additional C-S-H, which generally fills in the pores, creates denser hydration products and accordingly reduces the permeability [63].

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

All the results reported in the literature [18–20, 30, 56, 62, 63, 71, 72, 75, 79, 89, 91, 96, 97] show that the compressive strength of VS-based cement mortars/concretes increases with the curing age and decreases with the replacement level of volcanic scoria content (**Figure 7**). This reduction in the compressive strength is attributed mainly to slower pozzolanic activity at room temperature of volcanic scoria as natural pozzolan [71, 83]. This ascertainment is explained by the interaction between the reactive silica which is in the glassy portion of the addition and

containing volcanic scorias exhibit compressive strength comparable to those of the control

The author attempted to derive an equation in order to reasonably estimate the relative compressive strength of VS-based mortars. This prediction equation could be written as follows:

where RCS is the relative compressive strength, t is the curing age (day) and VS is the volcanic scoria content (%). This prediction equation having a relatively high coefficient of determination (R2 = 0.81) was obtained through the regression analysis of literature data (**Figure 8**). The variants in the equation are the curing age and the volcanic scoria content. So, knowing the

released by the hydration of the cement. It has also been noted that the mortars

=0.81) (2)

Similar observations were also reported in the literature [71, 72].

**Figure 6.** SEM of (a) control cement paste; (b) 20% VS-based cement paste [63].

**5. Properties of VS-based cement mortar/concrete**

RCS = (0.176lnt – 1.343) VS + 1.01 (R2

**5.1. Compressive and flexural strength**

Industry and Their Impact on the Human Health

220

mortar starting from the period of 90 days.

the Ca(OH)2

Drying shrinkage represents the strain caused by the loss of water from the hardened material. The shrinkage is believed to originate in the C-S-H and its associated porosity [83].

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to Industry and Their Impact on the Human Health 222

The increase of drying shrinkage with the cement replacement level [99] might be due to: (1) the pozzolanic reaction, generating an additional CSH, resulting in the decrease in spacing of CSH particles; (2) the transportation of large pores into fine pores (pore size refinement) increasing capillary tension [99–103]; (3) the higher water demand of scoria-based cements [99, 102]; (4) the porous microstructure of scoria [104] (**Figure 1d**). However, this increase was

The sulfate attack on the cement mortar is a complex process involving the hydration products produced by Portland cement. The damage caused by sulfate attack may involve cracking and expansion of mortar as a whole, as well as softening and disintegration of cement

This type of corrosion is initiated by the reaction between sulfate ions and calcium hydroxide

This reaction can be described as gypsum corrosion. Both reactions are accompanied by an expansion in solid volume causing internal stresses and ultimately lead to cracking [83].

A content will be subject to sulfoaluminate corrosion in

(aq) (Sulfate ion) → CŠH2 (Gypsum) + 2OH<sup>−</sup> (aq) (4)

AŠ3

H32 (Ettringite) (3)

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 223

lower than the maximum 0.03% allowed by ASTM C618 (**Figure 11**) [99].

**5.3. Sulfate attack**

C4

(CH):

paste [83]. Cements with a high C3

CH (Calcium hydroxide) + SO4

which ettringite is formed, as displayed in Eq. (3) [83, 105].

**Figure 11.** Drying shrinkage values of prismatic mortar specimens [99].

**Figure 11** shows the results of drying shrinkage of VS-based cement mortars.

AŠH12 (Monosulfate) + 2CŠH2 (Gypsum) + 16H (Water) → C6

2−

**Figure 9.** Effect of total alkali content (a and b) and K<sup>2</sup> O content (c and d) on compressive strength of VS-based cement mortars at 7 and 28 days curing.

**Figure 10.** Relationship between compressive and flexural strengths of VS-based cement mortars.

The increase of drying shrinkage with the cement replacement level [99] might be due to: (1) the pozzolanic reaction, generating an additional CSH, resulting in the decrease in spacing of CSH particles; (2) the transportation of large pores into fine pores (pore size refinement) increasing capillary tension [99–103]; (3) the higher water demand of scoria-based cements [99, 102]; (4) the porous microstructure of scoria [104] (**Figure 1d**). However, this increase was lower than the maximum 0.03% allowed by ASTM C618 (**Figure 11**) [99].

**Figure 11** shows the results of drying shrinkage of VS-based cement mortars.

#### **5.3. Sulfate attack**

**Figure 9.** Effect of total alkali content (a and b) and K<sup>2</sup>

Industry and Their Impact on the Human Health

222

**Figure 10.** Relationship between compressive and flexural strengths of VS-based cement mortars.

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

mortars at 7 and 28 days curing.

O content (c and d) on compressive strength of VS-based cement

The sulfate attack on the cement mortar is a complex process involving the hydration products produced by Portland cement. The damage caused by sulfate attack may involve cracking and expansion of mortar as a whole, as well as softening and disintegration of cement paste [83]. Cements with a high C3 A content will be subject to sulfoaluminate corrosion in which ettringite is formed, as displayed in Eq. (3) [83, 105].

$$\text{C}\_4\text{A}\_5^\text{K}\text{H}\_{\text{zz}}\text{(Monosulíate)} + 2\text{C}\_2^\text{K}\text{H}\_{\text{z}}\text{(Gypsum)} + 16\text{H (Water)} \rightarrow \text{C}\_6\text{A}\_3^\text{K}\text{H}\_{\text{zz}}\text{(Etringite)}\tag{3}$$

This type of corrosion is initiated by the reaction between sulfate ions and calcium hydroxide (CH):

$$\text{CH (Calcium hydroxide)} + \text{SO}\_4^{2-} \text{(aq) (Surface ion)} \rightarrow \text{C}\overset{\text{\textbullet}}{\text{SH}\_2} \text{(Gypsum)} + 2\text{OH}^- \text{(aq)} \quad \text{(4)}$$

This reaction can be described as gypsum corrosion. Both reactions are accompanied by an expansion in solid volume causing internal stresses and ultimately lead to cracking [83].

**Figure 11.** Drying shrinkage values of prismatic mortar specimens [99].

The beneficial effects of using volcanic scoria on the sulfate resistance of mortar as reported by many authors [5], **Figure 12**, may be ascribed to a number of mechanisms [5, 106–108], including:

#### **5.4. Acidic attack**

Sulfuric acid, among other aggressive acids such as HCl, HNO3 and CH3 COOH, is very damaging to mortar as it combines an acid attack and a sulfate attack [109]. At the first stage, deterioration of Ca(OH)2 results in an expansive gypsum formation. The gypsum then reacts with C3 A in the aqueous environment and forms a more expansive product called ettringite. These very expansive compounds cause internal pressure in the mortar, which leads to the formation of cracks [110] and the transformation of the mortar into a mushy or a noncohesive mass [111]. Sulfuric acid may also cause the decalcification of calcium silicate hydrates C-S-H and will ultimately transform the C-S-H into amorphous hydrous silica. The following equations express these reactions [110]:

$$\text{Ca(OH)}\_{2} + \text{H}\_{2}\text{SO}\_{4} \rightarrow \text{CaSO}\_{4}\text{2H}\_{2}\text{O(Gypsum)}\tag{5}$$

$$\begin{array}{l} \text{3(CaSO}\_4\text{2H}\_2\text{O)} + \text{3CaOAl}\_2\text{O}\_3.12\text{H}\_2\text{O} + 14\text{ H}\_2\text{O} \\ \rightarrow \text{ 3CaOAl}\_2\text{O}\_3\text{CaSO}\_4\text{32 H}\_2\text{O}\_3 \text{(Etringite)} \end{array} \tag{6}$$

the number of days needed to register a 10% loss in weight was considered in their evaluation. As shown in **Table 2**, the 10% weight loss was obtained with 35% VS-based cement mortars up to 6.2 and 6.70 days of exposure to sulfuric acid and 4.6 and 5.2 days of exposure to hydrochloric acid at 28 and 90 days curing, respectively. In addition, none of the mixtures containing 25% volcanic scoria and more lost 10% weight even after 100 days of exposure to

SO4 [5].

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 225

SO4 [99].

**Figure 12.** Length changes over time of prismatic mortars immersed in 5% Na2

**Figure 13.** Weight losses over time of 90 days-cured mortars exposed to 5% H2

nitric and acetic acids.

$$\text{CaOSiO}\_2\text{2H}\_2\text{O} + \text{H}\_2\text{SO}\_4 \rightarrow \text{CaSO}\_4 + \text{Si(OH)}\_4\text{(Hydroons silicon)} + \text{H}\_2\text{O} \tag{7}$$

The white gypsum, which covers the surface of mortar, can potentially lead to the blocking of pores on the surface, leading to a slower rate of attack initially. However, this effect lasts only temporarily [112].

The better performance of VS-based cement mortars in terms of the acid attack, as shown in **Figure 13** [99], can be due to the pozzolanic reaction [5, 113, 114]. This reaction between scoria and calcium hydroxide liberated during the hydration of cement [5, 114] leads to a refinement of the pore structure resulting in a highly impermeable matrix [5, 113]. The pozzolanic reaction also fixes Ca(OH)<sup>2</sup> , which is usually the most vulnerable product of the hydration of cement insofar as the acid attack is concerned [115]. In the study by al-Swaidani and Aliyan [5],

**Figure 12.** Length changes over time of prismatic mortars immersed in 5% Na2 SO4 [5].

The beneficial effects of using volcanic scoria on the sulfate resistance of mortar as reported by many authors [5], **Figure 12**, may be ascribed to a number of mechanisms [5, 106–108],

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

• alteration of hydrated aluminate phases, making them more resistant, for example, the

aging to mortar as it combines an acid attack and a sulfate attack [109]. At the first stage,

These very expansive compounds cause internal pressure in the mortar, which leads to the formation of cracks [110] and the transformation of the mortar into a mushy or a noncohesive mass [111]. Sulfuric acid may also cause the decalcification of calcium silicate hydrates C-S-H and will ultimately transform the C-S-H into amorphous hydrous silica. The following equa-

SO4 → CaSO4

.3CaSO4

SO4 → CaSO4 + Si (OH)

The white gypsum, which covers the surface of mortar, can potentially lead to the blocking of pores on the surface, leading to a slower rate of attack initially. However, this effect lasts only

The better performance of VS-based cement mortars in terms of the acid attack, as shown in **Figure 13** [99], can be due to the pozzolanic reaction [5, 113, 114]. This reaction between scoria and calcium hydroxide liberated during the hydration of cement [5, 114] leads to a refinement of the pore structure resulting in a highly impermeable matrix [5, 113]. The pozzolanic

cement insofar as the acid attack is concerned [115]. In the study by al-Swaidani and Aliyan [5],

O) + 3CaO.Al2

O3

A in the aqueous environment and forms a more expansive product called ettringite.

.2H2

O + 14 H2

, which is usually the most vulnerable product of the hydration of

O

<sup>4</sup> (Hydrous silica) + H2

O3 .12 H2

.32 H2

presence of reactive silica may favor the formation of strätlingite (C-A-S-H).

A phases and CH (both participants in reactions with sulfates) as a result

results in an expansive gypsum formation. The gypsum then reacts

and CH3

O (Gypsum) (5)

O3 (Ettringite) (6)

COOH, is very dam-

O (7)

including:

224

• reduced permeability,

Industry and Their Impact on the Human Health

of the partial replacement of Portland cement, • consumption of CH by pozzolanic reaction and

Sulfuric acid, among other aggressive acids such as HCl, HNO3

<sup>2</sup> + H2

.2H2

→ 3CaO.Al2

O + H2

3(CaSO4

.2H2

• dilution of the C3

**5.4. Acidic attack**

with C3

deterioration of Ca(OH)2

tions express these reactions [110]:

Ca (OH)

CaO.SiO2

temporarily [112].

reaction also fixes Ca(OH)<sup>2</sup>

**Figure 13.** Weight losses over time of 90 days-cured mortars exposed to 5% H2 SO4 [99].

the number of days needed to register a 10% loss in weight was considered in their evaluation. As shown in **Table 2**, the 10% weight loss was obtained with 35% VS-based cement mortars up to 6.2 and 6.70 days of exposure to sulfuric acid and 4.6 and 5.2 days of exposure to hydrochloric acid at 28 and 90 days curing, respectively. In addition, none of the mixtures containing 25% volcanic scoria and more lost 10% weight even after 100 days of exposure to nitric and acetic acids.

secondary-contributing pozzolanic reaction that makes the microstructure of concrete denser [71]. **Figure 15** clearly shows such improvement with the increase of volcanic scoria content

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 227

Analyzing the results of chloride penetrability gathered from different works [19, 62, 63, 98, 116, 117], an estimation equation with strong correlation (R2 ≈ 0.86) can be derived (**Figure 16**).

RCP = (−0.3lnt – 0.68) × VS + 1.06 (8)

**Figure 14.** Water penetration depths of VS-based cement concretes prepared with different w/c ratios and cured for

**Figure 15.** Chloride ion penetrability of VS-based cement concretes as reported by al-Swaidani [98].

and curing age.

different ages [98].

The estimation equation is.

**Table 2.** Number of days needed to register a 10% weight loss of mortar cubes [5].

#### **5.5. Permeability**

Permeability of concrete to water is closely related to the durability of concrete. Permeability is the rate at which aggressive agents penetrate through concrete [115].

#### *5.5.1. Water permeability*

Water penetration depth can be considered as an indication of permeable and impermeable concrete [115]. A depth of less than 50 mm classifies the concrete as impermeable and a depth of less than 30 mm as impermeable under aggressive conditions [115]. The water penetration depth test results for concretes containing VS-based cement concretes show their lower permeability when compared with plain Portland cement, particularly at late ages (**Figure 14**) [98].

#### *5.5.2. Chloride penetrability*

Although chloride ions in concrete do not directly cause severe damage to the concrete, they contribute to the corrosion of steel bars embedded in concrete that is considered as the factor causing most premature deterioration of reinforced concrete (RC) structures worldwide, especially in the marine environments. Therefore, the study of chloride penetrability is important for evaluating reinforcing steel corrosion in RC structures. This has prompted the search for economic methods of extending the service life of structures. One of these methods was the use of pozzolan such as volcanic scoria [5].

The improvement in resistance of volcanic scoria-based cement concretes to chloride penetration which was frequently noted in the literature may be related to their refined pore structure and their reduced electrical conductivity [71]. This refinement in pore structure is due to the secondary-contributing pozzolanic reaction that makes the microstructure of concrete denser [71]. **Figure 15** clearly shows such improvement with the increase of volcanic scoria content and curing age.

Analyzing the results of chloride penetrability gathered from different works [19, 62, 63, 98, 116, 117], an estimation equation with strong correlation (R2 ≈ 0.86) can be derived (**Figure 16**). The estimation equation is.

$$\text{RCP} = (-0.3 \text{Int} - 0.68) \times \text{VS} + 1.06 \tag{8}$$

**5.5. Permeability**

(**Figure 14**) [98].

*5.5.2. Chloride penetrability*

the use of pozzolan such as volcanic scoria [5].

**Cement type Number of days to register 10% weight loss**

**90 days curing**

**28 days curing**

**5% H2**

226

**28 days curing**

Industry and Their Impact on the Human Health

*5.5.1. Water permeability*

NR 10% weight loss was not reached.

Permeability of concrete to water is closely related to the durability of concrete. Permeability

**SO4 10% HCl 5% HNO3 10% CH3**

**28 days curing**

**90 days curing**

**90 days curing**

C1/CEMI 3.5 3.5 3.7 3.2 22.5 25.9 NR NR C2/10% 3.7 3.7 3.7 3.1 25.4 22.8 NR NR C3/15% 3.8 3.8 3.8 3.6 55.5 48.9 NR NR C4/20% 4.0 4.1 3.9 3.7 79.1 97.3 NR NR C5/25% 4.7 5.1 4.1 4.3 NR NR NR NR C6/30% 5.2 5.8 4.4 4.9 NR NR NR NR C7/35% 6.2 6.7 4.6 5.2 NR NR NR NR C8/SRPC 3.0 3.0 3.2 2.9 20.1 18.8 NR NR

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

**COOH**

**90 days curing**

**28 days curing**

Water penetration depth can be considered as an indication of permeable and impermeable concrete [115]. A depth of less than 50 mm classifies the concrete as impermeable and a depth of less than 30 mm as impermeable under aggressive conditions [115]. The water penetration depth test results for concretes containing VS-based cement concretes show their lower permeability when compared with plain Portland cement, particularly at late ages

Although chloride ions in concrete do not directly cause severe damage to the concrete, they contribute to the corrosion of steel bars embedded in concrete that is considered as the factor causing most premature deterioration of reinforced concrete (RC) structures worldwide, especially in the marine environments. Therefore, the study of chloride penetrability is important for evaluating reinforcing steel corrosion in RC structures. This has prompted the search for economic methods of extending the service life of structures. One of these methods was

The improvement in resistance of volcanic scoria-based cement concretes to chloride penetration which was frequently noted in the literature may be related to their refined pore structure and their reduced electrical conductivity [71]. This refinement in pore structure is due to the

is the rate at which aggressive agents penetrate through concrete [115].

**Table 2.** Number of days needed to register a 10% weight loss of mortar cubes [5].

**Figure 14.** Water penetration depths of VS-based cement concretes prepared with different w/c ratios and cured for different ages [98].

**Figure 15.** Chloride ion penetrability of VS-based cement concretes as reported by al-Swaidani [98].

**Author details**

Aref M. al-Swaidani

(AIU), Damascus, Syria

**References**

2008

Materials; 2007

research institute; 1983

1983:723-1446

UK: Oxford University Press; 2008

Address all correspondence to<EMAIL_ADDRESS><EMAIL_ADDRESS>
Performance. 2nd ed. London, UK: Taylor & Francis; 2009

2015;**9**:241. DOI: https://doi.org/10.1007/s40069-015-0101-z

New York, USA: McGraw-Hill; 2006

Faculty of Architectural Engineering, Arab International (Formerly European) University

Volcanic Scoria as Cement Replacement http://dx.doi.org/10.5772/intechopen.77970 229

[1] Aitcin PC, Mindess S. Sustainability of Concrete. 1st ed. London, UK: Spon Press; 2011 [2] Aïtcin PC. Binders for Durable and Sustainable Concrete. London, UK: Taylor & Francis;

[3] Brandt AM. Cement-Based Composites: Materials, Mechanical Properties and

[4] Mehta PK, Monteiro PJM. Concrete: Microstructure, Properties and Materials. 3rd ed:

[5] al-Swaidani AM, Aliyan SD. International Journal of Concrete Structures and Materials.

[6] ASTM C125. Standard Terminology Relating to Concrete and Concrete Aggregates. West Conshohocken, Pennsylvania, United States: American Society for Testing and

[7] Jahren P, Sui T. Concrete and Sustainability. Boca Raton, Florida, USA: CRC Press; 2014 [8] Dedeloudis C, Zervaki M, Sideris K, Juenger M, Alderete N, Kamali-Bernard S, Villagrán Y, Snellings R. Natural pozzolans. De Belie N et al, editors. In: Properties of Fresh and Hardened Concrete Containing Supplementary Cementitious Materials. 2018. RILEM

[9] Jackson M, Deocampo D, Marra F, Scheetz B. Mid-Pleistocene pozzolanic volcanic ash in

[10] Hammond AA. Pozzolana Cements for Low Cost Housing. Japan: Building and road

[11] Dictionary of Earth Sciences. A Dictionary Edited by Michael Allaby. 3rd ed. Oxford,

[12] Lefond SJ. Industrial Minerals and Rocks. Society of Mining Engineers. New York: American Institute of Mining, Metallurgical and Petroleum Engineers, Inc. Vol. 2;

[13] Sen G. Petrology: Principles and Practice. Berlin Heidelberg: Springer-Verlag; 2014

State-of-the-Art Reports 25. https://doi.org/10.1007/978-3-319-70606-1\_6

ancient roman concretes. Geoarchaeology. 2010;**25**(1):36-74

**Figure 16.** Experimental results versus calculated values of chloride penetrability.

where, RCP is relative chloride penetrability, t is curing age and VS is volcanic scoria content (% by mass). So, the chloride penetrability of VS-based cement concrete can be predicted from knowledge of curing time and volcanic scoria content.

#### **6. Conclusion**

#### **Author details**

#### Aref M. al-Swaidani

Address all correspondence to<EMAIL_ADDRESS><EMAIL_ADDRESS>
Faculty of Architectural Engineering, Arab International (Formerly European) University (AIU), Damascus, Syria

#### **References**

where, RCP is relative chloride penetrability, t is curing age and VS is volcanic scoria content (% by mass). So, the chloride penetrability of VS-based cement concrete can be predicted from

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

• Volcanic scoria has been used in construction since ancient times in pozzolan-lime concrete

• Incorporation of volcanic scoria in concrete has significant effects on the properties of con-

• The chloride permeability of VS-based cement concrete demonstrated better performance

• The wide availability of volcanic scoria in many countries, its low cost and the drive toward more sustainable construction have resulted in renewed interest in volcanic scoria as natural pozzolan for concrete. Historically, various types of volcanic scoria were successfully used in dams and aqueducts, where the strength demand is not high but the durability and

• Estimation equations for predicting the investigated concrete properties (i.e., compressive strength, water penetration depth and chloride penetration) incorporating the effect of curing time and the replacement level of volcanic scoria were derived. These equations permit the concrete properties of VS-based cement concretes to be predicted with a relatively high

• Investigating the volcanic scoria cones that have not been yet invested is highly recommended. In addition, making more sustainable and durable concrete using volcanic scoria

as compared to plain concrete, especially at the curing age of 28 days and longer.

O3

and Fe2

O3

are within

content for all sources are within the range of 40–60%; Al2

knowledge of curing time and volcanic scoria content.

Industry and Their Impact on the Human Health

228

providing durable structures that survived over 2000 years.

**Figure 16.** Experimental results versus calculated values of chloride penetrability.

the ranges from 10 to 20% and from 5 to 16%, respectively.

crete, particularly durability-related properties.

thermal cracking control are of major concerns.

degree of accuracy (R2 ≥ 0.8).

is highly encouraged.

**6. Conclusion**

• The SiO2

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**Chapter 11**

per-

**Provisional chapter**

**Volcanic Glass and its Uses as Adsorbent**

**Volcanic Glass and its Uses as Adsorbent**

DOI: 10.5772/intechopen.75063

Volcanic glasses are an amorphous phyllosilicates formed by the fast cooling of the magma. The physicochemical properties of volcanic glasses are directly related to their chemical composition. Thus, the rhyolitic magma, which presents the highest SiO2

centage, displays a high viscosity, which leads to explosive eruptions by the ex-solution

with interesting applications in construction, as abrasive, acoustic, filter as well as in the agriculture field. The macroporosity of volcanic glass allows to host large molecules as biomolecules, tensoactives, or dyes. On the other hand, the existence of hydroxyl groups in this amorphous aluminosilicate also favors the adsorption of cations and anions, so the volcanic glass is an economical adsorbent to retain heavy metals or radioactive cations.

Volcanic glass, also named as obsidian, is formed when the magma cools suddenly. This fact difficults the formation of an ordered structure, leading to an amorphous structure denoted as "*mineraloid*" [1]. Volcanic glasses are commonly dark or black, although these structures can also be brown, tan, green even blue, red, orange, or yellow depending on the trace elements or inclusions [2]. Like any crystal, volcanic glasses are chemically metastable, that is, with the passage of time, the volcanic glasses can crystallize. However, this process does not happen

**Keywords:** perlite, volcanic glass, metal adsorption, dyes adsorption

, when the pressure diminishes generates a macroporous structure

© 2016 The Author(s). Licensee InTech. 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.

© 2018 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.

Juan Antonio Cecilia, Miguel Armando Autie-Pérez,

Juan Antonio Cecilia, Miguel Armando Autie-Pérez,

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

Juan Manuel Labadie-Suarez, Enrique Rodríguez Castellón and

Juan Manuel Labadie-Suarez, Enrique Rodríguez Castellón and

http://dx.doi.org/10.5772/intechopen.75063

Antonia Infantes Molina

Antonia Infantes Molina

**Abstract**

of H2

O, CO2

, and SO2

**1. Genesis of the volcanic glass**

#### **Chapter 11 Provisional chapter**

#### **Volcanic Glass and its Uses as Adsorbent Volcanic Glass and its Uses as Adsorbent**

DOI: 10.5772/intechopen.75063

Juan Antonio Cecilia, Miguel Armando Autie-Pérez, Juan Manuel Labadie-Suarez, Enrique Rodríguez Castellón and Antonia Infantes Molina Juan Antonio Cecilia, Miguel Armando Autie-Pérez, Juan Manuel Labadie-Suarez, Enrique Rodríguez Castellón and Antonia Infantes Molina

Additional information is available at the end of the chapter Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.75063

#### **Abstract**

Volcanic glasses are an amorphous phyllosilicates formed by the fast cooling of the magma. The physicochemical properties of volcanic glasses are directly related to their chemical composition. Thus, the rhyolitic magma, which presents the highest SiO2 percentage, displays a high viscosity, which leads to explosive eruptions by the ex-solution of H2 O, CO2 , and SO2 , when the pressure diminishes generates a macroporous structure with interesting applications in construction, as abrasive, acoustic, filter as well as in the agriculture field. The macroporosity of volcanic glass allows to host large molecules as biomolecules, tensoactives, or dyes. On the other hand, the existence of hydroxyl groups in this amorphous aluminosilicate also favors the adsorption of cations and anions, so the volcanic glass is an economical adsorbent to retain heavy metals or radioactive cations.

**Keywords:** perlite, volcanic glass, metal adsorption, dyes adsorption

#### **1. Genesis of the volcanic glass**

Volcanic glass, also named as obsidian, is formed when the magma cools suddenly. This fact difficults the formation of an ordered structure, leading to an amorphous structure denoted as "*mineraloid*" [1]. Volcanic glasses are commonly dark or black, although these structures can also be brown, tan, green even blue, red, orange, or yellow depending on the trace elements or inclusions [2]. Like any crystal, volcanic glasses are chemically metastable, that is, with the passage of time, the volcanic glasses can crystallize. However, this process does not happen

© 2016 The Author(s). Licensee InTech. 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. © 2018 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.

**Figure 1.** Images of a typical volcanic glass (A) and volcanic glasses with inclusions (B).

at a uniform rate throughout the rock. The cracks are vulnerable zones to suffer devitrification (**Figure 1**). Another zone very sensitive to the devitrification is the edges of grain of the volcanic glass. In both cases, the volcanic glass tends to evolve to crystalline phases such as quartz, tridymite, and alkali feldspar [3].

The main volcanic glass is the obsidian; however, the sudden cooling of the magma can form

Pumice is formed when the magma erupts violently. This volcanic rock is commonly obtained from rhyolitic and andesitic magmas, although the pumice form basaltic magma is also known. Pumice presents a foaming structure due to a sudden depressurization and cooling of

trapped inside the matrix. These materials are used for construction (mortars and concretes),

Apache tears are dark volcanic glass with spherical structure, which are frequently associated

Tachylite is a dark volcanic glass obtained from the rapid cooling of basaltic magma so its chemical composition differs to that shown by obsidian since rhyolitic magma displays a

olivines, which have a stronger tendency to crystallize, because they have more freedom to

Sideromelane is an unusual glass obtained from a basaltic magma. This rock is formed at higher temperature and with more rapid chilling than tachylite. This rock is frequently formed during explosions of subglacial or submarine volcanoes. Sideromelane is usually embedded

Palagonite is also a glass obtained from basaltic magma, which is formed by the interaction between the basalt melt and water to form colored palagonite tuff cones. This tuff is composed of fragments of sideromelane and thicker basaltic rocks, which are embedded in a palagonite

The volcanic glasses are distributed in areas of recent volcanic activity throughout the world. These materials are not observed in zones where there was volcanic activity millions of years

content. These rocks appear mixed with other basaltic rocks such as feldspars or

and H2

Volcanic Glass and its Uses as Adsorbent http://dx.doi.org/10.5772/intechopen.75063 241

O and alkali content,

O) that are

the magma, which causes a decrease of the solubility of various gases (CO2

**Magma type Basaltic Andesitic Rhyolitic** Solidified rock Basalt Andesite Rhyolite Silica content 45–55% 55–65% 65–75% Gas content Least Intermediate Most Viscosity Least Intermediate Most

Type or eruption Effusive Sometimes explosive Usually explosive

Location Rifts, oceanic hotspots Subduction boundaries Continental hotspots

Melting temperature 1000–1200°C 800–1000°C 650–800°C

with perlite. These rocks are formed from rhyolitic magmas with high H2

other glasses.

**Table 1.** Characteristics of magma.

higher SiO2

cosmetics (exfoliant) or as abrasive [13].

leading to pebbles after the sudden cooling [14].

arrange themselves in a crystalline order [15].

matrix to form hyaloclastite deposits [15].

**3. Locations of the volcanic glass**

in a palagonite matrix forming hyaloclastite deposits [15].

#### **2. Chemical composition of the volcanic glass**

According to their chemical composition, magmas can be classified into basaltic magma (SiO<sup>2</sup> 45–55%), andesitic magma (SiO2 55–65%), and rhyolitic magma (SiO2 65–75%) (**Table 1**). The amount of gas occurring in a magma is genetically related with its chemical composition, that is, a rhyolitic magma has a higher gas content than a basaltic one.

The temperature of magmas is difficult to measure (due to the involved danger). However, the laboratory measurements coupled with the field observations have indicated that the temperature of eruption ranges from 1000 and 1200°C in a basaltic magma, from 800 and 1000°C in an andesitic magma and from 650 and 800°C in a rhyolitic magma [4–7].

The viscosity mainly depends on the magmatic composition and temperature. Thus, the magmas having a higher SiO2 content have a higher viscosity than the magmas having a lower SiO2 content. Moreover, low-temperature magmas have a higher viscosity than high-temperature magmas [7, 8].

The cooling of the magma depends on the viscosity of the lava, which is directly related with its chemical composition, as was indicated previously. The lava with lower viscosity, that is, the basaltic lava, cools down quickly, obtaining thin glasses with a thick below 1 cm. However, the viscous rhyolitic lava, which erupts on dry land, cooling with a low rate leading to volcanic glass with larger dimensions [7, 9].

Generally, the rhyolitic magmas (SiO2 ) higher than 60% give rise to explosive eruptions, resulting in large volume of pyroclastics and related to the ex-solution of volatiles, mainly H2 O, CO2 and SO2 as the pressure is reduced [7, 10, 11]. Because high viscosity inhibits crystallization, a sudden cooling and loss of volatiles, as when lava extrudes from a volcanic vent, tends to chill the material to a glass rather than to crystallize it, leading to the volcanic glass [12].

**Table 1.** Characteristics of magma.

at a uniform rate throughout the rock. The cracks are vulnerable zones to suffer devitrification (**Figure 1**). Another zone very sensitive to the devitrification is the edges of grain of the volcanic glass. In both cases, the volcanic glass tends to evolve to crystalline phases such as

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

According to their chemical composition, magmas can be classified into basaltic magma (SiO<sup>2</sup>

amount of gas occurring in a magma is genetically related with its chemical composition, that

The temperature of magmas is difficult to measure (due to the involved danger). However, the laboratory measurements coupled with the field observations have indicated that the temperature of eruption ranges from 1000 and 1200°C in a basaltic magma, from 800 and 1000°C

The viscosity mainly depends on the magmatic composition and temperature. Thus, the mag-

The cooling of the magma depends on the viscosity of the lava, which is directly related with its chemical composition, as was indicated previously. The lava with lower viscosity, that is, the basaltic lava, cools down quickly, obtaining thin glasses with a thick below 1 cm. However, the viscous rhyolitic lava, which erupts on dry land, cooling with a low rate leading

ing in large volume of pyroclastics and related to the ex-solution of volatiles, mainly H2

the material to a glass rather than to crystallize it, leading to the volcanic glass [12].

as the pressure is reduced [7, 10, 11]. Because high viscosity inhibits crystallization, a

sudden cooling and loss of volatiles, as when lava extrudes from a volcanic vent, tends to chill

content. Moreover, low-temperature magmas have a higher viscosity than high-temper-

content have a higher viscosity than the magmas having a lower

) higher than 60% give rise to explosive eruptions, result-

55–65%), and rhyolitic magma (SiO2

65–75%) (**Table 1**). The

O, CO2

quartz, tridymite, and alkali feldspar [3].

Industry and Their Impact on the Human Health

240

45–55%), andesitic magma (SiO2

mas having a higher SiO2

to volcanic glass with larger dimensions [7, 9].

Generally, the rhyolitic magmas (SiO2

ature magmas [7, 8].

SiO2

and SO2

**2. Chemical composition of the volcanic glass**

is, a rhyolitic magma has a higher gas content than a basaltic one.

**Figure 1.** Images of a typical volcanic glass (A) and volcanic glasses with inclusions (B).

in an andesitic magma and from 650 and 800°C in a rhyolitic magma [4–7].

The main volcanic glass is the obsidian; however, the sudden cooling of the magma can form other glasses.

Pumice is formed when the magma erupts violently. This volcanic rock is commonly obtained from rhyolitic and andesitic magmas, although the pumice form basaltic magma is also known. Pumice presents a foaming structure due to a sudden depressurization and cooling of the magma, which causes a decrease of the solubility of various gases (CO2 and H2 O) that are trapped inside the matrix. These materials are used for construction (mortars and concretes), cosmetics (exfoliant) or as abrasive [13].

Apache tears are dark volcanic glass with spherical structure, which are frequently associated with perlite. These rocks are formed from rhyolitic magmas with high H2 O and alkali content, leading to pebbles after the sudden cooling [14].

Tachylite is a dark volcanic glass obtained from the rapid cooling of basaltic magma so its chemical composition differs to that shown by obsidian since rhyolitic magma displays a higher SiO2 content. These rocks appear mixed with other basaltic rocks such as feldspars or olivines, which have a stronger tendency to crystallize, because they have more freedom to arrange themselves in a crystalline order [15].

Sideromelane is an unusual glass obtained from a basaltic magma. This rock is formed at higher temperature and with more rapid chilling than tachylite. This rock is frequently formed during explosions of subglacial or submarine volcanoes. Sideromelane is usually embedded in a palagonite matrix forming hyaloclastite deposits [15].

Palagonite is also a glass obtained from basaltic magma, which is formed by the interaction between the basalt melt and water to form colored palagonite tuff cones. This tuff is composed of fragments of sideromelane and thicker basaltic rocks, which are embedded in a palagonite matrix to form hyaloclastite deposits [15].

#### **3. Locations of the volcanic glass**

The volcanic glasses are distributed in areas of recent volcanic activity throughout the world. These materials are not observed in zones where there was volcanic activity millions of years

insulation, filtration, adsorbent, agriculture and horticulture, lightweight aggregate con-

Volcanic Glass and its Uses as Adsorbent http://dx.doi.org/10.5772/intechopen.75063 243

The wide variety of applications that exhibits the expanded perlite would lead to a monograph about this material. This chapter is only focused on some applications of the volcanic

struction, among other applications as indicated in **Figure 6**.

glass related with adsorption and separation processes.

**Figure 3.** Morphology of perlite in its rock, crushed and expanded form.

**Figure 4.** SEM image of expanded perlite.

**Figure 5.** Uses and applications of raw perlite.

**Figure 2.** Volcanic glass by country [16].

ago since obsidian is metastable material and is susceptible to geological and environmental effects, evolving mainly to smectites or zeolites [12].

As indicated, obsidian is distributed throughout the five continents. Thus, obsidian is found in several nations of America (Argentina, Chile, Peru, Colombia, Ecuador, Guatemala, Mexico, United States or Canada), Europe (France, Italy, Hungary, Greece, Iceland or Russia), Africa (Kenya, Tanzania or Ethiopia), Asia (Turkey, Iran, Indonesia or Japan) and Oceania (Australia and New Zealand) (**Figure 2**).

#### **4. Perlite (a surprising material)**

Perlite is also an amorphous volcanic glass with water retained in its structure [17]. The thermal treatment of the volcanic glass favors the removal of the structural water as well as an unusual expansion of its structure when the temperature reaches 850–900°C. The water trapped in the structure of the material vaporizes and escapes, leading to an expansion of the material to 7–20 times its original volume, acquiring a foam-like cellular structure (**Figures 3** and **4**) and obtaining a versatile and sustainable mineral that is mined and processed with a negligible impact on the environment. Thus, unexpanded ("raw") perlite has a bulk density around 1.1 g cm−3, while typical expanded perlite has a bulk density of about 0.03–0.150 g cm−3 [18]. The main uses and applications of perlite are indicated below.

Raw perlite can be used as sandblasting, slag coagulant or silica source. In addition, perlite has interesting applications in the field of foundry, steel industries or metal finishing (**Figure 5**). However, once the perlite structure is expanded, the number of uses and applications of this material is infinitely higher. Thus, the expanded perlite can be used as insulation in a wide range of temperatures, oil well treatment, flame resistant, acoustic insulation, filtration, adsorbent, agriculture and horticulture, lightweight aggregate construction, among other applications as indicated in **Figure 6**.

The wide variety of applications that exhibits the expanded perlite would lead to a monograph about this material. This chapter is only focused on some applications of the volcanic glass related with adsorption and separation processes.

**Figure 3.** Morphology of perlite in its rock, crushed and expanded form.

**Figure 4.** SEM image of expanded perlite.

ago since obsidian is metastable material and is susceptible to geological and environmental

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

As indicated, obsidian is distributed throughout the five continents. Thus, obsidian is found in several nations of America (Argentina, Chile, Peru, Colombia, Ecuador, Guatemala, Mexico, United States or Canada), Europe (France, Italy, Hungary, Greece, Iceland or Russia), Africa (Kenya, Tanzania or Ethiopia), Asia (Turkey, Iran, Indonesia or Japan) and Oceania (Australia

Perlite is also an amorphous volcanic glass with water retained in its structure [17]. The thermal treatment of the volcanic glass favors the removal of the structural water as well as an unusual expansion of its structure when the temperature reaches 850–900°C. The water trapped in the structure of the material vaporizes and escapes, leading to an expansion of the material to 7–20 times its original volume, acquiring a foam-like cellular structure (**Figures 3** and **4**) and obtaining a versatile and sustainable mineral that is mined and processed with a negligible impact on the environment. Thus, unexpanded ("raw") perlite has a bulk density around 1.1 g cm−3, while typical expanded perlite has a bulk density of about 0.03–0.150 g cm−3 [18]. The main uses and applications of perlite are indicated

Raw perlite can be used as sandblasting, slag coagulant or silica source. In addition, perlite has interesting applications in the field of foundry, steel industries or metal finishing (**Figure 5**). However, once the perlite structure is expanded, the number of uses and applications of this material is infinitely higher. Thus, the expanded perlite can be used as insulation in a wide range of temperatures, oil well treatment, flame resistant, acoustic

effects, evolving mainly to smectites or zeolites [12].

and New Zealand) (**Figure 2**).

**Figure 2.** Volcanic glass by country [16].

Industry and Their Impact on the Human Health

242

below.

**4. Perlite (a surprising material)**

**Figure 5.** Uses and applications of raw perlite.

its high efficiency, low-cost possibilities, easy handling, and the availability of different adsorbents. In this sense, perlite is a material with high potential due to its low cost and

**Table 2** reports the adsorption capacity of perlite in various cations [19, 23–39]. From these data, it can be observed how the thermal treatment to expand the perlite does not improve the adsorption capacity due to the thermal treatment causes the dehydroxylation of the -OH

these authors have pointed out that the adsorption follows a pseudo-second reaction and the

Several authors have established that the perlite can improve its adsorption capacity by a thermal treatment to expand the perlite structure, and then, this material has been coated by chitosan. This polymer has been increasingly studied as an adsorbent for the removal of Mn+ ions from aqueous solutions because the amino and hydroxyl groups on the chitosan chain act as a chelation or reaction sites for the substances to be removed [28, 29, 32, 36] (**Figure 9**). Other authors have pointed that expanded perlite can host certain oxides, which adsorb certain cations with high selectivity. Thus, it has been proposed in the literature that the incorpo-

Perlite can also act as a barrier to isolate radioactive wastes [35, 40, 41]. Thus, Akkaya has carried out several studies where polyacrylamide or poly-2-hydroxyethylmethacrylate is incorporated (**Figure 11**) onto the expanded perlite to favor a selective adsorption of Th4+ and UO2

species from aqueous solutions (**Table 3**) [40, 41]. The adsorption data revealed that Th4+ is more susceptible to be adsorbed and that the poly-acrylamide-expanded perlite composite is more efficient adsorbent than poly-2-hydroxyethylmethacrylate-expanded perlite probably due to the cations that show higher affinity by the amine groups of the acrylamide species. In the same way, Akkaya evaluated several adsorption parameters onto polyacrylamide-

in a leaching solution), obtaining the following trend: 208Tl (0.4 MBq kg−1) > 212Pb and 212Bi

into the macrochannels of perlite, favoring the selective adsorption of

by Mn+ is disfavored [24]. On the other hand,

Volcanic Glass and its Uses as Adsorbent http://dx.doi.org/10.5772/intechopen.75063 245

2+

, Ra2+, Bi3+, Ac3+, and Pb2+

high availability.

**Figure 7.** Hydroxyl groups in silica species.

**Figure 8.** Hydroxyl groups in aluminum species.

ration of Fe2

O3

or MnO2

groups so the possible cationic exchange H+

maximum adsorption capacity takes place at pH = 5–6.5.

harmful cations, such as As (III), Cr(VI) or Sb(V) [37–39] (**Figure 10**).

expanded perlite in five radio nuclides of the U- and Th- series (TI<sup>+</sup>

(0.3 MBq kg−1) > 228Ac and (0.1 MBq kg−1) > 226Ra (0.04 MBq kg−1) [42].

**Figure 6.** Uses and applications of expanded perlite.

### **5. Volcanic glass as adsorbent**

The adsorption capacity of perlite is attributed to the presence of hydroxyl groups on its surface [19, 20]. Thus, silicon atoms tend to maintain their coordination at room temperature by attachment to the monovalent hydroxyl groups, forming silanol groups as follows (**Figure 7**):

while the hydrous oxide surface groups in alumina (**Figure 8**) are given by:

#### **5.1. Adsorption of cations/anions**

Heavy metals are among the most common pollutants that harm the aqueous environment and damage the health of human, animals, and plants [21]. Domestic and industrial wastewaters containing toxic metal ions are increasingly discharged into the environment, especially in developing countries. These metal ions are of significant importance as they are not biodegradable and cannot be metabolized by the environment but tend to accumulate in living organisms, causing various diseases and disorders. Also, they can only be diluted or transformed, not destroyed [22]. These heavy metal ions pose serious health implications to the vital organs of human beings and animals when consumed above certain threshold concentrations. There are various techniques for the removal of these toxic metal ions such as chemical precipitation, solvent extraction, ion exchange, reverse osmosis, and nanofiltration. Among these techniques, adsorption is considered effective and economic due to

**Figure 8.** Hydroxyl groups in aluminum species.

**5. Volcanic glass as adsorbent**

Industry and Their Impact on the Human Health

244

**Figure 6.** Uses and applications of expanded perlite.

**5.1. Adsorption of cations/anions**

The adsorption capacity of perlite is attributed to the presence of hydroxyl groups on its surface [19, 20]. Thus, silicon atoms tend to maintain their coordination at room temperature by attachment to the monovalent hydroxyl groups, forming silanol groups as follows (**Figure 7**):

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

Heavy metals are among the most common pollutants that harm the aqueous environment and damage the health of human, animals, and plants [21]. Domestic and industrial wastewaters containing toxic metal ions are increasingly discharged into the environment, especially in developing countries. These metal ions are of significant importance as they are not biodegradable and cannot be metabolized by the environment but tend to accumulate in living organisms, causing various diseases and disorders. Also, they can only be diluted or transformed, not destroyed [22]. These heavy metal ions pose serious health implications to the vital organs of human beings and animals when consumed above certain threshold concentrations. There are various techniques for the removal of these toxic metal ions such as chemical precipitation, solvent extraction, ion exchange, reverse osmosis, and nanofiltration. Among these techniques, adsorption is considered effective and economic due to

while the hydrous oxide surface groups in alumina (**Figure 8**) are given by:

its high efficiency, low-cost possibilities, easy handling, and the availability of different adsorbents. In this sense, perlite is a material with high potential due to its low cost and high availability.

**Table 2** reports the adsorption capacity of perlite in various cations [19, 23–39]. From these data, it can be observed how the thermal treatment to expand the perlite does not improve the adsorption capacity due to the thermal treatment causes the dehydroxylation of the -OH groups so the possible cationic exchange H+ by Mn+ is disfavored [24]. On the other hand, these authors have pointed out that the adsorption follows a pseudo-second reaction and the maximum adsorption capacity takes place at pH = 5–6.5.

Several authors have established that the perlite can improve its adsorption capacity by a thermal treatment to expand the perlite structure, and then, this material has been coated by chitosan. This polymer has been increasingly studied as an adsorbent for the removal of Mn+ ions from aqueous solutions because the amino and hydroxyl groups on the chitosan chain act as a chelation or reaction sites for the substances to be removed [28, 29, 32, 36] (**Figure 9**).

Other authors have pointed that expanded perlite can host certain oxides, which adsorb certain cations with high selectivity. Thus, it has been proposed in the literature that the incorporation of Fe2 O3 or MnO2 into the macrochannels of perlite, favoring the selective adsorption of harmful cations, such as As (III), Cr(VI) or Sb(V) [37–39] (**Figure 10**).

Perlite can also act as a barrier to isolate radioactive wastes [35, 40, 41]. Thus, Akkaya has carried out several studies where polyacrylamide or poly-2-hydroxyethylmethacrylate is incorporated (**Figure 11**) onto the expanded perlite to favor a selective adsorption of Th4+ and UO2 2+ species from aqueous solutions (**Table 3**) [40, 41]. The adsorption data revealed that Th4+ is more susceptible to be adsorbed and that the poly-acrylamide-expanded perlite composite is more efficient adsorbent than poly-2-hydroxyethylmethacrylate-expanded perlite probably due to the cations that show higher affinity by the amine groups of the acrylamide species. In the same way, Akkaya evaluated several adsorption parameters onto polyacrylamideexpanded perlite in five radio nuclides of the U- and Th- series (TI<sup>+</sup> , Ra2+, Bi3+, Ac3+, and Pb2+ in a leaching solution), obtaining the following trend: 208Tl (0.4 MBq kg−1) > 212Pb and 212Bi (0.3 MBq kg−1) > 228Ac and (0.1 MBq kg−1) > 226Ra (0.04 MBq kg−1) [42].

Perlite has also been used as a sorbent to retain F<sup>−</sup>

**Figure 9.** Chemical interaction between chitosan and the cations in solution.

**Table 2.** Cations adsorption onto perlite reported in the literature.

[43]. This process takes place by electrostatic interactions between F<sup>−</sup>

−

−

is found frequently in fertilizers, while F<sup>−</sup>

supply; however, an excess of F<sup>−</sup>

**AsO4 2−**

**Sb3+** α-MnO<sup>2</sup>

of the chitosan. In the case of the NO3

which interacts directly with the NO3

**5.2. Adsorption of dyes/surfactants**

 or NO3 −

a chitosan-coated perlite to adsorb fluoride species, obtaining the highest value of 64.4 mg g−1

**Material Adsorbed (mg g−1) Reference**

Unexpanded perlite 0.003 [35]

Dyes and pigments are highly used organic compounds as colorants in a wide variety of products. These processes generate wastes that are often released together with wastewater. The treatment of these wastewaters is one of the main environmental issues since these residues are very dangerous for the environment and harmful to health. Wastewater from the textile industry is processed in biological treatment plants. These processes are not very efficient so it is necessary to use complementary or alternative processes to eliminate these organic compounds from the water. Several processes such as precipitation, flocculation, coagulation, ion exchange, reverse osmosis, ozonization or adsorption have emerged as processes to remedy these emissions of dyes and pigments. Adsorption is one of the processes mostly used to remove organic compounds from wastewater. Active carbon is the adsorbent that has shown the greatest adsorption capacity; however, this adsorbent is synthesized from various physical and chemical processes, which raises the price of the process in comparison with the natural adsorbent that are inexpensive and highly available,

from aqueous solutions since NO3

Volcanic Glass and its Uses as Adsorbent http://dx.doi.org/10.5772/intechopen.75063

species and -NH2

species are added in a controlled way in the water

can cause severe damages to health. Thus, Vijaya et al. used

species, expanded perlite was used to support γ-Fe<sup>2</sup>

species, reaching an adsorption of 32.6 mg g−1 [44].

−

247

species

O3 ,

**Table 2.** Cations adsorption onto perlite reported in the literature.

 Chemical interaction between chitosan and the cations in solution.

Perlite has also been used as a sorbent to retain F<sup>−</sup> or NO3 − from aqueous solutions since NO3 − is found frequently in fertilizers, while F<sup>−</sup> species are added in a controlled way in the water supply; however, an excess of F<sup>−</sup> can cause severe damages to health. Thus, Vijaya et al. used a chitosan-coated perlite to adsorb fluoride species, obtaining the highest value of 64.4 mg g−1 [43]. This process takes place by electrostatic interactions between F<sup>−</sup> species and -NH2 species of the chitosan. In the case of the NO3 − species, expanded perlite was used to support γ-Fe<sup>2</sup> O3 , which interacts directly with the NO3 − species, reaching an adsorption of 32.6 mg g−1 [44].

#### **5.2. Adsorption of dyes/surfactants**

Dyes and pigments are highly used organic compounds as colorants in a wide variety of products. These processes generate wastes that are often released together with wastewater. The treatment of these wastewaters is one of the main environmental issues since these residues are very dangerous for the environment and harmful to health. Wastewater from the textile industry is processed in biological treatment plants. These processes are not very efficient so it is necessary to use complementary or alternative processes to eliminate these organic compounds from the water. Several processes such as precipitation, flocculation, coagulation, ion exchange, reverse osmosis, ozonization or adsorption have emerged as processes to remedy these emissions of dyes and pigments. Adsorption is one of the processes mostly used to remove organic compounds from wastewater. Active carbon is the adsorbent that has shown the greatest adsorption capacity; however, this adsorbent is synthesized from various physical and chemical processes, which raises the price of the process in comparison with the natural adsorbent that are inexpensive and highly available,

−M − OH + OH<sup>−</sup> → −M − O<sup>−</sup> + H2 O

**Table 3.** Radioactive cations adsorption onto perlite reported in the literature.

−M − O<sup>−</sup> + Dye+ → −M − O − Dye

interactions increase, as indicated in the following scheme.

−M − OH + H+ → −M − OH2

well as chitosan, orthophenanthroline or γ-Fe<sup>2</sup>

surfactant, so nonelectrostatic interactions appear.

−M − OH2

**UO2 2+**

**Th4+**

In the same way, anionic dyes have been adsorbed in expanded and unexpanded perlite as

**Material Adsorbed (mol kg−1) Reference**

Unexpanded perlite 1.59 [35] poly-acrylamide-expanded perlite 0.66 [40] poly-2-hydroxyethylmethacrylate-expanded perlite 0.29 [41]

Unexpanded perlite 4.63 [35] poly-acrylamide-expanded perlite 0.74 [40] poly-2-hydroxyethylmethacrylate-expanded perlite 0.44 [41]

The adsorption processes are favored under slightly acid conditions since the electrostatic

<sup>+</sup> + Dye<sup>−</sup> → −M − OH2

Surfactants are among the most versatile of the products of the chemical industry, being used as detergent, in pharmaceuticals, in prospecting for petroleum. However, the application of surfactants can also produce environmental pollution and raises a series of problems for wastewater treatment plants. One of the characteristic features of surfactants is their tendency to adsorb at interfaces in an oriented fashion. Similarly to the dyes, the surfactants can be classified into cationic and anionic so the adsorbent-surfactant interactions should be similar; however, the long hydrocarbon chains give rise to a polar section and another nonpolar in the

Considering this premises, an inexpensive adsorbed as perlite has been used to adsorb a cationic surfactant such as cetyltrimethylammonium bromide (CTAB), obtaining a maximum adsorption value of 0.04 mmol g−1 for unexpanded perlite and 0.11 mmol g−1 for expanded perlite [55]. As takes places in cationic dyes, the adsorption is favored in basic conditions since the negatively charged surface of the perlite interacts with the cationic surfactant. The

O3

coated-perlite (**Figure 13** and **Table 5**).

Volcanic Glass and its Uses as Adsorbent http://dx.doi.org/10.5772/intechopen.75063 249

+

<sup>+</sup> Dye<sup>−</sup>

**Figure 10.** Chemical adsorption of As(V) in γ-Fe<sup>2</sup> O3 species.

**Figure 11.** Interaction of polyacrylamide and poly-2-hydroxyethylmethacrylate with cations.

although its adsorption capacity is lower. Among these adsorbents, perlite is a low-cost material with great potential to adsorb pigments and dyes. Thus, several studies have been carried out for the adsorption of cationic dyes as methylene blue [20], methyl violet [45, 46], C.I. basic blue 41 [47], rhodamine B [48], maxilon blue G5 [49], or rhodamine B [50] (**Figure 12** and **Table 4**).

In all cases, the adsorption process is favored under basic conditions since perlite (negatively charged) interacts with the dye (positively charged) as indicates the following reactions::

**Table 3.** Radioactive cations adsorption onto perlite reported in the literature.

**Figure 11.** Interaction of polyacrylamide and poly-2-hydroxyethylmethacrylate with cations.

O3 species.

Volcanoes - Geological and Geophysical Setting, Theoretical Aspects and Numerical Modeling, Applications to

(**Figure 12** and **Table 4**).

**Figure 10.** Chemical adsorption of As(V) in γ-Fe<sup>2</sup>

Industry and Their Impact on the Human Health

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although its adsorption capacity is lower. Among these adsorbents, perlite is a low-cost material with great potential to adsorb pigments and dyes. Thus, several studies have been carried out for the adsorption of cationic dyes as methylene blue [20], methyl violet [45, 46], C.I. basic blue 41 [47], rhodamine B [48], maxilon blue G5 [49], or rhodamine B [50]

In all cases, the adsorption process is favored under basic conditions since perlite (negatively charged) interacts with the dye (positively charged) as indicates the following reactions::

 −M − OH + OH<sup>−</sup> → −M − O<sup>−</sup> + H2 O −M − O<sup>−</sup> + Dye+ → −M − O − Dye

In the same way, anionic dyes have been adsorbed in expanded and unexpanded perlite as well as chitosan, orthophenanthroline or γ-Fe<sup>2</sup> O3 coated-perlite (**Figure 13** and **Table 5**).

The adsorption processes are favored under slightly acid conditions since the electrostatic interactions increase, as indicated in the following scheme.

 −M − OH + H+ → −M − OH2 + −M − OH2 <sup>+</sup> + Dye<sup>−</sup> → −M − OH2 <sup>+</sup> Dye<sup>−</sup>

Surfactants are among the most versatile of the products of the chemical industry, being used as detergent, in pharmaceuticals, in prospecting for petroleum. However, the application of surfactants can also produce environmental pollution and raises a series of problems for wastewater treatment plants. One of the characteristic features of surfactants is their tendency to adsorb at interfaces in an oriented fashion. Similarly to the dyes, the surfactants can be classified into cationic and anionic so the adsorbent-surfactant interactions should be similar; however, the long hydrocarbon chains give rise to a polar section and another nonpolar in the surfactant, so nonelectrostatic interactions appear.

Considering this premises, an inexpensive adsorbed as perlite has been used to adsorb a cationic surfactant such as cetyltrimethylammonium bromide (CTAB), obtaining a maximum adsorption value of 0.04 mmol g−1 for unexpanded perlite and 0.11 mmol g−1 for expanded perlite [55]. As takes places in cationic dyes, the adsorption is favored in basic conditions since the negatively charged surface of the perlite interacts with the cationic surfactant. The

**Figure 12.** Cationic dyes adsorbed onto perlite.

amount of the cation is another key factor due to CTA+

**Table 5.** Adsorption of anionic dyes onto perlite reported in the literature.