Soil Pollution: Origin, Monitoring & Remediation

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Part 1

Soil — Its Nature and Origin

Soil is essentially a natural body of mineral and organic constituents produced by solid material recycling during a myriad of complex processes of solid crust modifications, which are closely related to the hydrologic cycle. It is the interface at which all forces, acting on the Earth’s crust meet to produce a medium of unconsolidated material that acts as an environment for further changes and developments keeping pace with the evolution of the global Earth system as a whole. It offers shelter and habitat for countless number of organisms and provides incubation and living medium for plants, while perfectly playing its role in the universal cycle of material flow between the four main geospheres (atmosphere, lithosphere, hydrosphere and biosphere). For this reason, some authors consider soil as a separate geosphere and give it the name pedosphere. The pedosphere, is formed by, and is eternally changing by weathering forces, which despite their complicated nature and intricately structured processes are found to belong to few basic types, the Nature of which and importance for the evolution of our Earth environments will be the subject of close inspection in the first few chapters of the present work.

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Chapter 1

The Origin of Soil

Prof. Dr.Ibrahim A. Mirsal¹

(1)

Oberroßbacherstr. 53, 35685, Dillenburg, Germany

Prof. Dr.Ibrahim A. Mirsal

Email: [email protected]

1.1 Physical or mechanical weathering

Physical and biological agents, such as wind, running water, temperature changes, and living organisms, perpetually modify the Earth’s crust, changing its upper surface into products that are more nearly in equilibrium with the atmosphere, the hydrosphere, and the biosphere. Earth scientists sum up all processes through which these alterations take place under the collective term weathering. One speaks of mechanical weathering in case the dominant forces are mainly mechanical such as the eroding action of running water, the abrading action of stream load or the physical action of wind and severe temperature fluctuations. Similarly, one speaks of biological weathering when the forces producing changes are directly or indirectly related to living organisms. Of these, we can mention several examples such as the action of burrowing animals, penetration forces of plant roots, and the destructive action of algae, bacteria, and their acid-producing symbiotic community of the lichens or simply the destructive action of man, who continuously disturbs the Earth’s crust through various activities.

Processes of disintegration, during which mantle rocks are broken down to form particles of smaller size, without considerable change in chemical or mineralogical composition are known as physical weathering processes. Changes of this type prevail under extreme climatic conditions as in deserts or arctic regions. They are also prevailing in areas of mountainous relief. The most prominent agents of physical weathering are:

a)

Differential stress caused by unloading of deep-seated rocks on emerging to the surface.

b)

Differential thermal expansion under extreme climatic conditions.

c)

Expansion of interstitial water volume by freezing, that leads to rupture along crystal boundaries.

Other mechanical agents enhance the effect of mechanical weathering. These may include processes such as gravity, abrasion by glacial ice or wind blown particles.

1.2 Chemical weathering

Chemical weathering depends principally on the presence of water. It is initiated largely by the preceding physical weathering; since disintegration of the solid material leads to activation of the solid phase and eventually to more favourable energetic conditions for subsequent chemical alterations. The effect of chemical weathering is by far more decisive in the geologic cycle, whereby dramatic changes may completely obliterate the parent rock and vast geomorphologic changes may occur. Chemical weathering is normally performed through one of the following chemical reactions:

a) Oxidation: In the vadose (aerated) zone (fig.91, p. 187) where most processes leading to soil formation take place, availability of oxygen, water, and dissolved gases leads to a dominance of oxidation reactions leaving their finger prints on the formed soil horizons represented by the characteristic colours of the resulting products. The typical yellow, brown, or red colour of soil in some warm areas (e.g. Mediterranean terra rossa) is due largely to the oxidation of ferrous iron in the minerals pyroxene, amphibole, and olivine into ferric iron. Beside Fe+2, Mn+2 and S+2 are the most commonly affected elements by oxidation. They are normally oxidised to Mn+4 and S+6. Other examples are V, Cr, Cu, As, Se, Mo, Pd, Sn, Sb, W, Pt, Hg, and U.

A good example of oxidation reactions during weathering is the oxidation of pyrite to form sulphuric acid, which attacks the rocks (see equation 1.1), developing solution pits and stains.

(1.1)

Oxidation functions most effectively in the vadose zone, yet in some places oxidation fluids can descend to depths far below the water table before their oxidising power is consumed (Rose et. al., 1979).

b. Hydration and hydrolysis: Hydration and hydrolysis are the most important processes encountered during soil formation by weathering. While in hydrolysis a proper chemical reaction between water and the mineral substance takes place to produce or consume a proton (H+) or an electron (OH)−, water in hydration forms an envelope around the cations to form a hydrate — a compound in which it is integrated within the crystalline structure of the substance. A typical example of hydration is the conversion of anhydrite (CaSO4) into gypsum (CaSO4.2H2O).

Clays that, together with organic substance and other colloidal matter, give soil its characteristic nature are typical products of hydrolysis processes steering the change of aluminium or iron silicates into clay minerals and/or iron oxides. An example of this is the reaction of the mineral albite in the course of weathering with weak acids to yield kaolinite (clay), silica and Sodium ions (Na+).

(1.2)

The protons involved in this reaction are generally provided by naturally occurring acids, such as carbonic acid or by the rather abundant humic acids. The released Na-cations will be sorbed on the surface of colloidal particles or released to the solution. SiO2 precipitates as colloidal silica or quartz.

1.3 Weathering by biological agents

Biological effect is a factor, which has never been absent in any soil forming process during weathering. It is always there, whether the dominant processes were mechanical or chemical; it always accompany emergence and evolution of soil. One needs only to consider the mechanical forces exerted by intruding roots, or the enormous work of worms and rodents in mixing and disintegrating rock bodies in the upper surface environment to realise how important this factor is for soil formation and its later evolution. The chemical dimension of biological weathering vary from simple dissolution reactions occurring at the extensive acidic environment at root tips, to complex biochemical processes by which certain elements are extracted, concentrated or bound into complex by plants or by bacterial action. As an example, we may take the oxidation of iron and sulphur or the fixation of nitrogen by bacteria.

1.4 Factors controlling soil formation

Climate: Weathering in general and soil formation processes in particular are dependent largely on climatic factors. These, not only control the main processes and directions in the main cycles of material flow, but also affect organic addition, and the rate of mineral transformation via crystal lattice break down. S. Ross, (1989) found that in such transformations the rates of chemical reaction double for every 10 °C rise in temperature and that the maximum rate of organic matter decay takes place in the temperature range from 25- 35 °C. This may also follow from the observation that, on a global level, the rate of mineral transformation and organic matter decay increase from high to low latitudes.

Biota: Actually, the role of organisms cannot be discussed apart from the climatic control effect, since these are generally related to bio geographical conditions. Aside from the mechanical work done by rodents and burrowing animals, the chemical reactions triggered off by bacteria and plant roots play, as mentioned before, a crucial role in the process of soil formation

Parent material. Since the principal source of soil is the pre-existing rock or parent material, the main control on soil formation will be directly related to the susceptibility of this material to weathering processes and the chemical and physical changes accompanying them. Physical properties such as hardness, cleavage, porosity and grain size form primary factors determining whether water can percolate into a rock layer to initiate its disintegration into an unconsolidated material or its decomposition into a different mineralogical constitution, properties and characteristics of the resulting soil will also be directly related to parent material. Soils formed on parent material highly resistant to weathering will normally have relatively less thickness than those formed on easily weathered landscapes. They also contain more regolith or stony material than the latter.

1.5 Morphology of soil

One of the characteristic properties of soil is the organisation of its constituents into layers related to present day surface. Each of these layers, which may easily be identified in the field through colour or texture, reflects subtle differences in chemical properties and composition, of which the most significant are pH, organic matter content, mineral assemblages, and metal concentrations, especially Fe and Mn.

Soil layers, normally referred to as horizons, may range from few centimetres to a meter or more in thickness. They are classified according to their position in profile, which is also closely related to their mineralogical constitution and grain size into few basic types as shown in figure 1.

Fig. 1.

Diagrammatic representation of a hypothetical soil profile

At the top of the profile, a layer of partially decomposed organic debris is referred to as the O-horizon (also A0). It contains about 20–30 % organic matter, derived from plant and animal litter. In this region, the principle process of soil formation, known as humification i.e. complete change of organic debris into soil organic matter, takes place. The resulting material (humus) made of a mixture of organic substances, which is characterised by its dark colour and rather acidic nature, is mainly produced by the work of consumers and decomposers among the micro- organisms, living in the site of soil formation.

In best-developed soils, rendering ideal profiles, three main horizons follow. They form a transition between the O-horizon and the base of the profile, made of the parent material, which is given the name R-horizon. This may be rock in situ, transported alluvial, glacial or wind blown overburden or even soil of a past pedological cycle.

The three middle horizons, identified by the letters A, B, and C, are composed of sand, silt clay and other weathered by-products (table 1 presents a description of grain size). They represent two main subsequent stages of soil formation, whereby the lowest one (C-horizon) represents the stage nearest to the parent material. It is made up of partially or poorly weathered bedrock having minimum content of organic matter and clay. The A and B- horizons are viewed together as representing the real soil emerging from the complete weathering of the C-horizon. They are summed together under the name solum.

Table 1.

Grain sizes of clastic sediments and related rock types

The A-horizon, which is generally a dark coloured horizon, rich in organic matter, may in some cases have a structure made up of three identifiable subdivisions known as A1, A2, and A3. Marked colour differences resulting from leaching processes make it possible to identify these subdivisions in the field. In fact, the resolution of the A-horizon into a dark upper layer containing humus with mineral grains (A1) and an underlying light coloured horizon with little organic matter is due to leaching processes initiated by water percolating downward through the rich organic material on the top of the A-horizon. On its course downwards, water carrying in solution organic acids and complexing agents generated in the humus by bacterial action performs a process of leaching known as eluviation — a word from Latin meaning to wash out. Eluviation, enhanced by carbonic acid resulting from the decay of humus, displaces bases (Ca, Na, Mg, K) from the exchange sites of clay minerals. These bases move down the soil profile as colloidal particles, dissolved ions or as free ions complexed with hydroxyl. Silica is also leached in the course of eluviation. It is largely dissolved as silicic acid or colloidal silica. Resistant primary mineral matter, however, remains behind in the upper soil (ROSE et al. 1979)

Material dissolved in the A-horizon finds in some cases its way to the saturated zone of ground water, yet the greatest part of it is normally redeposited in the underlying layers forming the B-horizon. In this process, known as illuviation (from the Latin to wash in), colloidal material and metal oxides are deposited or precipitated in the B-horizon, resulting in an enrichment of its layers in clay and aluminium oxide. Fe oxides, if present, give the horizon its red or yellow brown colour.

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Chapter 2

Soil Constituents

Prof. Dr.Ibrahim A. Mirsal¹

(1)

Oberroßbacherstr. 53, 35685, Dillenburg, Germany

Prof. Dr.Ibrahim A. Mirsal

Email: [email protected]

Generally speaking Soil is a three dimensional system, made of a solid, a liquid and a gaseous phase, each in an amount depending on the abundance of its constituents and their kinetic roles in the complex series of reactions, leading to soil formation. Figure 2 illustrates the composition by volume of an average soil.

Fig. 2.

Composition by volume of an average soil

2.1 The mineral solid phase

Mineral matter in soil depends largely on the nature and composition of the parent rock. However, since about three fourths of the earth’s crust is made up of silicon and oxygen, we find that silicate minerals occupy a central position in any description of the mineral constituents of a given soil. All silicates are formed of a fundamental structural unit, comprising one silicon ion (Si+4) and four oxygen ions O−2, closely surrounding the silico in a tetrahedral lattice, as shown by figure 3.

Fig. 3.

A Silicate Tetrahedron

The tetrahedra may, based on their net and residual charges, combine in a multiform of combinatorial structures and three-dimensional arrangements to form various kinds and varieties of silicates, which can be categorised into the following fundamental groups:

1.

Orthosilicates: These are discrete units of individual or grouped tetrahedra, made of one, two, three or six tetrahedra per unit — a property, which, as we can see later, is used for further classification of the group

2.

Chain silicates: In this group individual tetrahedra catinate together, by sharing the four tetrahedrally co-ordinated oxygen atoms with the neighbouring silicon atoms, to form infinite chains of formula (SiO3)−2n,

3.

Sheet silicates: In this group three co-ordinated oxygen atoms at the corners of a tetrahedron are shared with adjacent silicon atoms, resulting in the formation of a sheet or a layer of tetrahedra connected together at the three basal corners.

4.

Frame work silicates: These are formed, if all four oxygen atoms per SiO⁴ tetrahedron are shared with adjacent tetrahedra in a framework structure. In the following, each of these four silicate groups or classes will be discussed in some detail.

2.1.1 The orthosilicates

The orthosilicates comprise two subcategories — nesosilicates and sorosilicates. In the first category, the SiO4 — tetrahedra occur as separate units, without shared oxygen atoms, and are linked by metallic cations. This structure (Figure 4a) is not very common in minerals. However, some minerals like olivine, (Mg, Fe, Mn) 2 Si O4, which is an important constituent of basalt, adopt it. Other minerals, made of single silicon tetrahedra are zircon ZrSiO4; topaz A12 (FOH) 2 SiO4, and the garnets, with the general formula:

Fig. 4.

Structure of the orthosilicates

MII3 MIII2 (SIO4) 3, where MII can be Ca²+, Mg²+ or Fe²+, and MIII is Al³+, Cr³+, or Fe+3. This group of minerals occurs in soils formed on igneous rocks due to their higher resistance to weathering. The sorosilicates, themselves, may further be classified into two groups — the pyrosilicates and the cyclosilicates. In the pyrosilicates, (also called disilicates) discrete groups of two tetrahedra share one of the co-ordinated oxygen atoms to form the disilicate anion Si2O7 (see fig 4b). An example is the mineral hemimorphite that has the general formula Zn4 (OH) 2 Si2 O7. It sometimes occurs in soils formed on limestones. However, generally minerals having this structure are quite rare. In the cyclosilicates (the second category of the sorosilicates), three or six tetrahedra may share one or more of their coordinated oxygen atoms to form a trigonal ring, Si3 O9, (Figure 4c) or a hexagonal ring Si6O18 (Figure 4d). Sorosilicates forming trigonal rings are represented by minerals like wollastonite, Ca3Si3O9; or rhodonite, Mn3Si3O9. Cyclosilicates having hexagonal ring structures are represented by minerals like beryl, Be3A12Si6O18, or dioptase Cu6Si6O18. 6H2O.

Figure 5 summarises the classification of the orthosilicates.