Values of the Avrami exponent (n) for different types of crystal nucleation and growth.
\r\n\t
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The number of studies related to the physical properties of oils and fats has been increasing; these properties are broadly the melting and crystallization behavior and the crystalline and oxidative stability of oils and fats.
The crystallization behavior of lipids has important implications in the industrial processing of food products whose physical characteristics depend largely on fat crystals. Such products include chocolates, margarines, spreads, fats for confectionery and bakery, dairy products, and commonly used shortenings [1]. Meanwhile, crystallization is the most important physical problem of oils and fats [2], particularly problems such as unwanted polymorphic transitions, oil exudation, the development of fat bloom, formation of crystalline agglomerates, and fatty bases with a maximum solid fat content or incompatibility of induction periods with certain industrial applications. Thus, recent research has focused on understanding the phenomena involved in the crystallization of lipids in an attempt to achieve effective solutions to stabilize or modify this process, depending on the nature of the raw material and its industrial application. To that effect, the use of emulsifying agents as crystallization modifiers has marked the trend of research in the oils and fats field. In the past, studies were based on the effect of emulsifiers on the crystallization of pure triglycerides or model systems [3, 4, 5], while recent research has focused on the effect of emulsifiers on the crystallization properties of different types of fats such as milk fat [6, 7, 8], low-trans fats [9, 10], palm oil and its fractions [11, 12], cocoa butter [13], in the crystallization of emulsions [14, 15], and production of organogels, which constitute the structuring oils of emulsifiers [16]. While studying the effects of emulsifiers in fatty systems is of great interest for the improvement of industrial bases, particularly with respect to fat for use in chocolate, confectionery, and baking, there is limited research on the role of these compounds as crystallization modifiers of natural and commercial fats [17].
Crystallization of lipids is a serious problem in the food industry with respect to actual industrial processes and post-crystallization events. The crystallization issue presents additional aggravating considerations related to climatic differences between countries and the transport and storage conditions imposed by long distances between producing regions and final distribution regions. Thus, there is a need for appropriate solutions for processes involving crystallization and stabilization of raw materials of significant industrial relevance, such as palm oil and fractionated and interesterified fats, which are now replacing partially hydrogenated fats (or trans fats) in most industrial applications. Therefore, the topic discussed in this chapter is highly relevant to the oils and fats production sector.
Edible oils and fats are essential nutrients of the human diet, playing a vital role in providing essential fatty acids and energy. Chemically, natural oils and fats consist of multi-component mixtures of triacylglycerols (TAGs), which are glycerol esters and fatty acids. Additionally, polar lipids (minority lipids) such as diacylglycerols (DAGs),monoacylglycerols (MAGs), free fatty acids, phospholipids, glycolipids and sterols are found solubilized in the triacylglycerol matrix. The triacylglycerol composition determines the physical properties of oils and fats, affecting the structure, stability, flavor, aroma, storage quality, and sensory and visual characteristics of foods [18].
The physical properties of an oil or fat are of fundamental importance to determine its use. This is particularly true for a large quantity and variety of oils and fats used in various forms, including foods. The difference between the words “oil” and “fat” refers to a fundamental physical property, the fluidity or consistency at room temperature. The components of fat characterize it as a material composed of an intimate mixture in the liquid and solid phases, and its physical state can vary from a viscous fluid to a solid or brittle plastic [19].
Plastic fats consist of a lattice network in a continuous oil matrix. The crystallization process is a spontaneous ordering of the system, characterized by the total or partial restriction of movement caused by physical or chemical links between the triacylglycerol molecules. Differences in crystal shapes result from different molecular packings. A crystal, therefore, consists of molecules arranged in a fixed pattern known as a lattice. Its high degree of molecular complexity allows the same set of TAGs be packaged into several different and relatively stable structures [20].
Crystallization of fats determines important properties of foods, including: (i) the consistency and plasticity of fat-rich products such as butter, margarine and chocolate during the stages of production and storage; (ii) sensory properties such as the melting sensation in the mouth; (iii) physical stability with respect to the formation and settling of crystals, oil exudation and coalescence of particles and emulsions; and (iv) visual appearance, for example the shininess of chocolates and toppings [21]. In most foods, isolated crystallization of TAGs is considered the event of greatest importance, although the crystallization of minority lipids such as DAGs, MAGs and phospholipids plays a fundamental role in the quality of various products [22].
Crystallization is generally divided into four distinct phases. Initially, in order to obtain the formation of crystals from the liquid state, the system must reach the supersaturation zone, in which there is a driving force for crystallization. Once the appropriate driving force to overcome the energy barrier for crystallization is reached, nucleation occurs and molecules in the liquid state join together to create a stable nucleus. After the formation of stable nuclei, a rapid transition to the next stage of crystallization occurs, crystal growth, i.e., during which additional molecules (or growth units) are incorporated into the crystal lattice, decreasing the driving force of supersaturation. Unless restricted by a kinetic constraint, growth continues until the system reaches equilibrium, at which the driving force for crystallization approaches zero and the maximum volume of the crystal phase is obtained [23].
According to Boistelle [24], nucleation involves the formation of molecule aggregates that exceed a critical size, and are therefore stable. Once a crystal nucleus has formed, it begins to grow due to the incorporation of other molecules from the adjacent liquid layer that is continuously filled by the supersaturated liquid surrounding the crystal [24].
A crystal nucleus is the smallest crystal that can exist in solution at a given temperature and concentration. The formation of a nucleus from the liquid phase, i.e., the nucleation process, requires the organization of molecules in a crystalline lattice of critical size after overcoming an energy barrier. The mechanisms of nucleation are generally classified as primary nucleation, which can be homogeneous or heterogeneous, and secondary nucleation. It is currently suggested that nucleation occurs via a two-step process. Molecular oscillations in the liquid phase lead to local organization of molecules into amorphous clusters (instead of crystal embryos, as postulated by classical nucleation theory – Gibbs, 1800), which then aggregate to form an amorphous cluster of critical size. This formation of amorphous aggregates is the first step in nucleation. At some point the molecules in the cluster are transformed into a crystalline structure, which is the second step for the formation of a stable nucleus. The combination of these two events characterizes the induction time before the onset of visual nucleation. This type of nucleation, however, rarely occurs under the conditions of industrial processes. In practice, nucleation is usually dominated by the heterogeneous mechanism in the majority of systems, where external surfaces or catalytic sites, such as molecules of different composition, are used to reduce the energy barrier. Although the exact mechanism of heterogeneous nucleation is not yet fully elucidated, the phenomenon can be described as the result of interactions between the solid particle and the supersaturated fluid, causing the local ordering of molecules for formation of the nucleus. Secondary nucleation is the formation of a new nucleus in the presence of existing crystals, which may occur if microscopic crystalline elements are separate from an already formed surface, thus resulting in crystal fracture into small stable nuclei [22, 23, 25, 26].
When the nuclei formed achieve favorable dimensions, these elements become crystallites whose growth depends not only on external factors (supersaturation, solvents, temperature, impurities), but also internal factors (structure, connections, defects). Consequently, the crystal growth rate can vary by several orders of magnitude. Growth occurs by binding of molecules to a crystalline surface. At the same time, molecules are also detached. There is a continuous movement of molecules on the crystal surface, and the result of these processes determines the rate of growth, which is directly proportional to subcooling and varies inversely with the viscosity of the system [21]. Although nucleation and crystal growth are often considered separate events, they are not mutually exclusive. Nucleation also occurs as crystals grow from existing nuclei [27].
Recrystallization was defined by Fennema [28] as any change in the number, size, shape, orientation or perfection of the crystals after completion of initial solidification.
The basic mechanism of the recrystallization process is size-dependent equilibrium (melting temperature or solubility) documented by the Gibbs-Thomson effect. Small crystals, due to the small radius of curvature of the surface, are slightly more soluble or have a slightly lower melting point than larger crystals. Over time, these differences promote the disappearance of small crystals and growth of larger crystals. These changes generally occur without a change in volume of the crystalline phase, and are driven by the difference in thermodynamic equilibrium based on the size of the crystals. These crystals occur slowly at a constant temperature, but their presence increases with temperature swings as the phenomenon referred to as Melting-Recrystallization becomes dominant. When the temperature rises during a temperature cycle, the crystals melt or dissolve to maintain phase equilibrium. The small crystals, which are less stable, disappear first. When the temperature starts to decrease during the temperature cycle, the volume of the crystal phase increases, but only by growing and without the formation of new nuclei. The mass of small crystals that melted is redispersed among the larger crystals. As the average size of the crystals increases, the number of crystals decreases as a result of these thermodynamic effects. Thus, a dispersion of many small crystals tends to minimize the surface energy (and surface area) by recrystallization [23, 29].
The final stage of crystallization in foods occurs during storage, and a population of crystals undergoes a recrystallization step, reaching a more broad equilibrium state. This phenomenon is of primary concern during storage of foods, and is responsible for changes to the texture of ice cream, fat bloom in chocolates and toppings and exudation of oil in products rich in fat. In lipid systems, the recrystallization process involves changes to the internal arrangement of the crystalline structure via polymorphic transformation [30].
Crystallization kinetics intensively influences the final structure of fats and shows to be closely related to their rheological and plasticity properties. When monitoring the formation of the solid crystalline material with respect to time it is possible to verify the nature of the crystallization process. Characterization of crystallization kinetics can be performed according to the induction time (τSFC) or the nucleation period (relative to the beginning of crystal formation) and the maximum solid fat content-SFCmax. The induction time reflects the time required for formation of a stable nucleus of critical size in the liquid phase [31]. As a definition, the τSFC is the time required for obtaining one crystalline nucleus per unit volume. The τSFC generally increases with increasing isothermal crystallization temperature and decrease of the sample melting point. Another useful parameter for evaluating isothermal crystallization is the crystallization stability time (tcs), defined as the total time for stabilization of the solid fat content at a given temperature. This parameter consists of the sum of the time characteristics for nucleation and crystal growth [32].
The model most widely used to describe the kinetics of isothermal phase transformation is the Avrami model, developed in 1940, which relates the kinetics determined experimentally with the form of growth and final structure of the crystal lattice [33]. The Avrami equation gives an indication of the nature of the crystal growth process and is given by
where SFC(t) describes the solid fat content (%) as a function of time, SFC(∞) is the limit of the solid fat content when time tends to infinity, k is the Avrami constant (min-n), which takes into account both nucleation and growth rate of the crystals and n is the Avrami exponent, which indicates the mechanism of crystal growth [27]. The crystallization half-life (t1/2) reflects the magnitude k and n according to the relationship
Currently, the most common analytical technique for the investigation of crystallization kinetics of fats is nuclear magnetic resonance (NMR). However, various analytical techniques such as differential scanning calorimetry (DSC), polarized light microscopy (PLM), as well as rheological and turbidimetric techniques can be successfully employed. Understanding of the phenomena involved in crystallization kinetics is improved when considering combined use of various instrumental methods [34].
Long-chain compounds, such as fatty acids and their esters, may exist in different crystal forms. Solids of the same composition which may exist in more than one crystal form are called polymorphs. Polymorphism can be defined in terms of the manifestation ability of different cellular structures, resulting from different molecular packings. The crystal habit is defined as the crystal shape. From a crystallographic perspective, the habit reflects the growth direction within the crystal, while morphology outlines the set of faces determined by the symmetrical components of the crystal. This distinction allows crystals of the same morphology to present different crystal habits [26].In fat, crystals are solids with atoms arranged in a regular three-dimensional pattern. A cell is the repeating unit that makes up the complete structure of a given crystal. A sub-cell, in turn, is the smallest structure in the real unit of the cell, defined as the mode of transverse packing of aliphatic chains in the TAGs. The polymorphic forms of a fat are identified based on their sub-cell structure [24]. In lipids three specific sub-cell types predominate, referring to the polymorphsα, β’ and β, according to current polymorphic nomenclature (Figure 1). The α form is metastable with hexagonal chain packing. The β’ form has intermediate stability and orthorhombic perpendicular packing, while the β form has greater stability and triclinic parallel packing. The melting point increases with increasing stability (α→ β ’ →β), as a result of differences in the molecular packing density [35].
The polymorphic nature of the TAGs is well established. It is also well-known that the mixing of different fatty acid fractions in a TAG produces a more complex polymorphic behavior. Thus, saturated monoacid TAGs present simple polymorphism, followed by TAGs with mixed saturated fatty acids. The mixed saturated/unsaturated fatty acids exhibit more complex polymorphisms [36]. TAGs typically crystallize in the α and β’ forms first, although the β form is most stable. This phenomenon is related to the fact that the β form has a higher free energy of activation for nucleation. Polymorphic transformation is an irreversible transformation process of the less stable form to the more stable form (transformation of the monotrophic stage), depending on the temperature and time involved. At constant temperature, the α and β’ forms can transform, as a function of time, to the β form via the liquid-solid or solid-solid mechanisms [37]. The transformation velocity is dependent on the degree of homogeneity of the TAGs. Fats with low variability of TAGs quickly transform into the stable β form. Fats which consist of a random distribution of TAGs can present the β’ form indefinitely. Additionally, factors such as formulation, cooling rate, heat of crystallization and degree of agitation affect the number and type of crystals formed. However, because fats are complex mixtures of TAGs, at a given temperature the different polymorphic forms and liquid oil can coexist [1].
Spatial projections of the crystalline forms α, β \'and β. Packings: (a) H: hexagonal; (b): orthorhombic; (c) T: triclinic [40].
Fats with a tendency to crystalize in the β’ form include soybean, peanut, canola, corn and olive oil, as well as lard. In contrast, cotton and palm oils, milk fat and suet tend to produce β’ crystals that commonly persist for long periods [21]. In particular, for cocoa butter six polymorphic forms are verified as a result of its unique triacylglycerol composition, wherein symmetrical monounsaturated TAGs predominate. The characteristic nomenclature of cocoa butter polymorphs are based on the roman numeral system (I to VI), where the I form is the least stable and the V form is associated with the desirable crystalline habit in chocolates, which may transform during storage into the VI form, which presents improved stability. However, combinations of this nomenclature with Greek nomenclature are typically encountered, where the forms V and VI are recognized as βV and βVI [38, 39].
The crystal structure of fats is important for the formulation of shortenings, margarines and fat products in general, since each crystal shape has unique properties with respect to plasticity, texture, solubility, and aeration. Fat with crystals in the β’ form present greater functionality, because they are softer and provide good aeration and creaminess properties. Therefore, the β’ form is the polymorph of interest for the production of fat-rich foods such as margarine and confectionary and baking products. For the production of chocolates with good physical and sensory characteristics the βV form is the desirable polymorph, since it is associated with properties such as brightness, uniformity, snap characteristic and improved shelf life [18].
X-ray diffraction is an analytical technique used to identify the polymorphism of crystals by determining the dimensions of the crystalline unit and sub-cells. Due to different geometrical configurations, polymorphs diffract x-rays at different angles. In fats, high diffraction angles correspond to short spacings (distances between parallel acyl groups in the TAG) of sub-cells and allow for verifying the different polymorphs [41].
The lipid composition and crystallization conditions influence the crystal habit, i.e., different crystal morphologies are possible. Crystals aggregate into larger structures forming a lattice, which characterizes the microstructural level of a fat. The microstructure concept includes information regarding the state, quantity, shape, size, and spatial and interaction relationship between all components of the crystal lattice and has tremendous influence on the macroscopic properties of fats [42].
According in [43], the microstructural structure or meso-scale of a crystalline lattice for a fat may be defined as the set of structures with dimensions between 0.5μm and 200μm. Its quantification is achieved primarily by visualization of its geometry. Structural levels in a typical crystal lattice are defined when the fat crystallizes after its complete fusion. Like nanostructural elements (0.4-250nm), TAGs crystallize in specific polymorphic states. Most tags crystallize as spherulites, which implies that crystal growth occurs radially. The formed crystals grow to dimensions of 1 to 4 μm and then combine to form agglomerates (larger than 100μm) in a process governed by mass and heat transfer. The aggregation process continues until a continuous three-dimensional network is formed from the combination of these microstructures, trapped in the liquid fat phase [44]. This structural hierarchy has been recognized by several researchers. However, the arrangement of molecules in the crystalline state also depends on factors such as the cooling rate, crystallization temperature and stirring speed, if necessary [45].
Crystal growth can occur in one, two or three dimensions, characterizing the formation of needle, disk, or spherulite-shaped crystals, respectively [46], and these shapes can be predicted from the results shown by the value of the Avrami exponent (n) (Table 1). According in [47], the application of fats in food products requires that the average diameter of the crystals is less than 30μm to avoid a sensation of grittiness in the mouth.
\n\t\t\t\tAvrami exponent (n)\n\t\t\t | \n\t\t\t\n\t\t\t\tType of crystal growth \n\t\t\t | \n\t\t\t\n\t\t\t\tExpected nucleation \n\t\t\t | \n\t\t
3+1 = 4 | \n\t\t\tgrowth of spherulites | \n\t\t\tsporadic nucleation | \n\t\t
3+0 = 3 | \n\t\t\tgrowth of spherulites | \n\t\t\tinstantaneous nucleation | \n\t\t
2+1 = 3 | \n\t\t\tgrowth of disks | \n\t\t\tsporadic nucleation | \n\t\t
2+0 = 2 | \n\t\t\tgrowth of disks | \n\t\t\tinstantaneous nucleation | \n\t\t
1+1 = 2 | \n\t\t\tgrowth of rods | \n\t\t\tsporadic nucleation | \n\t\t
1+0 = 1 | \n\t\t\tgrowth of rods | \n\t\t\tinstantaneous nucleation | \n\t\t
Values of the Avrami exponent (n) for different types of crystal nucleation and growth.
(SHARPLES, 1966) [48]
Another factor that characterizes the formation of the microstructural network of fats is the fractal dimension. The fractal dimension is a parameter that describes the spatial distribution of the mass within the crystal lattice [44]. Fractal geometry was proposed by Benoit Mandelbrot (1982) as a method for quantifying natural objects with a complex geometrical structure which challenged quantification by regular geometric methods (Euclidean geometry). In classical Euclidean geometry, objects have integer dimensions: the reader would be familiar with the reasoning that a line is one-dimensional, a plain a two-dimensional object and the volume of an object is three-dimensional. Thus, Euclidean geometry is suitable for measuring objects that are ideal, or regular. One can imagine that if enough twists are placed on a line or a plane, the resulting object can be classified as an intermediate between a line and a plane. The dimension of such an object is fractional (i.e., between 1 and 2 or between 2 and 3) and such an object can be classified as a fractal object, based on the fact that instead of presenting a Euclidean dimension (integer), it has a fractional dimension [49]. One of the most important characteristics of fractal objects is their similarity, in other words, fractals objects look the same in different magnitudes, at least in a certain range of scales.
Most scientific research on crystallization of fats has been directed towards establishing relationships between lipid composition or polymorphism and macroscopic properties of fats, without in-depth consideration of the microstructure of the crystal lattice, which can lead to failures in predicting the macroscopic properties [50]. In Marangoni and Rousseau [51] investigated the possibility that the solid fat content and/or polymorphic shape of the crystals is not determinant for the mechanical properties of mixtures containing milk fat with canola oil, but instead the macroscopic structure of the crystal lattice in the liquid oil matrix. From the study of fractal dimensions and the application of this theory to the rheological study of milk fat with canola oil moistures, it was observed that the fractal dimension (Db) was the only “indicator” in accordance with the associated changes to the rheology of the product resulting from interesterification. Traditional physical indicators, such as polymorphism and solid fat content, failed to demonstrate the expected changes. Thus, the study confirmed the importance of the fractal dimension, a fundamental indicator of the crystal lattice capable of explaining changes in rheology of fats not attributed to other measurable properties of the network [49]. According in [27], systems with higher fractal dimension values demonstrate higher packing orders of the microstructural elements.
One of the methods most used for calculating the fractal dimension is the box counting method, where grids with length li are placed on the micrographs of the crystalline lattice of a fat obtained by the polarized light microscopy technique. Any lattice containing particles above a threshold value is considered an occupied lattice (solid). The number of occupied grids Ni of side length li is counted. This process is repeated for grids with different lateral lengths. The fractal dimension of box counting, Db, is calculated as the opposite slope of the linear regression curve for the log-log graph of the number of occupied grids Nb versus the lateral length lb, given by
To reduce errors, the grids with extreme sizes should be exempted from the calculation [52]. Polarized light microscopy (PLM) is the most widely used technique for visualization of microstructural network of fats and has been applied so as to explain the differences in texture of fat mixtures, showing crystalline types and morphological alterations in crystal growth [53].
Control of crystallization to prevent crystal growth or to achieve the desired crystalline attributes is crucial for obtaining high-quality products with long useful life. Understanding the principles that underlie the crystallization phenomena is necessary to achieve this control [23]. Figure 2 presents a schematic of the crystallization process, storage of fats and associated mechanisms.
The behavior of crystallization, polymorphic transformation and microstructure of a fat is due to a combination of individual physical properties of each TAG and phase behavior of different TAG mixtures. In general, the specific composition of a fat is one of the most important factors for final development of the crystal structure [54].
Process schematic of the process involving crystallization and storage of fats. Adapted from [55].
Crystallization of fats is a critical factor associated with the structure and properties of most foods. The stability of many processed food products is influenced by changes in the physical state of the fats and changes in the crystallization processes, since the events of nucleation and crystal growth occur simultaneously at different rates as they are affected by conditions such as degree and rate of super-cooling, viscosity and agitation [13].
In the initial stages of food processing, the relative rates of nucleation and crystal growth determine the distribution, shape and size of the crystals, parameters that are directly related to the characteristics of consistency and texture. However, during the storage phase, several post-crystallization phenomena may occur, significantly affecting the properties and stability of foods. These include polymorphic transitions to thermodynamically more stable phases, formation of new crystals and crystal growth, and migration of oil or small crystals. It should be noted, however, that such events are not chronological; polymorphic transitions can occur even in the early stages of processing [31].
Additionally, in post-crystallization processes the phenomena known as sintering or bonding of adjacent surfaces can be verified, as well as spontaneous dissolution, also known as Ostwald ripening. The term sintering is described as the formation of solid bridges between fat crystals, with formation of a cohesive network associated with the undesirable increase in the hardness of the fat phase. Ostwald ripening, in turn, is associated with dissolution of previously existing small crystals in the fat phase and development of crystals with undesirable dimensions and weak crystal lattices, which causes loss of consistency of the products [56].
Furthermore, in some specific products the control of crystallization means, above all, avoiding this process, even if it is thermodynamically favored or due to storage or processing conditions [8]. Thus, control of crystallization and polymorphic transitions in fats is a factor of fundamental importance for the food industry.
Interesterification is a technological alternative to the partial hydrogenation process, since it enables the production of oils and fats with specific functionalities. Due to the growing concern of the nutritional impact of trans fatty acids on health, interesterification has been indicated as the main method for obtaining plastic fats with low levels of trans isomers or absence of these compounds. In contrast to hydrogenation, this process does not promote the isomerization of double bonds of fatty acids and does not affect the their degree of saturation [57].
In the interesterification process the fatty acids are rearranged in the glycerol molecule. Interesterification is promoted by an alkaline catalyst (chemical interesterification) or by lipases (enzymatic interesterification). The alkaline catalysts most frequently used are sodium methoxide and sodium ethylate [58]. In chemical interesterification the fatty acids are randomly distributed in the glycerol molecule along the three available positions within each molecule. When specific lipases are used to catalyze the interesterification reaction, rearrangement can occur in the sn1 and sn3 positions of the glycerol molecule, maintaining the sn2 position [59].
Chemical interesterification is currently the process most utilized by industry. The random distribution of fatty acids along the glycerol molecules leads to changes in the triacylglycerol composition, which alters the overall solids profile of the fat. In interesterified fats, the random distribution of fatty acids results in great variability of TAGs, with intermediate melting points (S2U and U2S). Such variability in TAGs, associated with the formation of partial acylglycerols, promotes slower crystallization and indefinite maintenance of the polymorphic form β´ [58, 60, 61]. Other observations, such as decreased size of the crystals as well as distribution in the crystal lattice, were also observed in some studies [62].
Palm oil is obtained from the mesocarp of the fruit Elaesis guineensis. It is semi-solid at room temperature, consisting primarily of TAGs of palmitic and oleic acids. Palm oil is the vegetable oil most used worldwide in the food industry. In June 2013, world production of palm oil reached 58 million tons, surpassing the production of soybean oil [63]. As a result of increased production, many studies are focused on palm oil, especially regarding its crystallization behavior and nutritional aspects. Compared to other vegetable oils, palm oil presents a unique and differentiated fatty acid composition, containing similar percentages of saturated and unsaturated fatty acids. It also presents a significant content of saturated fatty acids (10 to 16%) in the sn-2 position of the TAGs, as well as significant levels of palmitic acid (44%). In addition to these features, palm oil contains small percentages of MAGs and DAGs as minor components, which are produced during maturation of palm fruits and oil processing. The DAGs, specifically, correspond to 4-8% of the composition of palm oil, with variations according to origin and processing conditions. The removal of these compounds, however, is difficult even under optimal refining conditions [18, 64, 65].
The crystallization behavior of palm oil is extremely important from a commercial point of view, because it is characterized by the crystal habit β’, a fact that, combined with its characteristics of plasticity, ensures its application in margarines, spreads, bakery and confectionery fats, as well as general purpose shortenings. The functional properties of palm oil and its fractions appear to be strongly related to its composition and the quantity and type of crystals formed at the temperature of application. However, the crystals of palm oil require a long time for α→ β ’ transition, a factor considered inadequate from an industrial process standpoint. Resistance to transformation into β’ is mainly attributed to the DAGs. Recent studies on the interactions between TAGs and DAGs in palm oil during crystallization show that the latter have a deleterious effect on the characteristics of crystallization, with intensity proportional to the concentration of these minority lipids in palm oil and its fractions [66, 67]. According in [68], the negative effect of DAGs on the crystallization of palm oil may be related to the low nucleation rate of TAGs in the presence of these compounds.
In addition to the slow crystallization of palm oil, another factor of great concern in industry is its post-processing stability. Palm oil is often associated with hardening problems during storage. In some products based on this raw material, undesired crystal growth occurs which results in gritty texture and poor spreadability [69]. These crystalline shapes may reach dimensions greater than 50 μm after a few weeks of storage, leading to non-uniformity of the processed products [68]. In margarines, specifically, the formation of crystal agglomerates with mean diameter between 0.1 and 3mm is observed, which can easily be observed with the naked eye [70]. In [71] found that the main TAGs of palm oil, 1-palmityl-2-oleoyl-palmitine (POP) and 1-palmityl-diolein (POO), have limited miscibility with each other, which results in formation of large POP crystals surrounded by POO. When these agglomerates are formed, there occurs the joining of other saturated TAGs in a process that promotes β’ →β transition. Therefore, to ensure the stability of the β’ polymorph in palm oil-based products this is a question of great industrial interest, given the great economic importance associated with the use of this raw material.
The product of the first fractionation stage of palm olein is termed the soft palm mid fraction (soft PMF), which presents high levels of monounsaturated triacylglycerols, rapid melting and tendency to crystallize in β’, making it an excellent raw material for the production of margarines and shortenings in general [72, 73].
Classically, two methods are proposed for the production of soft PMF: the olein route (most common in Asia) and the stearin route, which is preferentially used in South America because of the need for olein with high iodine index in the first fractionation stage. The best CBE’s are obtained via the olein route, where the second fractionation stage of the triacylglycerols SSU-SUS focuses selectively on soft PMF. In dry fractionation, soft PMF concentrates more than 73% of SSU-SUS triacylglycerols, and the content of SSS triacylglycerols is low. Thus, refractionation of soft PMF produces an excellent hard PMF, particularly enriched in SSU-SUS triglycerides (85%-90%) with low content of SSS triglycerides, and the DAG content can be kept low enough to avoid any adverse effect on the crystallization properties of the fraction [74].
Due to the closely related structural properties, TAGs can produce co-crystals by intersolubility, which frequently present solid solutions, monotectic interactions, eutectic systems and formation of molecular compounds [1]. As a result, the efficiency of fractionation depends not only on the separation efficiency, but is limited by the phase behavior of TAGs in the solid state. Thus, intersolubility of TAGs is a challenge in the dry fractionation process, including the route: olein
Most natural oils and fats have limited application in their unaltered forms, imposed by their particular composition of fatty acids and TAGs. Thus, oils and fats for various industrial applications are chemically modified by hydrogenation or interesterification, or physically by fractionation or mixture [75]. Although used for a long time, partial hydrogenation results in significant formation of trans fatty acids, associated with negative health effects [76].
In Brazil, controversial issues surrounding the role of trans fatty acids in the diet have led to progressive changes in legislation, aiming to include more information for consumers. Resolution RDC No. 360, of December 23, 2003, approved by the MERCOSUR, obligated the declaration of trans fatty acids on the nutritional label of foods. Companies had until July 31, 2006 to meet regulations, so that the trans fat content is declared in relation to the standard portion of a certain food, together with statements of total and saturated fats [77]. In response, Brazilian industries opted for the progressive substitution of trans fat in many products through the development of base fats with functionality and economic viability equivalent to partially hydrogenated fats, but without substantial increase in the content of saturated fatty acids in foods.
In this sense, interesterification was found to be the main alternative for obtaining plastic fats with low levels of trans isomers or lack thereof. In particular, chemical interesterification of liquid oils with fully hydrogenated oils (hardfats) is currently the alternative of greatest versatility to produce zero trans fats, producing base fats favorable for the preparation of commonly used shortenings [61]. The use of blends, i.e., mixtures of fats with different physical properties, and fractionation also represent additional alternatives to obtain base fats with appropriate physical and plasticity properties to be used in various products, although with potential limited by the chemical composition of the raw materials [21].
Although the interesterification, fractionation and mixing processes are very functional from a technological point of view, the substitution of partially hydrogenated fats in food products, especially in shortenings and confectionery products, is currently a challenge since appropriate crystallization and texture properties are difficult to obtain in the absence of trans fatty acids [78].
In particular, adequacy of crystallization kinetics of these base fats is of utmost importance so that their use may be adjusted to the limitations of industrial processes and to improve control of processing steps that involve recrystallization of the fat fraction, ensuring quality of the final product [79]. Contrarily, previously standardized processing times and equipment must be altered according to the characteristics of the fat used. This fact becomes particularly important as new fat fractions began to replace partially hydrogenated fats in most industrial applications, mainly in the production of biscuits and bakery products, where it is noted that fats with the same apparent solids profile present very different crystallization properties [80]. In the specific case of interesterified fats, the formation of partial acylglycerols, such as MAGs and DAGs as a result of chemical interesterification, can influence the crystallization kinetics via alterations to the crystal nucleation process [81]. According in [82], 0.1% of the catalyst sodium methoxide, used for randomization, can produce between 1.2 and 2.4% of MAGs+DAGs. Because the typical catalyst content used industrially ranges from 0.1 to 0.4%, concentrations of these minority lipids may be greater than 9%. Although minority lipids present influence on the crystallization properties of these fats, their complete removal is still difficult and expensive, especially on a large scale [22].
Considering that in the Brazilian industry this substitution process is relatively recent, the problems of crystallization behavior due to the unsuitability of new fat fractions are numerous and aggravated, mainly due to regional differences in climate and conditions of transport and storage. In this context, highlighted problems include unwanted polymorphic transitions, oil exudation, development of fat bloom, formation of crystalline agglomerates, and base fats with a maximum solid fat content or induction periods incompatible with certain industrial applications. Studies on modification, stabilization and control of crystallization of these base fats are therefore of crucial importance for development of the edible oils industry.
In a classic definition, an emulsifier is an expression applied to molecules which migrate to interfaces between two physical phases, and are therefore more concentrated in the interfacial region than in the solution phase [83]. The main molecular characteristic of an emulsifier is its amphiphilic nature, characterized by an ionic group (polar region) and a hydrocarbon chain (nonpolar region). According to their polar and nonpolar regions, emulsifiers are designated as hydrophilic or lipophilic, which affects their solubility in water or oil [84]. Thus, the term hydrophilic-lipophilic balance (HLB) was suggested, which measures the affinity of an emulsifier for oil or water. Regarding emulsifiers in foods, lipophilic properties are generally the most important, but the hydrophilic-lipophilic balance (HLB) may vary considerably according to the chemical composition of the emulsifier. The dual affinity of emulsifiers results in the formation of a single phase between initially immiscible substances (emulsion). Furthermore, these compounds perform functions that in some products are not related to emulsification, including modification of the crystal habit during crystallization of oils and fats [83].
The concept of HLB makes it possible to characterize the various emulsifiers or mixtures of emulsifiers. In general, the following guidelines are used for applying an emulsifier based on its HLB:
HLB of 3-6: a good water/oil emulsifier;
HLB of 7-9: a good wetting agent;
HLB of 10-18: a good oil/water emulsifier.
Nevertheless, the HLB value is limited because it provides a one-dimensional description of the emulsifier properties, and omits information such as the molecular weight and temperature dependence. It is also difficult to calculate useful HLB values for various important emulsifiers in food applications (eg: phospholipids). Additionally, HLB values do not include the important crystallization properties of emulsifiers [85].
Regarding the crystallization properties, in the crystal structure of emulsifiers, the predominant factor is the hydrophilic portion which is the relatively larger portion of the molecule. The size of the hydrophilic group, along with the extension and spatial distribution of hydrogen bonding between adjacent groups, has a much larger influence on the molecular packing of the crystal than the nature of the fatty acid chain. A simple emulsifier, such as a monoacylglycerol, generally crystallizes in the double chain length (DCL), while those with larger hydrophilic groups more frequently crystallize in the SCL configuration (Figure 3) [83].
Configurations in (a) DCL (double chain length) and (b) SCL (single chain length) (STAUFFER, 1999)
Among crystallization properties, an important feature of emulsifiers is their ability to create mesophases. Mixtures of emulsifiers with water form different physical structures, depending on the emulsifier/water ratio and temperature. These mixtures are opalescent dispersions, often called “liquid crystals”, but are better known as mesophases. This term (which means “between stages”) reflects the nature of the mixture. On a micromolecular level, the emulsifier agent and water are separated phases, but at the macro level the mixture becomes uniform and is stable (that is, the phases do not separate) [86]. Liquid crystals are thermodynamic mesophases of the condensed material with a certain degree of ordering between the crystalline solid and liquid states [87]. There are two main families of liquid crystals: thermotropic and lyotropic. Thermotropic liquid crystals are composed of molecules, or mixture of molecules, which exhibit shape anisotropy (also known as anisometry). These molecules may have the shape of rods (most common), disks and arcs, among others. The structural and ordering differences of these individual molecules occur as a function of temperature, and therefore are called thermotropic. On the other hand, lyotropic liquid crystals are mixtures of amphiphilic molecules and polar solvents, which under determined conditions of temperature, pressure and relative concentrations of different components, present the formation of aggregated molecular superstructures, which are organized in space, showing some degree of order [88]. The amphiphilic molecules such as emulsifiers may present both behaviors (thermotropic and lyotropic) in this case, called amphotropic liquid crystals [88, 89]. A simplified schematic of the formation of some thermotropic and lyotropic mesophase structures is shown in Figure 4.
Structural schematic of the thermotropic and lyotropic mesophases formed by n-octyl β-D-glucopyranoside. Adapted from [89].
In addition to their known functions of emulsification and stabilization of emulsions, emulsifiers can modify the behavior of the continuous phase of a food product, giving it specific benefits. In fat-rich products, emulsifiers may be used to control or modify the crystallization properties of the fat phase. Study of the effects of emulsifiers in fat systems is of great interest to improve industrial products, particularly with respect to fat for use in chocolate, confectionery and baking. However, the role of these compounds as modifiers of crystallization in natural and commercial fats is little exploited in technical literature [17]. To date, the vast majority of studies on the use of emulsifiers as modifiers of the crystallization process in fats were carried out with fully hydrogenated oils, model systems or pure TAGs, and therefore do not reflect the need to control crystallization in fats for industrial application [9, 90].
In general, the effect of emulsifiers appears to be related to different crystalline organizations and the creation of imperfections. Some of them can slow transformations via steric hindrance, while others promote these transformations by favoring molecular displacements [3]. Two different mechanisms have been reported in literature to interpret the effect of emulsifiers on crystallization of fats. The first refers to the action of these additives as hetero-nuclei, accelerating crystallization by direct catalytic action as impurities. During crystal growth, emulsifiers would be adsorbed at the surface of the crystals and would therefore modify the incorporation rate of TAGs and crystal morphology. The second mechanism, of greater consensus among various authors, considers that the TAGs and emulsifiers would be amenable to co-crystallize due to the similarity between their chemical structures. Thus, the structural dissimilarity also entails delays in nucleation and potential inhibition of crystal growth [7, 86].
According to this second mechanism, emulsifiers are associated with triacylglycerol molecules by their hydrophobic groups, especially through acyl-acyl interactions. The acyl group of emulsifiers determines its functionality with respect to the TAGs. The main effects of these additives on the crystallization of fats occur during the stages of nucleation, polymorphic transition and crystal growth, altering physical properties such as crystal size, solid fat content and microstructure. The question of promoting or inhibiting crystallization, however, is still debatable. In general, studies indicate that emulsifiers with acyl groups similar to the fat to be crystallized accelerate this process [12].
Currently, it is known that the behavior of emulsifiers during the crystallization of fats can be divided into three cases: (1) limited miscibility between emulsifier molecules and TAGs: in this situation the emulsifier acts as an impurity and the interaction results in imperfect crystals, which may promote or retard crystal growth and polymorphic transitions, depending on the compatibility of hydrophobic ends in their structures; (2) high degree of miscibility between emulsifiers and TAGs that promotes the formation of molecular compounds; (3) total immiscibility between emulsifiers and TAGs, where emulsifiers can act as crystallization germs and microstructure modifiers [11, 86].
Emulsifiers with high potential for controlling crystallization of base fats include sorbitan esters of fatty acids, fatty esters and polyesters of sucrose, commercial standard lecithin and chemically modified lecithin, and the polyglycerol polyricinoleate [30]. Many studies have confirmed that emulsifier affect the crystallization induction times, the composition of nucleation germs, rates of crystal growth and polymorphic transitions [91]. However, the results are still very incipient, and require greater explanation.
While the derivatization of oils and fats to produce a variety of emulsifiers with a wide range of application has shown to be well established for many years [92], the industrial production of emulsifiers based on oils, fats and carbohydrates is relatively new. Such emulsifiers result from a product concept based on the exclusive use of renewable resources, where sucrose, glucose and sorbitol are the most used raw materials in industry. The sugar-based emulsifiers most used in the food industry are sorbitan and sucrose esters.
Sorbitol is a hexameric alcohol, obtained by the hydrogenation of glucose. Its free hydroxyl groups can react with fatty acids to form sorbitan esters (SE). In SE production, a reaction mixture containing a specific fatty acid, sorbitol and the catalyst (sodium or zinc stearate) is heated in an inert atmosphere to promote simultaneous esterification and cyclization reactions. The fatty acid/sorbitol mole ratio determines the formation of monoesters and triesters. The SE most well-known and used industrially include lauric, palmitic, stearic and oleic acids [17]. Figure 5 shows the chemical structure of a sorbitan tristearate.
Sorbitan tristearate (STS or Span 65) and sorbitan monostearate (SMS) are recognized for their ability to efficiently modify crystal morphology and consistency of fats, such as anti-bloom agents in confectionery products containing cocoa butter and in substitutes of cocoa butter, indicated as potential controllers of crystallization. It is assumed that these compounds can delay or inhibit the transition of fat crystals to a more stable form. Moreover, the SE showed to be particularly effective in stabilizing the polymorph β’ in margarines and modification of the solid fat content of fats in general, promoting fusion profiles adequate for the body temperature [18]. They can also be selective as dynamic controllers of polymorphic transitions in fat, due to their ability to create hydrogen bonds with neighboring TAGs, in a process known as The Button Syndrome, whereby the presence of a specific emulsifier does not form a preferred polymorph, but rather controls the degree of mobility of the molecules and their potential to undergo configurational changes. In this process, emulsifiers can modulate the polymorphic transformations in the solid state or via the liquid state, and the temperature regime used to control the physical state of crystals during the polymorphic transition and extension of the mobility of the molecules, thereby regulating the rate of polymorphic transformation [4].
Chemical structure of Sorbitan Tristearate (STS).
According in [91], STS is the additive with greatest potential for modification of crystallization in cocoa butter, particularly in inhibiting the βV →β VI transition and fat bloom due to its high melting point (55°C) and chemical structure similar to the TAGs present in the oils and fats, permitting facilitated co-crystallization by this emulsifier and formation of solid solutions with these TAGs. In [93], the addition of 0.5% (w/w) of STS to base fats for margin had a stabilizing effect on the polymorph β’. According in [11] observed the formation of small crystal aggregates in mixtures of palm oil/palm kernel olein when adding 0.09% (w/w) of STS, in addition to increasing the rate of crystallization of these mixtures. In a review article, in [16] emphasized the use of STS and/or combinations thereof with other emulsifiers such as soy lecithin, the current alternative of greatest interest for the control of polymorphic transitions and structuring of the crystal lattice in fats, since the TAGs-STS interaction promotes the formation of regular crystals that melt at 40°C, the melting point characteristic of most base fats for industrial applications.
Sucrose fatty esters can be used in a wide range of food applications and are mainly utilized in the bakery, confectionery, desserts and special emulsion industries [94]. Sucrose esters, particularly mono-and di-esters, are extremely functional emulsifiers, since they provide a number of unique advantages for the food industry. They are non-toxic compounds, without taste or odor, easily digested sucrose and fatty acids, as well as biodegradable under aerobic and anaerobic conditions. They are produced by interesterification of sucrose and fatty acids by various reaction types and conditions. Their structure is typically composed of polar and nonpolar groups in the same molecule as other emulsifiers, but the eight possible positions for esterification with fatty acids allow for these molecules to obtain different lipophilic/hydrophilic properties. Partially esterified sucrose esters, especially the mono-, di-and tri-esters, are more versatile for use in food applications, where the degree of esterification is controlled by the fatty acids/sucrose ratio in the reaction mixture. Monoesters (~70% of monoesters) are hydrophilic, while the di-, tri-, and polyesters are increasingly hydrophobic [95]. The degree of saturation and size of fatty acid chains used also significantly influences the properties of these compounds [17, 86]. Figure 6 shows the chemical structure of a sucrose ester of stearic acid and that of behenicacid.
Chemical structures of: (a) sucrose stearate and (b) sucrose behenate.
The fatty acids most commonly used in sucrose esters are the lauric (C12), myristic (C14), palmitic (C16), stearic (C18), oleic (C18) and behenic acids (C22). By changing the nature or number of fatty acid groups, a wide range of HLB values can be obtained. Commercial sucrose esters are mixtures with various degrees of esterification, due to their complexity, and exhibit diverse behaviors, like lipids. Consequently, they are used in studies on the crystallization of fats. The sucrose esters most studied to date are esters of stearic acid and palmitic acid, especially in the studies of [9, 96, 97]. However, according to [9], few studies explore the effect of these emulsifiers on the induction period, and the rate of crystallization and development of polymorphic forms in fatty systems.
We thank the financial support of FAPESP (Brazil) Grant Proc. 2009/53006-0. M. A. F. Domingues was the recipient of a scholarship from the Brazilian Ministry of Education (CAPES).
Increasing world population has resulted in higher consumption of goods and services that has driven a substantial increase of organic wastes originating from households, industry, and agriculture [1]. Much of the organic wastes are highly infectious as they contain a variety of pathogenic microorganisms. Dumping of organic wastes in open areas generates serious environmental issues such as the accumulation of heavy metals in soil, pollution of ground and surface waters due to leaching and run-off of nutrients. These organic wastes when applied directly to agricultural fields cause soil environment-related problems including phytotoxicity [2]. These wastes represent a valuable organic resource, which could be recycled and transformed into nutrient rich fertilizer and/or soil conditioner [3, 4, 5]. Moreover growing awareness about adverse effects of agricultural chemicals on human health has increased interest in organic agriculture [6]. Organic agriculture also promotes ecological conservation due to judicious use of natural resources [7, 8, 9]. In demand for safe and sustainable strategies to treat organic wastes includes best known practices of composting and vermicomposting for biological stabilization of solid organic wastes by transforming them into a safer and more stabilized material that can be used as a source of nutrients and soil conditioner in agricultural applications [10, 11, 12]. Vermicomposting is one of the most efficient means to mitigate and manage environmental pollution problems [13]. Recently, many studies are being done to establish vermicompost as one of the preferred organic substitutes to chemical fertilizers [14, 15]. Vermicompost is more rich in NPK, micronutrients and beneficial soil microbes (nitrogen fixing and phosphate solubilizing bacteria and actinomycetes), an excellent growth promoter and protector for crop plants [16, 17] than compost [18, 19].
\nVermicomposting (vermis from the Latin for worm) is a mesophilic process [20] which involves a joint action of earthworms (active at 10–32°C) and mesophilic microbes [21] for the conversion of organic wastes into a valuable end product known as vermicompost. Whereas, composting involves the degradation of organic waste by microorganisms under controlled conditions, in which the organic material undergoes a characteristic thermophilic stage that allows sanitization of the waste by elimination of pathogenic microorganisms [22]. Composting is also used to treat manures, green wastes or municipal solid wastes [23]. However, vermicomposting gives a higher-quality end product than composting due to joint action of enzymatic and microbial activities that occur during the process [24]. This process is faster than traditional composting as the material passes through the earthworm gut, whereby the resulting earthworm castings are rich in microbial activity and plant growth regulators, and fortified with pest repellence attributes as well [25, 26]. Compared to traditional composting method, vermicomposting also results in mass reduction, shorter processing time, and high levels of humus with reduced phytotoxicity [27]. Thus, vermicompost is considered an ideal manure for organic agriculture as it is nutrient rich and contains high quality humus, plant growth hormones, enzymes, and substances that are able to protect crops against pests and diseases [28, 29]. Moreover, vermicompost has high porosity, aeration, drainage, and water-holding capacity [20]. In addition to increased N availability, C, P, K, Ca and Mg plant nutrient availability in the earthworm casts are also found [30]. Plant growth hormones namely cytokinins and auxins are found in organic wastes processed by earthworms [31]. They also release certain metabolites, such as vitamin B, vitamin D and similar substances into the compost [32]. Thus, earthworms accelerate the mineralization rate and convert the manures into casts with higher nutritional value and degree of humification than traditional method of composting [33]. The composition of commonly available nutrients in vermicompost is as follows: Organic carbon 9.5–17.98%, Nitrogen 0.5–1.50%, Phosphorous 0.1–0.30%, Potassium 0.15–0.56%, Sodium 0.06–0.30%, Calcium and Magnesium 22.67–47.60 meq/100 g, Copper 2–9.50 mg/kg, Iron 2–9.30 mg/kg, Zinc 5.70–11.50 mg/kg, Sulfur 128–548 mg/kg [34]. Hence, vermicomposting enables biological transformation of wastes into a valuable organic fertilizer [35, 36]. Vermicompost is popularly called as black gold and has become one of the major components of organic farming system [26].
\nEarthworms are invertebrates belonging to the phylum Annelida, class Oligochaeta and family Lumbricidae. The earthworms are long, elongated, cylindrical, soft bodied animals with uniform ring like structures consisting of segments along the length of their body outwardly highlighted by circular grooves called annuli. On the ventral surface of sides of the body each segment bears four pairs of short, stubby bristles, or setae used for its movement. Earthworms have an opening at the anterior end is mouth and the one at the posterior is anus. Earthworms possess both male and female gonads, so are called as hermaphrodites. They deposit their eggs in a cocoon without any larval stage. At the time of egg laying, the sexually mature worms contain a distinctive epidermal ring just beneath the anterior segments called, clitellum, which has gland cells to form a viscid, girdle like structure known as cocoon. The number of fertilized ova in each cocoon has 1–20 lumbricid worms.
\nThere are about 3320 species of earthworms all over the world [37], but hardly 8–10 species are suitable for vermicompost preparation. Earthworms have been extensively utilized for the recycling of a variety of organic wastes like municipal solid wastes [38] wheat straw [39], sewage sludge [40], forestry waste [41], vegetable waste [42], farmyard manure [43], sorghum stalk, wheat straw, paddy straw [44], coir pith [45]. Renowned scientists, Charles Darwin called earthworms as the ‘unheralded soldiers of mankind’, and Aristotle described them as the ‘intestine of earth’, as they could digest a wide range of organic materials [46, 47]. On the basis of morpho-ecological characteristics, earthworms have been classified into three categories [48]; Anecic (Greek word “out of the earth”) – these are burrowing worms that only come to the surface at night to drag food down into their permanent burrows deep within the mineral layers of the soil. Endogeic (Greek word “within the earth”) – these are also burrowing worms but their burrows are typically more shallow and they feed on the organic matter inside the soil, so they come to the surface only rarely. Epigeic (Greek word “upon the earth”) – these worms live on the surface litter and feed on decaying organic matter. They do not have any permanent burrows. These “decomposers” are the type of worm used in vermicomposting. Two tropical species, African night crawler, Eudrilus eugeniae (Kinberg) and Oriental earthworm, Perionyx excavates (Perrier) and two temperate ones, red earthworm, Eisenia andrei (Bouche) and tiger earthworm, Eisenia fetida (Savigny) are extensively used in vermicomposting [49, 50, 51]. Most vermicomposting facilities and studies are using the worms E. andrei and E. fetida due to their high rate of consumption, digestion, and assimilation of organic matter, tolerance to a wide range of environmental factors, short life cycles, high reproductive rates and endurance and resistance during handling [52]. A few other species Drawida nepalensis, Lampito mauritrr. Dichogaster spp., Polypheretima elongate, Amynthas spp. Dendrobaena octaedra, Eisenia hortensis [53] have also been used for composting under specific conditions.
\nEarthworms promote the growth of “beneficial decomposer aerobic bacteria” in organic waste material and also act as a grinder, crusher, chemical degrader and a biological stimulator of waste material [54, 55]. Earthworm hosts millions of decomposer (biodegrader) microbes [56], hydrolytic enzymes and hormones that helps in rapid decomposition of complex organic matter into vermicompost in a relatively smaller duration of 1–2 months [57] as compared to traditional composting method which takes nearly 5 months [58]. The mechanism of formation of vermicompost by earthworms occurs in following steps; organic material consumed by earthworm is softened by the saliva in the mouth of the earthworms. Food in esophagus is further softening and neutralization by calcium and physical breakdown in muscular gizzard results in particles of size <2 μ, thereby giving an enhanced surface area for microbial processing. This finally ground material is exposed to various enzymes such as protease, amylase, lipase, cellulase and chitinase secreted in lumen by stomach and small intestine [12]. Moreover, microbes associated with intestine facilitate breaking down of complex biomolecules into simple compounds. Only 5–10% of the ingested material is absorbed into the tissues of worms for its growth and the rest is excreted as vermicast. The vermicast is a good organic fertilizer and soil conditioner. High-quality vermicast can be produced by worms such as the red wrigglers (E. fetida) as it contains humus with high levels of nutrients that has good potential for the production of organic fertilizer. Vermiwash is a liquid fertilizer and used as a foliar spray produced by passing water through columns of vermiculture beds [59].
\nOptimum conditions of temperature 15–20°C (limits 4–30°C), Moisture content 80–90% (limits 60–90%), Oxygen – Aerobicity, Ammonia content of the waste Low: <1 mg·g–1 (0.016 oz.1b–1), Salt content Low < 0.5% and pH of 5–9 are preferred for stable life cycle of earthworm.
\nTo attain the desired earthworm population their starter food includes 1:1 mixture of cow dung and decaying leaves in a cement tank/wooden box/plastic bucket with proper drainage facilities and on attaining sufficient number of earthworms, subsequently other sources of organic wastes can be provided. Compost worms being voracious feeders, consume in excess of their body weight each day but they prefer some foods to others. Manures are the most commonly used worm feedstock, with dairy and beef manures generally considered the best natural food for E. fetida [60]. The unit should be kept in shade. Sufficient moisture level should be maintained by occasional sprinkling of water. Within 1–2 months, the worms multiply 300 times, which can be used for large scale vermicomposting.
\nEarthworms are used to convert organic waste material into dark brown nutrient rich humus that is a good source of manure for plants. Worms can also degrade specific pollutants and might allow community formation of useful microorganisms. Three commonly used methods for vermicomposting are discussed below:
Bin composting: The most common method for small scale composting is bin composting method. The bin can be constructed of several materials such as wooden/plastic/recycled containers like bathtubs and barrels. A vermicompost bin may be in different sizes and shapes, but its average dimensions are 45 × 30 × 45 cm. Around 10 holes with 1–1.5 cm in diameter holes in bottom, sides and cap of bin is useful for aeration and drainage.
Pit composting: For large scale composting, pits of sizes 2.5 m × 1 m × 0.3 m under thatched sheds with sides left open are advisable. The bottom and sides of the pit should be made hard with a wooden mallet.
Pile composting: Pile method is mostly used for vermicomposting in larger scale. The piles can be made in porch place like greenhouse or in a floor with some facilities for drainage in warm climate. The pile size may vary in length and width, however, its height is average height of bin used for bin composting.
Prior to the vermicomposting process, it is preferred to assign pre-composting of organic waste (thermophilic composting), which comprises a short period of high temperature for facilitating mass reduction, waste stabilization, and pathogen reduction [61, 62]. Thermophilic composting results in sanitization of organic wastes and elimination of toxic compounds [63]. Although pathogen removal occurs during transit in the worm gut [64] but thermophilic composting prior to vermicomposting is advisable to avoid the earthworm mortality. Then, after some days of high temperature, pre-mature compost is cooled by spreading it as thin layers on vermicomposting beds. Vermicomposting can be done either in containers, pits or piles.
Materials required for vermicomposting: Carbon and nitrogen-rich organic materials, spade, ground space, stakes, hollow blocks, plastic sheets or used sacks, water (according to the season) and water sprinklers, shading materials, nylon net or any substitute to cover the beds, and composting earthworms.
Site Selection: Vermicompost production can be done at any place which is having shades, cool and has high humidity. For instance, abandoned cattle shed, or poultry shed or unused buildings or artificial shading could also be provided.
Shredding of organic waste material: The collected organic waste material should be processed for shredding along with mechanical separation of the metal, glass and ceramics that should be kept aside.
Pre-digestion of organic waste material: Pre-digestion of organic waste should be done for at least 20–25 days prior by mixing the waste material along with raw material (e.g., cattle dung slurry). Regular watering is required for partially digesting it and making it fit for earthworm consumption. Raw material to be used includes for composting – cow dung, crop residues, farm wastes, vegetable market wastes and fruit wastes. Cow dung should be at least 20–25 days old to avoid excess heat generation during the composting process. Moreover addition of higher quantities of acid-rich substances such as citrus wastes should be avoided. It is important to mix carbonaceous with nitrogenous organic materials at the right proportions to obtain a C: N ratio of about 30:1, as it results in product of highest stability, the best fertilizer-value and with lowest potential for environmental pollution. For example, rice straw and fresh manure are mixed at about 25:75 ratio by weight. When the material with higher carbon content is used with C:N ratio exceeding 40:1, it is advisable to add nitrogen supplements to ensure its effective decomposition.
Earthworm bed preparation: An hospitable living environment for worms called bedding is prepared. Bedding is a material that provides the worms with a relatively stable habitat with following characteristics:
High absorbency: As earthworms breathes through their skins and therefore bedding must be able to absorb and retain water fairly well. Worms dies if its skin dries out.
Good bulking potential: Worms respire aerobically and different bedding materials affect the overall porosity of the bedding, including the range of particle size and shape, the texture, and the strength and rigidity of its structure. If bedding material is too dense or packs too tightly, then the flow of air is reduced or eliminated. This overall effect is referred as the material’s bulking potential.
Low protein and/or nitrogen content/high Carbon: Earthworms consume their bedding as it breaks down and it is very important for this process to be slow. High protein/nitrogen levels can result in rapid degradation of bedding and its associated heating, creating inhospitable or fatal conditions. High carbon content is required as earthworms and microbes in the feed mixtures activate microbial respiration and degradation of organic wastes, thereby increasing the loss of organic carbon during the vermicomposting process [65, 66]. Various bedding material according to absorbency, bulking potential and C:N are enlisted in Table 1.
Vermiculture bed: Vermiculture bed can be prepared by placing a first layer of saw dust, newspaper, straw, coir waste, sugarcane trash etc. at the bottom of tub/container. Newspaper is one of bedding material that high in absorbency whereas for the sawdust the level of absorbency is poor to medium. A second layer of moistened fine sand of 3 cm thick should be spread over the culture bed followed by a layer of garden soil (3 cm). The floor of the unit should be compacted to prevent earthworm’s migration into the soil.
Loading of organic waste mixture in bed: Third layer of the pre-digested organic waste prepared is added. Thereafter a thin layer of cow dung mixture is placed on the surface of waste material as starter food for compost worms. Then compost worms are to be added without spreading them out. Earthworms consume various organic wastes and reduce the volume by 40–60%. Earthworm eats waste equivalent to its body weight, and produce cast about 50% of the wastes, it consumes in a day.
Composting process: After addition of compost worms wait for at least 15 days for the thermophillic process to end. During this process there is a rapid increase in temperature followed by a gradual decrease. During this period turning to the material 2–3 times at 4–5 days interval is required. Its temperature should be maintained at 30°C, when temperature approaches ambient temperature (<35°C) covering is to be removed and for temperature maintenance, upturning and regular sprinkling of water is advisable. Prominent precautionary measures include; Composting pit should be covered with nylon net or any substitute material to serve as barrier against predators like ants, birds, lizards as it may disturb the activity of earthworm, Blockage of side air vents should be avoided as it can quickly lead to putrefaction and extreme weather conditions such as frost, heavy rainfall, drought and overheating should be avoided. No smell comes out of composting site if the right products or bedding and feed are used. The vermicompost once formed completely will give the smell of moist soil. Maturity could be judged visually also by observing the formation of granular structure of the compost at the surface of the tank. Next step is to make a heap in sunlight on a plastic sheet and keep it for 1-2 hours. The worms will gather at the bottom of heap. After removing vermicompost on top, the worms settled down at the bottom can be carefully collected for use in the next batch of vermicomposting.
Bedding Material | \nAbsorbency | \nBulking Pot. | \nC:N Ratio | \n
---|---|---|---|
Horse manure | \nMedium-good | \nGood | \n22–56 | \n
Peat moss | \nGood | \nMedium | \n58 | \n
Corn silage | \nMedium-Good | \nMedium | \n38–43 | \n
Hay–general | \nPoor | \nMedium | \n15–32 | \n
Straw–general | \nPoor | \nMedium-Good | \n48–150 | \n
Straw–oat | \nPoor | \nMedium | \n48–98 | \n
Straw–wheat | \nPoor | \nMedium-Good | \n100–150 | \n
Paper from municipal waste stream | \nMedium-Good | \nMedium | \n127–178 | \n
Newspaper | \nGood | \nMedium | \n170 | \n
Bark–hardwoods | \nPoor | \nGood | \n116–436 | \n
Bark–softwoods | \nPoor | \nGood | \n131–1285 | \n
Corrugated cardboard | \nGood | \nMedium | \n563 | \n
Lumber mill waste–chipped | \nPoor | \nGood | \n170 | \n
Paper fibre sludge | \nMedium-Good | \nMedium | \n250 | \n
Paper mill sludge | \nGood | \nMedium | \n54 | \n
Sawdust | \nPoor-Medium | \nPoor-Medium | \n142–750 | \n
Shrub trimmings | \nPoor | \nGood | \n53 | \n
Hardwood chips, shavings | \nPoor | \nGood | \n451–819 | \n
Softwood chips, shavings | \nPoor | \nGood | \n212–1313 | \n
Leaves (dry, loose) | \nPoor-Medium | \nPoor-Medium | \n40–80 | \n
Corn stalks | \nPoor | \nGood | \n60–73 | \n
Corn cobs | \nPoor-Medium | \nGood | \n56–123 | \n
Paper mill sludge | \nGood | \nMedium | \n54 | \n
Sawdust | \nPoor-Medium | \nPoor-Medium | \n142–750 | \n
Shrub trimmings | \nPoor | \nGood | \n53 | \n
Hardwood chips, shavings | \nPoor | \nGood | \n451–819 | \n
Softwood chips, shavings | \nPoor | \nGood | \n212–1313 | \n
Leaves (dry, loose) | \nPoor-Medium | \nPoor-Medium | \n40–80 | \n
Corn stalks | \nPoor | \nGood | \n60–73 | \n
Corn cobs | \nPoor-Medium | \nGood | \n56–123 | \n
List of some of the commonly used earthworm bedding material.
The most important abiotic factors which affect vermicomposting process include moisture, pH, temperature, aeration, pH value, ammonia and salt content.
Moisture: A strong relationship exists between the moisture content of organic wastes and the growth rate of earthworms. In a comparative study on vermicomposting process and earthworm’s growth at different temperature and moisture ranges showed that 65–75% is most suitable range of moisture at all ranges of vermicomposting temperature [67]. The bedding used for vermicomposting must be able to hold sufficient moisture as earthworms respire through their skins and moisture content in the bedding of less than of 45% can be fatal to the worms. Although epigenic species, E. fetida and E. andrei can survive moisture ranges between 50% and 90%, but they grow more rapidly between 80% and 90% [20, 68]. The bacteria also plays vital role in vermicomposting. Its activity decreases in moisture content lower than 40% and it almost stops in lower than 10% [69].
Temperature: Earthworm’s activity, metabolism, growth, respiration and reproduction are greatly influenced by temperature [70]. The temperature for the stable development of earthworm population should not exceed 25°C [71]. Although E. fetida cocoons survive extended periods of deep freezing and remain viable [72] but they do not reproduce and do not consume sufficient food at single digit temperatures. It is generally considered necessary to keep the temperatures preferably 15°C for vermicomposting efficiency and 20°C for effective reproductive vermiculture operations. Temperatures above 35°C will cause the worms to leave the area or if they cannot leave, they will quickly die. Bacterial activity is also greatly depended on temperature as it multiplies by two per each 10°C increase in temperature and is quite active around 15–30°C.
Aeration: Earthworms are oxygen breathers and cannot survive in anaerobic conditions. They operate best when compost material is porous and well aerated. Earthworms also help themselves by aerating their bedding by their movement through it. E. fetida have been reported to migrate in high numbers from oxygen depleted water saturated substrate, or in which carbon dioxide or hydrogen sulfide has accumulated.
pH value: The pH value is also one of the important factors affecting the vermicomposting process [73]. Epigenic worms can survive in a pH range of 5–9 [74]. The pH of worm beds tends to drop over time. If the food source/bedding is alkaline, than pH of bed drop to neutral or slightly alkaline and if the food source is acidic than the pH of the beds can drop well below 7. The pH can be adjusted upwards by adding calcium carbonate or peat moss for adjusting pH downward can be introduced into the mix. Although microorganisms which are active in vermicomposting which can maintain their activity even in lower pH of around 4 but recommended pH range for compost is around 6.5–7.5.
Ammonia and salt content: Earthworms cannot survive in organic wastes containing high levels of ammonia. Worms are also very sensitive to salts and they prefer salt contents less than 0.5% [75]. However, many types of manures have high salt contents and if they are to be used as bedding, they should be leached first to reduce the salt content, it is done by simply running water through the material for a period of time [60].
The vermicompost is ready within 60–90 days and ultimately the material becomes black, granular, lightweight, moderately loose, crumbly and humus-rich. Watering must be avoided two to three days before emptying the beds to facilitate the separation of worms from the compost. Common procedures for harvesting the vermicompost are briefly described below. Any method may be adopted exclusively by preference. Moreover, two or more methods may be applied on the same pile. Except for the first method, the rest are intended for bulk harvesting.
\nThis method is practiced if one wants to collect small amounts of vermicast just a few days after the compost pile is stocked with composting worms. In this case only top layer is covered with a thin layer of vermicast and rest of pile has not fully decomposed. The vermicast on top of the pile are simply gathered by hand/trowel and transferred directly into a container. This method is recommended if there is need of organic soil amendment in preparing a fertile potting mix. With time, as vermicompost is collected at the bottom of the pile it is further collected by hand.
\nThe vermicompost is first gathered to form a pyramid like heap within the composting enclosure provided that the heap is exposed to light or it is transferred on to a flat surface elsewhere in open sun on a plastic sheet or a sack. This method of harvesting vermicompost takes the advantage of the earthworm’s sensitivity towards light as they will tend to move deep into the pyramid. Vermicompost from the bottom, sides, and top surface of the heap is then collected by hand or with a trowel. After the first cycle of vermicompost collection, a few minutes are passed to provide sufficient time for the earthworms to move deeper and another cycle is commenced. For faster rate of harvesting vermicompost, the original heap is divided into several smaller heaps.
\nThis method of vermicompost harvesting is done manually with tool consists of mesh wire nailed on wood called sieve. A small portion from vermicompost pile spread on flat floor is transferred into a sieve and it is shaken so that fine vermicompost falls on the ground. Any undecomposed subtrates and earthworms are retained in the screener and the worms are separated manually.
\nThis method of harvesting vermicompost is based on earthworms’ ability to detect sources of food. Earthworms have the habit of abandoning the pile exhausted of food and moving towards fresher palatable source. Despite many modifications in this technique, but the basic principle is the same to provide fresh or more palatable food to cause the migration of earthworms from the exhausted pile to the new food source.
\nThe harvested vermicompost should be stored in dark and cool place as sunlight will lead to loss of moisture and nutrient content. Moreover, harvested vermicompost material should be stored in open rather than packed in sacs. Packing should be done at the time of selling and laminated sac is always advisable. During compost storage in open place, periodical sprinkling of water should be done to maintain moisture level and beneficial microbial population. Vermicompost can be stored for longer periods of one year without loss of its quality, if its moisture is maintained at 40% level.
\nThe key role of vermicompost is change in physical, chemical and biological properties of soil by earthworm activities and they thus called as soil managers [59]. It substantially improves soil structure, texture, aeration and prevents soil erosion. It increases the macropore space ranging from 50 to 500 μm, resulting in improved air-water relationship in the soil thereby favorably affecting plant growth [76]. It also favorably affects soil pH, its microbial population and soil enzyme activities [77]. Moreover, vermicompost is rich source of nutrients such as nitrates, phosphates and exchangeable calcium and soluble potassium [30]. Apart from adding mineralogical nutrients, vermicompost is also rich in beneficial micro flora such as N-fixers, P-solubilizers, cellulose decomposing micro-flora, etc. It also reduces the proportion of water soluble chemical, which causes possible environmental contamination [78]. Mucus excreted by earthworm’s digestive canal produces some antibiotics and hormone-like biochemicals thereby boosting plant growth [70] and enhancing the decomposition of organic matter in soil [79]. Vermicompost has been reported to have favorable influence on the growth and yield parameters of several crops like paddy, sugarcane, brinjal, tomato, and okra [59]. Thus, vermicompost acts a soil conditioner [80] and a slow-release fertilizer [81] that ultimately improves soil structure, soil fertility, plant growth and suppresses diseases caused by soil-borne plant pathogens, increases crop yield [82, 83, 84].
\nChemical fertilizers are produced from “vanishing resources” of earth and crops grown on chemical fertilizers have low and contaminated nutrient value in comparison to grown naturally or organic way. To preserve the agro-ecosystem and protect human health from the harmful chemical fertilizers ‘Ecological Agriculture and Organic Farming’ has to be promoted as the new emerging concept of “Organic Farming” focuses mainly on production of chemical free foods. Organic farming with use of organic fertilizers like “vermicompost” could substitute the chemical fertilizers and can reduce the economic cost and may also lead to organic products which fetches higher price in the market.
\nNo conflict of interest is indulged.
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\\n\\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\\n\\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\\n\\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\\n\\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\\n\\n5. TERMINATION
\\n\\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\\n\\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\\n\\n6. INTECHOPEN’S DUTIES AND RIGHTS
\\n\\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\\n\\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\\n\\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\\n\\n7. MISCELLANEOUS
\\n\\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\\n\\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\\n\\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\\n\\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\\n\\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\\n\\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\\n\\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\\n\\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\\n\\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\\n\\nLast updated: 2020-11-27
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n1. DEFINITIONS
\n\nCorresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
\n\nCo-Author: All other Authors of the Chapter besides the Corresponding Author.
\n\nIntechOpen: IntechOpen Ltd., the Publisher of the Book.
\n\nBook: The publication as a collection of chapters compiled by IntechOpen including the Chapter. Chapter: The original literary work created by Corresponding Author and any Co-Author that is the subject of this Agreement.
\n\n2. CORRESPONDING AUTHOR'S GRANT OF RIGHTS
\n\n2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\n\nThe aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
\n\n2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\n\nThe Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\n\nSubject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\n\nSubject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
\n\n2.3 All rights granted to IntechOpen in this Article are assignable, sublicensable or otherwise transferrable to third parties without the Corresponding Author's or any Co-Author’s specific approval.
\n\n2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\n\n3. CORRESPONDING AUTHOR'S DUTIES
\n\n3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
\n\n3.2 When submitting the Chapter, the Corresponding Author agrees to:
\n\nThe Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
\n\nAll payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
\n\n3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\n\nThe Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\n\n3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\n4. CORRESPONDING AUTHOR'S WARRANTY
\n\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n5. TERMINATION
\n\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\n\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\n\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\n7. MISCELLANEOUS
\n\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
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