Valorization of Food Processing By-Products as Smart Food Packaging Materials and Its Application

*Saroat Rawdkuen and Pimonpan Kaewprachu*

## **Abstract**

Traditional food packaging systems cannot provide any information related to the food quality during storage to consumers. Recently, the renewable resources have been considered as starting materials for making biodegradable packaging film. A variety of food processing by-products have been utilized, either alone or in mixtures, to produce packaging films with proper properties. It shows high possibility for smart biodegradable filmmaking as well as is applicable in the food industry. In order to monitor the food quality and to reduce the food loss and waste, a new packaging technology has been increasingly developed. Smart packaging refers to packaging systems which can monitor, detect, and inform about the qualities of food in real time. Indicator is the most commonly used device, which can communicate through direct visual change, especially in color. Natural extract and synthetic color are usually added into smart packaging films. However, synthetic dyes may be harmful to the consumers' health. Thus, the use of natural extract has been increased. Smart packaging films can be applied to various types of food products in order to monitor the food quality during transportation and storage. Thus, smart packaging could be used as a nondestructive tool to detect the food quality.

**Keywords:** biodegradable, by-products, food packaging, indicators, natural extract, smart films, valorization

#### **1. Introduction**

Nowadays, the food industry is continuously growing due to increasing levels of population and globalization and is providing a wide variety of food products to meet customer needs. The major food industries of the world include meat, poultry, fish and seafood, fruits and vegetables, dairy, and cereal. During food processing, a large number of by-products are thrown away into the environment, resulting in accumulation in the environment, and may also interfere with natural process of ecosystem. According to the FAO, 1.3 billion tons of foods are by-products. The global food losses and waste are strongly dependent on the kind of foods. The highest percentage of by-product is found in fruits and vegetables, plus roots and tubers (45%), followed by fish and seafood (35%), oilseed, meat, and dairy (20%),

respectively [1]. In developing countries, food waste is generally generated at postharvest and processing levels at around 40%, while in industrialized countries, the sector contributing a huge by-product (more than 40%) is households [1]. These by-products still contain the organic matter that have a potential for making the packaging or developing new valuable products from them for commercial applications. Thus, valorization of food processing products is an interesting concept that offers sustainability rather than landfilling or disposal.

Traditional food packaging has a role to protect the packaged food from mechanical damage and physical stress, communicate with the consumers, provide convenience, and contain the product [2]. This packaging system cannot monitor the quality of packaged food products and inform the status of environment and food conditions to the consumers at any time and cannot meet the consumer preferences. Thus, a new packaging technology has been developed and also proposed with the aim to reduce the food loss and waste throughout the food supply chain. Thus, smart packaging or intelligent packaging concept has been raised, which is considered as innovative packaging. According to EC [3], intelligent materials and articles are materials and articles which monitor the condition of packaged food products or the surrounding environment of the food. Yam [4] defined intelligent packaging (also described as smart packaging) as a packaging system that used to monitor the condition that the packaged food product is exposed to and provide information about the packaged food quality to the consumers through the visual color changes.

Generally, there are three main types of smart packaging, which include sensors, indicators, and radio-frequency identification (RFID) devices [5]. Food spoilage or fermentation process is commonly accompanied with a pH change. Thus, pH indicator has gained much popularity, compared with others. Thus, pH indicator generally comprises a dye that changes in color in a function of pH. There are two main sources of indicators: chemical dye and natural extract. Chemical dyes include methyl red, methyl orange, bromothymol blue, bromocresol green, phenol red, and their combinations. A natural dye can be obtained from the root, flower, leaves of plants, and other parts of plant materials that contain a natural pigment, such as anthocyanins. The advantage of natural dye is safety and being eco-friendly to the consumers, compared to chemical dye. Thus, the natural dye has been increasingly used in smart packaging. These indicators can interact with the internal (metabolites in the head space and food components) and/or external factors (environmental surrounding). As a result of this reaction, they generate the response through the color changes or electrical signal and depend on types of intelligent packaging, which relate to the actual status of packaged food product. Thus, the use of smart packaging could help to decrease the number of food loss and waste by sensing or communicating the actual quality of the packaged food product to the consumer in real time through visible color changes.

Smart packaging has been widely applied on various types of food products [6–9]. The use of these packaging systems could facilitate the consumers to know the quality and the condition of packaged food (food spoilage, ripeness, or degree of fermentation) without damaging the package. From the food quality and safety point of view, smart packaging is very useful to the producers, sellers, and consumers to give information regarding the packaged food condition through a change of tools. In this context, the valorization of food processing by-products to produce packaging films is reviewed. The principle and types of smart/intelligent packaging are presented. The current researches on the applications of smart packaging on various kinds of food products are also discussed.

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**Table 1.**

*Source: Ezejiofor et al. [10].*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

A large amount of food materials as by-products, which are generated along the chain of food production and transformation, are thrown into the environment. Food processing by-products generally include the residues or remain that were discarded after removing the desirable portion for further processing or direct consumption as food. According to Ezejiofor et al. [10], residues from food processing make up 30–60% of the product that is used for human consumption and animal feeding. Most of the by-products commonly contain an organic component, such as proteins, carbohydrates, and lipids, which are promising sources of value-added substances that can be extracted and utilized as a starting material for forming a smart packaging film. The different types of by-products produced by various food processing industries are listed in **Table 1**. Current trends in the world are to recover and utilize the food processing by-products into useful materials and to recycle by-products as a means of achieving goal of sustainable development. Hence, considerable efforts in the valorization of food processing by-products have been made with the purpose of minimizing the amounts of by-products, reducing the environment pollution, and increasing sustainability of these by-products. This section reviews by-products from various food processing industries that have a potential to be produced as smart packaging.

The meat processing industry has emerged as a major food industry of the world.

As per the FAO [11], the world pork meat production recorded 118 million tons, followed by poultry (117 million tons), sheep (9 million tons), and goat (5 million tons). A huge by-product is generated during the various stages of meat and poultry processing in industries. By-products generated during processing of large animals include the skin (6–10% of live weight), bones (15–20% of live weight), blood (3–9% of live weight), fat (3–4% of live weight), head (6–8% of live weight), and viscera (10–15% of live weight), while poultry by-products include the bones (8–10% of live weight), blood (3–5% of live weight), feather (5–7% of live weight), liver and heart (4–6% of live weight), and viscera (18–20% of live weight) [12]. Valorization of these by-products is a current trend concept for promoting the sustainable development. However, high value-added by-products from the meat and poultry industries are not exploited to its full potential when compared to the by-products from other

In general, humans will not consume bones; hence they are disposed into the environment. They are commonly used for animal feeding. However, bones and skin by-products obtained from meat and poultry are important source of proteins, which can be extracted as collagen and gelatin. Gelatin is a soluble protein obtained by degradation of collagen, which is commonly found in animal skin, bones, and connective tissue. Gelatin from poultry is an alternative source

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

**2. Valorization of food processing by-products**

**2.1 Meat and poultry processing by-products**

industries such as fruits, vegetables, dairy, etc.

**Food processing industries Generated by-products**

Dairy product Whey, lactose Fruits and vegetables Peels, pulp, seeds

*Various food processing industries and their by-products.*

Meat and poultry Skin, bones, blood, head, feather, viscera Fish and seafood Skin, viscera, heads, backbones, blood, shells *Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### **2. Valorization of food processing by-products**

*Food Preservation and Waste Exploitation*

color changes.

visible color changes.

offers sustainability rather than landfilling or disposal.

respectively [1]. In developing countries, food waste is generally generated at postharvest and processing levels at around 40%, while in industrialized countries, the sector contributing a huge by-product (more than 40%) is households [1]. These by-products still contain the organic matter that have a potential for making the packaging or developing new valuable products from them for commercial applications. Thus, valorization of food processing products is an interesting concept that

Traditional food packaging has a role to protect the packaged food from mechanical damage and physical stress, communicate with the consumers, provide convenience, and contain the product [2]. This packaging system cannot monitor the quality of packaged food products and inform the status of environment and food conditions to the consumers at any time and cannot meet the consumer preferences. Thus, a new packaging technology has been developed and also proposed with the aim to reduce the food loss and waste throughout the food supply chain. Thus, smart packaging or intelligent packaging concept has been raised, which is considered as innovative packaging. According to EC [3], intelligent materials and articles are materials and articles which monitor the condition of packaged food products or the surrounding environment of the food. Yam [4] defined intelligent packaging (also described as smart packaging) as a packaging system that used to monitor the condition that the packaged food product is exposed to and provide information about the packaged food quality to the consumers through the visual

Generally, there are three main types of smart packaging, which include sensors, indicators, and radio-frequency identification (RFID) devices [5]. Food spoilage or fermentation process is commonly accompanied with a pH change. Thus, pH indicator has gained much popularity, compared with others. Thus, pH indicator generally comprises a dye that changes in color in a function of pH. There are two main sources of indicators: chemical dye and natural extract. Chemical dyes include methyl red, methyl orange, bromothymol blue, bromocresol green, phenol red, and their combinations. A natural dye can be obtained from the root, flower, leaves of plants, and other parts of plant materials that contain a natural pigment, such as anthocyanins. The advantage of natural dye is safety and being eco-friendly to the consumers, compared to chemical dye. Thus, the natural dye has been increasingly used in smart packaging. These indicators can interact with the internal (metabolites in the head space and food components) and/or external factors (environmental surrounding). As a result of this reaction, they generate the response through the color changes or electrical signal and depend on types of intelligent packaging, which relate to the actual status of packaged food product. Thus, the use of smart packaging could help to decrease the number of food loss and waste by sensing or communicating the actual quality of the packaged food product to the consumer in real time through

Smart packaging has been widely applied on various types of food products [6–9]. The use of these packaging systems could facilitate the consumers to know the quality and the condition of packaged food (food spoilage, ripeness, or degree of fermentation) without damaging the package. From the food quality and safety point of view, smart packaging is very useful to the producers, sellers, and consumers to give information regarding the packaged food condition through a change of tools. In this context, the valorization of food processing by-products to produce packaging films is reviewed. The principle and types of smart/intelligent packaging are presented. The current researches on the applications of smart packaging on various kinds of food products are

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also discussed.

A large amount of food materials as by-products, which are generated along the chain of food production and transformation, are thrown into the environment. Food processing by-products generally include the residues or remain that were discarded after removing the desirable portion for further processing or direct consumption as food. According to Ezejiofor et al. [10], residues from food processing make up 30–60% of the product that is used for human consumption and animal feeding. Most of the by-products commonly contain an organic component, such as proteins, carbohydrates, and lipids, which are promising sources of value-added substances that can be extracted and utilized as a starting material for forming a smart packaging film. The different types of by-products produced by various food processing industries are listed in **Table 1**. Current trends in the world are to recover and utilize the food processing by-products into useful materials and to recycle by-products as a means of achieving goal of sustainable development. Hence, considerable efforts in the valorization of food processing by-products have been made with the purpose of minimizing the amounts of by-products, reducing the environment pollution, and increasing sustainability of these by-products. This section reviews by-products from various food processing industries that have a potential to be produced as smart packaging.

#### **2.1 Meat and poultry processing by-products**

The meat processing industry has emerged as a major food industry of the world. As per the FAO [11], the world pork meat production recorded 118 million tons, followed by poultry (117 million tons), sheep (9 million tons), and goat (5 million tons). A huge by-product is generated during the various stages of meat and poultry processing in industries. By-products generated during processing of large animals include the skin (6–10% of live weight), bones (15–20% of live weight), blood (3–9% of live weight), fat (3–4% of live weight), head (6–8% of live weight), and viscera (10–15% of live weight), while poultry by-products include the bones (8–10% of live weight), blood (3–5% of live weight), feather (5–7% of live weight), liver and heart (4–6% of live weight), and viscera (18–20% of live weight) [12]. Valorization of these by-products is a current trend concept for promoting the sustainable development. However, high value-added by-products from the meat and poultry industries are not exploited to its full potential when compared to the by-products from other industries such as fruits, vegetables, dairy, etc.

In general, humans will not consume bones; hence they are disposed into the environment. They are commonly used for animal feeding. However, bones and skin by-products obtained from meat and poultry are important source of proteins, which can be extracted as collagen and gelatin. Gelatin is a soluble protein obtained by degradation of collagen, which is commonly found in animal skin, bones, and connective tissue. Gelatin from poultry is an alternative source


#### **Table 1.** *Various food processing industries and their by-products.*

for the halal and kosher market. They have many applications in food industry and have been extensively used as a raw material in packaging. Feathers are byproducts from industrial poultry production and are mostly discharged without any pretreatment, causing environmental problems. Chicken feather can be considered as attractive sources for the production of packaging films. Proteins (91%), lipids (1%), and water (8%) are the main components in chicken feathers [13]. Keratins are proteins found in chicken feathers. Thus, keratins from chicken feather protein are abundant and a cheap source, can be utilized as edible film material, and can reduce the environment pollution related to the by-products disposed by the processing industries.

#### **2.2 By-products from fish and seafood processing**

The industrial fish and seafood processing generates huge amounts of nonedible parts, which are discarded. According to Olsen et al. [14], fish and seafood by-products contribute to around 70% of the initial weight of the catch. Fish and seafood by-products generally contained valuable components such as oil, enzymes, collagen, gelatin, chitin, chitosan, and muscle protein. These valuable compounds have a high potential for using in food, packaging, pharmaceutical, medicine, and other industries. Some of these components from fish and seafood by-products have been isolated and currently sold commercially. The composition and the percentage of nonedible parts of fish and seafood processing are greatly dependent on fish and seafood types and processing methods. For example, by-products generated in finfish processing include the head (14–20%), gut (15–20%), skin (1–3%), bones (10–16%), and trimming (filets) (15–20%), while shrimp generates 65–85% (wet weight basis) of by-products, which is mainly obtained from the head and shell [15].

A high value-added compound can be isolated from fish and seafood processing by-product, which include collage, gelatin, chitin, chitosan, etc. Some of these valuable compounds are able to be formed as packaging films [16], which can reduce the environmental pollution at the same time (films are biodegradable). Collagen is the main structural component, which is widely found in the skin, bone, tendon, and cartilage. Collagen and gelatin have a wide range of applications in various industries. Nowadays, collagen and gelatin extracted from fish and seafood by-products have gained great attention due to the requirement of "halal and kosher" food products and the consumers' concern about bovine spongiform encephalopathy in collagen and/or gelatin from mammals [17–19]. Thus, fish and seafood processing by-products are one of the most important sources of marinederived collagen and gelatin.

The crustacean by-products contain chitin content between 2 and 75%, which are dependent on composition, processing methods, and their species [20]. Chitin possesses repeating units of poly-*β*-(1,4)-*N*-acetyl-d-glucosamine (**Figure 1**). It is the second most abundant natural polysaccharide on earth, after cellulose [21]. It is widely distributed in the nature as a structural polymer in the exoskeleton of insects and crustaceans, which is an important source for chitin industry. Chitin is insoluble in water and even in most organic solvents due to being highly hydrophobic [21]. Chitosan is the *N*-deacetylated derivative of chitin. On the other hand, chitosan is soluble in water, which makes it more convenient to use in different fields. Due to being biodegradable, nontoxic, and biocompatible, chitin and chitosan, which are an agent recovered from shellfish and/or crustacean processing by-products, have been recently found in various industrial applications such as antimicrobial agent, packaging films, pharmaceutical, cosmetic, etc.

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**Figure 1.**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

and food industries such as protease inhibitor in surimi processing [23].

The total worldwide annual production of fruit was reported to be more than 892 million metric tons in 2016 [11]. During fruit and vegetable processing, enormous numbers of peel, pulp, and seed are generated which are disposed into the environment. These by-products represent approximately 30–50% of the total weight, which can affect the environment and health sectors, due to their methane emissions and biodegradability [10]. These by-products are commonly utilized as animal feed; however, they still comprise of huge amounts of organic components such as polysaccharides, proteins, lipids, and other aliphatic and aromatic compounds. Thus, these by-products can be further utilized or extracted as high-value substance and can be used as alternative sources with a high potential for the

Banana (*Musa paradisiaca* L., Musaceae) is the most important fruit crop, with a global annual production of 113 million tons in 2016 [11]. Banana peels are usually discarded during the banana processing or used in the form of animal feed. Peels, by-products from banana, can represent 40% of the total weight [24]. However, this by-product is considered as a good and cheap source of valuable compounds. Moreover, a huge amount of banana that does not meet the standard exportation is obtained. The whole banana is a good source of polysaccharide, especially starch. Unripe banana generally contains starch more than 70% with other components (protein, fiber, and lipid) [25]. Banana starch and flour have been used as a starting

Dairy processing generates enormous volume of by-products during the processing of milk and manufacture of varied products. These by-products are comprised of high amounts of lipids, proteins, vitamin, etc. The utilization of these by-products can hugely enhance dairy sector profitability. Whey, being a major by-product of the dairy industry, is generated during the manufacturing of cheese. It contains high amounts of proteins which can be converted into various whey protein products, including whey protein concentrates (WPC) and whey protein isolate (WPI). WPC contains 25–85% protein, while WPI contains >90% protein. The pretreatment prior to membrane separation and the membrane used typically affects the whey protein content [22]. Thus, the whey protein obtained has potential for use in the packaging

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

**2.3 Dairy processing by-products**

**2.4 Fruit and vegetable by-products**

development of new packaging technologies.

material to form edible films [25, 26].

*Chemical structure of chitin and chitosan.*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### **2.3 Dairy processing by-products**

*Food Preservation and Waste Exploitation*

disposed by the processing industries.

obtained from the head and shell [15].

derived collagen and gelatin.

**2.2 By-products from fish and seafood processing**

for the halal and kosher market. They have many applications in food industry and have been extensively used as a raw material in packaging. Feathers are byproducts from industrial poultry production and are mostly discharged without any pretreatment, causing environmental problems. Chicken feather can be considered as attractive sources for the production of packaging films. Proteins (91%), lipids (1%), and water (8%) are the main components in chicken feathers [13]. Keratins are proteins found in chicken feathers. Thus, keratins from chicken feather protein are abundant and a cheap source, can be utilized as edible film material, and can reduce the environment pollution related to the by-products

The industrial fish and seafood processing generates huge amounts of nonedible parts, which are discarded. According to Olsen et al. [14], fish and seafood by-products contribute to around 70% of the initial weight of the catch. Fish and seafood by-products generally contained valuable components such as oil, enzymes, collagen, gelatin, chitin, chitosan, and muscle protein. These valuable compounds have a high potential for using in food, packaging, pharmaceutical, medicine, and other industries. Some of these components from fish and seafood by-products have been isolated and currently sold commercially. The composition and the percentage of nonedible parts of fish and seafood processing are greatly dependent on fish and seafood types and processing methods. For example, by-products generated in finfish processing include the head (14–20%), gut (15–20%), skin (1–3%), bones (10–16%), and trimming (filets) (15–20%), while shrimp generates 65–85% (wet weight basis) of by-products, which is mainly

A high value-added compound can be isolated from fish and seafood processing by-product, which include collage, gelatin, chitin, chitosan, etc. Some of these valuable compounds are able to be formed as packaging films [16], which can reduce the environmental pollution at the same time (films are biodegradable). Collagen is the main structural component, which is widely found in the skin, bone, tendon, and cartilage. Collagen and gelatin have a wide range of applications in various industries. Nowadays, collagen and gelatin extracted from fish and seafood by-products have gained great attention due to the requirement of "halal and kosher" food products and the consumers' concern about bovine spongiform encephalopathy in collagen and/or gelatin from mammals [17–19]. Thus, fish and seafood processing by-products are one of the most important sources of marine-

The crustacean by-products contain chitin content between 2 and 75%, which are dependent on composition, processing methods, and their species [20]. Chitin possesses repeating units of poly-*β*-(1,4)-*N*-acetyl-d-glucosamine (**Figure 1**). It is the second most abundant natural polysaccharide on earth, after cellulose [21]. It is widely distributed in the nature as a structural polymer in the exoskeleton of insects and crustaceans, which is an important source for chitin industry. Chitin is insoluble in water and even in most organic solvents due to being highly hydrophobic [21]. Chitosan is the *N*-deacetylated derivative of chitin. On the other hand, chitosan is soluble in water, which makes it more convenient to use in different fields. Due to being biodegradable, nontoxic, and biocompatible, chitin and chitosan, which are an agent recovered from shellfish and/or crustacean processing by-products, have been recently found in various industrial applications such as antimicrobial agent, packaging films, pharmaceu-

**110**

tical, cosmetic, etc.

Dairy processing generates enormous volume of by-products during the processing of milk and manufacture of varied products. These by-products are comprised of high amounts of lipids, proteins, vitamin, etc. The utilization of these by-products can hugely enhance dairy sector profitability. Whey, being a major by-product of the dairy industry, is generated during the manufacturing of cheese. It contains high amounts of proteins which can be converted into various whey protein products, including whey protein concentrates (WPC) and whey protein isolate (WPI). WPC contains 25–85% protein, while WPI contains >90% protein. The pretreatment prior to membrane separation and the membrane used typically affects the whey protein content [22]. Thus, the whey protein obtained has potential for use in the packaging and food industries such as protease inhibitor in surimi processing [23].

#### **2.4 Fruit and vegetable by-products**

The total worldwide annual production of fruit was reported to be more than 892 million metric tons in 2016 [11]. During fruit and vegetable processing, enormous numbers of peel, pulp, and seed are generated which are disposed into the environment. These by-products represent approximately 30–50% of the total weight, which can affect the environment and health sectors, due to their methane emissions and biodegradability [10]. These by-products are commonly utilized as animal feed; however, they still comprise of huge amounts of organic components such as polysaccharides, proteins, lipids, and other aliphatic and aromatic compounds. Thus, these by-products can be further utilized or extracted as high-value substance and can be used as alternative sources with a high potential for the development of new packaging technologies.

Banana (*Musa paradisiaca* L., Musaceae) is the most important fruit crop, with a global annual production of 113 million tons in 2016 [11]. Banana peels are usually discarded during the banana processing or used in the form of animal feed. Peels, by-products from banana, can represent 40% of the total weight [24]. However, this by-product is considered as a good and cheap source of valuable compounds. Moreover, a huge amount of banana that does not meet the standard exportation is obtained. The whole banana is a good source of polysaccharide, especially starch. Unripe banana generally contains starch more than 70% with other components (protein, fiber, and lipid) [25]. Banana starch and flour have been used as a starting material to form edible films [25, 26].

**Figure 1.** *Chemical structure of chitin and chitosan.*

Mango (*Mangifera indica* L., Anacardiaceae) is the most important fruit in the tropical region, especially in Thailand. The major by-products of industrial mango processing are peels and kernels which represent about 35–60% of the total fruit weight [27]. Mango kernels are promising sources of edible oil, starch, flour, and essential amino acids [27–29]. Mango peels have been reported as a good source of pectin, which is considered a high-quality dietary fiber [27]. Thus, pectin extracted from mango peels has a potential for developing packaging films.

Rice (*Oryza sativa*) is one of the most common foods that people usually consume around the world. According to the FAOSTAT database, the worldwide annual production of rice was over 740 million tons in 2016 [11]. Rice milling process is required to remove unwanted material, prior to cooking. After rice milling process, 70% rice is obtained, while rice hull (20%), rice bran (8%), and rice germ (2%) are the by-products [24]. However, some amount of broken rice also occurred during milling process. Broken rice is a good source of starch and flour and can be used to produce as rice starch/flour films. Rice bran is a rich source of fat, protein, carbohydrate, vitamins, minerals, and antioxidants [30]. Rice bran has a potential to produce packaging film; however, it is very scarce to use rice bran as a starting material for film production.

According to the FAOSTAT database, the worldwide annual production of soybean was over 334 million tons in 2016 [11]. Soybean is the most important of legume crops. Soy protein resin is obtained from soybean harvesting and processing as by-products. Soy protein is typically categorized as soy flour (50–59% protein), soy protein concentrate (SPC) (65–72% protein), and soy protein isolate (SPI) (>90% protein) [31]. They are widely used as a starting material to form film due to their abundant, biodegradable, cheap, functional properties and high nutritional quality. Thus, the utilization of soy protein in packaging technology can provide a value to soybean by creating a new route for the marketing of soy protein materials.

#### **3. Intelligent packaging**

#### **3.1 Principle**

According to EC [3], intelligent materials and articles are materials and articles which monitor the condition of packaged food products or the surrounding environment of the food. Intelligent packaging refers to packaging materials that provide a total packaging solution and monitor changes in the quality of product or its environment [32]. Poças et al. [33] defined smart or intelligent packaging as a packaging system that is associated with communication. Intelligent packaging can also be defined as the packaging material that contains the communication functions for recording the internal and external environment changes and then inform the users about the packaged food product's status [4].

This packaging system utilizes a variety of sensors or indicators to detect the quality and safety of packaged food products and may inform the product's status and/or environment condition to the producers, retailer, or consumer at any given time. Food freshness, pH level, microbial growth, gas (carbon dioxide: CO2 and oxygen: O2) in the package headspace, time or temperature are an example of sensors or indicators. Smart packaging concepts and types including sensors, i.e., gas sensor and biosensor; indicators, i.e., freshness indicators, time-temperature indicators (TTI), and gas indicators; and radio-frequency identification devices are described in this chapter.

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of analyte.

**3.3 Indicators**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

the physical or chemical information about the sample into the signal [5].

Gas sensors are devices that respond to the presence of a gaseous analyte by changing the physical parameters of the sensor and are monitored by external devices [34]. It includes organic conducting polymers, metal-oxide-semiconductor field-effect transistors, potentiometric carbon dioxide sensors, piezoelectric crystal sensors, and amperometric oxygen sensors [5]. Systems commonly contained a solid-state material, which operate on the principle of luminescence quenching or absorbance changes caused by direct contact with the gas analyte [34]. Optochemical sensor based on gas-phase protonated tetraphenylporphyrin (TPP) was developed by Tuerdi et al. [35]. This system was used for detecting volatile amines (ammonia, NH3). The authors concluded that this sensor could detect NH3 gas at very low levels (0.1 ppm). Thus, this system is a noninvasive technique, has high sensitivity and fast response-recovery times for gas analysis, and is potentially

Yam et al. [2] defined biosensors as compact analytical devices that are used for detecting, recording, and transmitting information to biological reactions. Biosensors usually comprise of the bioreceptors and transducers [5]. The bioreceptors, including organic or biological materials (enzyme, hormone, microbes, etc.), recognize a target analyte. The transducers, such as electrochemical, acoustic, or optical, can convert biological signals into quantifiable electronic response [2]. Chemiluminescence biosensor for the detection of putrescine (biogenic amines) in meat product was developed by Omanovic-Miklicanin and Valzacchi [36] by covering the Co(II) and enzyme (putrescine oxidase or diamine oxidase) onto glass supports with hydroxyethyl cellulose membrane. Recently, biosensors based on heme entrapped in recombinant silk film on a glass carbon electrode modified with multiwalled carbon nanotubes for detecting nitric oxide (NO) at nanomolar levels in the presence and absence of oxygen were prepared by Musameh et al. [37]. This system should have high sensitivity, accuracy, precision, and stable detection

Indicators may also be defined as a substance that indicates the absence or presence of another substance or the degree of reaction between two or more substances by means of characteristic changes, especially in color [34]. The difference between

Many smart or intelligent packaging concepts involve the use of sensors. This system is generally used in terms of a combination of sensors with packaging technique such as modified atmosphere (MAP) and vacuum packaging. Kerry [5] defined sensors as a small device that used to detect, locate or quantify energy or matter, giving a signal for the detection or measurement of a physical or chemical property to which the device responds. To qualify as a sensor, a device must provide continuous output of a signal. Most sensors commonly comprise of two basic functional parts, a receptor and a transducer. In the receptor, physical or chemical information is transformed into an energy form, which may be detected by a transducer. The transducer is a device capable of transforming the energy carrying

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

suitable for applications as smart packaging.

**3.2 Sensors**

*3.2.1 Gas sensors*

*3.2.2 Biosensor*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### **3.2 Sensors**

*Food Preservation and Waste Exploitation*

material for film production.

protein materials.

**3.1 Principle**

**3. Intelligent packaging**

ing films.

Mango (*Mangifera indica* L., Anacardiaceae) is the most important fruit in the tropical region, especially in Thailand. The major by-products of industrial mango processing are peels and kernels which represent about 35–60% of the total fruit weight [27]. Mango kernels are promising sources of edible oil, starch, flour, and essential amino acids [27–29]. Mango peels have been reported as a good source of pectin, which is considered a high-quality dietary fiber [27]. Thus, pectin extracted from mango peels has a potential for developing packag-

Rice (*Oryza sativa*) is one of the most common foods that people usually consume around the world. According to the FAOSTAT database, the worldwide annual production of rice was over 740 million tons in 2016 [11]. Rice milling process is required to remove unwanted material, prior to cooking. After rice milling process, 70% rice is obtained, while rice hull (20%), rice bran (8%), and rice germ (2%) are the by-products [24]. However, some amount of broken rice also occurred during milling process. Broken rice is a good source of starch and flour and can be used to produce as rice starch/flour films. Rice bran is a rich source of fat, protein, carbohydrate, vitamins, minerals, and antioxidants [30]. Rice bran has a potential to produce packaging film; however, it is very scarce to use rice bran as a starting

According to the FAOSTAT database, the worldwide annual production of soybean was over 334 million tons in 2016 [11]. Soybean is the most important of legume crops. Soy protein resin is obtained from soybean harvesting and processing as by-products. Soy protein is typically categorized as soy flour (50–59% protein), soy protein concentrate (SPC) (65–72% protein), and soy protein isolate (SPI) (>90% protein) [31]. They are widely used as a starting material to form film due to their abundant, biodegradable, cheap, functional properties and high nutritional quality. Thus, the utilization of soy protein in packaging technology can provide a value to soybean by creating a new route for the marketing of soy

According to EC [3], intelligent materials and articles are materials and articles

This packaging system utilizes a variety of sensors or indicators to detect the quality and safety of packaged food products and may inform the product's status and/or environment condition to the producers, retailer, or consumer at any given time. Food freshness, pH level, microbial growth, gas (carbon dioxide: CO2 and oxygen: O2) in the package headspace, time or temperature are an example of sensors or indicators. Smart packaging concepts and types including sensors, i.e., gas sensor and biosensor; indicators, i.e., freshness indicators, time-temperature indicators (TTI), and gas indicators; and radio-frequency identification devices are

which monitor the condition of packaged food products or the surrounding environment of the food. Intelligent packaging refers to packaging materials that provide a total packaging solution and monitor changes in the quality of product or its environment [32]. Poças et al. [33] defined smart or intelligent packaging as a packaging system that is associated with communication. Intelligent packaging can also be defined as the packaging material that contains the communication functions for recording the internal and external environment changes and then inform

the users about the packaged food product's status [4].

**112**

described in this chapter.

Many smart or intelligent packaging concepts involve the use of sensors. This system is generally used in terms of a combination of sensors with packaging technique such as modified atmosphere (MAP) and vacuum packaging. Kerry [5] defined sensors as a small device that used to detect, locate or quantify energy or matter, giving a signal for the detection or measurement of a physical or chemical property to which the device responds. To qualify as a sensor, a device must provide continuous output of a signal. Most sensors commonly comprise of two basic functional parts, a receptor and a transducer. In the receptor, physical or chemical information is transformed into an energy form, which may be detected by a transducer. The transducer is a device capable of transforming the energy carrying the physical or chemical information about the sample into the signal [5].

#### *3.2.1 Gas sensors*

Gas sensors are devices that respond to the presence of a gaseous analyte by changing the physical parameters of the sensor and are monitored by external devices [34]. It includes organic conducting polymers, metal-oxide-semiconductor field-effect transistors, potentiometric carbon dioxide sensors, piezoelectric crystal sensors, and amperometric oxygen sensors [5]. Systems commonly contained a solid-state material, which operate on the principle of luminescence quenching or absorbance changes caused by direct contact with the gas analyte [34]. Optochemical sensor based on gas-phase protonated tetraphenylporphyrin (TPP) was developed by Tuerdi et al. [35]. This system was used for detecting volatile amines (ammonia, NH3). The authors concluded that this sensor could detect NH3 gas at very low levels (0.1 ppm). Thus, this system is a noninvasive technique, has high sensitivity and fast response-recovery times for gas analysis, and is potentially suitable for applications as smart packaging.

#### *3.2.2 Biosensor*

Yam et al. [2] defined biosensors as compact analytical devices that are used for detecting, recording, and transmitting information to biological reactions. Biosensors usually comprise of the bioreceptors and transducers [5]. The bioreceptors, including organic or biological materials (enzyme, hormone, microbes, etc.), recognize a target analyte. The transducers, such as electrochemical, acoustic, or optical, can convert biological signals into quantifiable electronic response [2]. Chemiluminescence biosensor for the detection of putrescine (biogenic amines) in meat product was developed by Omanovic-Miklicanin and Valzacchi [36] by covering the Co(II) and enzyme (putrescine oxidase or diamine oxidase) onto glass supports with hydroxyethyl cellulose membrane. Recently, biosensors based on heme entrapped in recombinant silk film on a glass carbon electrode modified with multiwalled carbon nanotubes for detecting nitric oxide (NO) at nanomolar levels in the presence and absence of oxygen were prepared by Musameh et al. [37]. This system should have high sensitivity, accuracy, precision, and stable detection of analyte.

#### **3.3 Indicators**

Indicators may also be defined as a substance that indicates the absence or presence of another substance or the degree of reaction between two or more substances by means of characteristic changes, especially in color [34]. The difference between

sensors and indicators is the components; indicators do not contain receptor and transducer components as the sensor, so it provides qualitative information through directly visible color change. According to Smolander [38], changes in color of pH dye indicator can be proposed to investigate acidic and/or basic volatile compounds and provide an irreversible color change in an appearance.

#### *3.3.1 Freshness indicators*

Freshness indicators are devices that are printed on the packaging film or in the form of a package label and then attached inside the packaging materials. Freshness indicators have been developed with the aim of investigating the food spoilage process, degree of fermentation, or ripening stage of fruits and vegetables and then informing the users about the freshness of packaged goods through color changes that can be directly detected by the naked eye. Freshness indicators provide direct information of the packaged food quality resulting from chemical changes or microbial growth within a food product. Indicator may react to metabolites that are generated in the package as a result of metabolism or the microbial growth [34]. Freshness indicator concepts based on pH sensing film, using CO2 as the major target, have been reported [39]. Besides CO2, also other metabolites like the volatile compounds trimethylamine (TMA), dimethylamine (DMA), and ammonia, collectively known as TVB-N; biogenic amines such as histamine, putrescine, tyramine, and cadaverine; ethanol; sulfuric compounds; and organic acids have been studied as suitable target molecules for these pHsensing indicators [34]. It can sense and share information to the producer, retailer, or consumer at any time. Thus, the development of freshness indicator is based on a broad knowledge of quality-related metabolites closely related to product types, packaging material, the growth of microorganisms, and storage condition.

Various kinds of freshness indicators have been developed [40–43]. Freshness indicators are normally comprised of food spoilage and ripeness indicators [44]. Food spoilage indicators commonly investigate the spoilage of food due to the chemical changes, microbial growth, temperature abuse, or packaging leakage. The concepts for food spoilage indicators are based on changes in color indicator which response to microbial metabolites produced during spoilage process. Ripeness indicators are mostly used in fruit and some kind of vegetable product. However, this indicator is suitable for climacteric fruit rather than non-climacteric fruit because after harvest they still continue to ripen which is easily detected by indicators. During fruit ripening, there are many changes that occur such as loss of chlorophyll; ethylene production; conversion of starch to sugar; aroma development; changes in organic acids, proteins, and fats; etc. [33]. Changes in color indicator can help the consumers to decide the product when these fruits are fully mature, ripen, and ready to eat, e.g., durian, mango, and banana [7, 40]. However, freshness indicator has a disadvantage; it provides the broad-spectrum color change, which needs to be resolved before being used commercially.

Chen et al. [45] developed on-package indicator labels for the determination of lean pork freshness. The indicator label was based on methylcellulose immobilized with mixed dye (bromothymol blue/methyl red, 3:2). These labels were used to monitor freshness of pork at 5°C for 8 days. The indicator label presented visual color changes due to the presence of volatile compound (TVB-N) and aerobic plate counts. The authors reported that the colorimetric freshness indicator was able to recognize fresh (0–3 days) (red), medium fresh (4–5 days) (goldenrod), and spoiled stage (6–8 days) (green). Therefore, the indicator labels could be used

**115**

*3.3.3 Gas indicators*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

to monitor the real-time pork freshness as intelligent packaging tool and could

Meng et al. [6] defined time-temperature indicators (TTI) as a small device placed on a product or package that can be used to record, monitor, and indicate the time-temperature history on the quality of perishable product during the cold chain transportation and storage from the point of producer to the end consumer. Temperature is a critical factor influencing the food quality and safety during retail outlet or distribution and storage. The temperature history of packaged food is very difficult to control and monitor; thus, it is difficult to predict their shelf life. Thus, TTI can help to monitor and record the temperature condition during distribution and storage. The principle of TTI operation is based on chemical, enzymatic, mechanical, electrochemical, or microbiological change, generally expressed as a visible response in the form of a mechanical deformation, irreversible visible color development, or color change movement [46]. TTI should also be low-cost, reliable, with good stability, flexible to a wide range of temperatures, nontoxic, and easily

The TTI is useful because it can inform the consumers when the product has been temperature abused. If the temperature of the product is higher than the temperature recommended, the food quality can quickly deteriorate. TTI is mostly used in chilled or frozen foods, where the cold storage during distribution is important for food quality and safety. The role of developed system is to detect the quality changes by evaluating the pH alteration of the packaged foods during transportation and storage. Different kinds of food material will be stored at different temperatures; the system had the ability to detect temperature changes indirectly with the help of variation of pH of the food products, which occurred due to the improper temperature for the transportation and storage. Recently, a prototype diffusion-based TTI has been developed by Suppakul et al. [47]. A polydiacetylene (PDA)/SiO2 nanocomposite was used as the color-developing substance and loaded on the diffusion path. Tween 20 was used as a moving substance. The authors said that when Tween 20 reached the test line of the PDA/SiO2 nanocomposite, the color of the line changed from blue to red, indicating the TTI endpoint. Moreover, four TTIs were designed by matching the TTI endpoint with the deterioration time of food during storage at different temperatures (5, 10, 15, and 25°C). When diffusionbased TTI was applied on the tested food, the line of the PDA/SiO2 nanocomposite

It is very difficult to assess the packaged food quality because of many factors such as the production of gas by microorganisms within the package, changing concentration of gas and gas leakage from outside or inside of the packaging materials, or continuing fruit and vegetable respiration. Thus, gas indicators have been developed to solve these problems. Gas indicators, commonly produced in the form of label, are attached inside the food package for monitoring the changes of the level of gas, such as O2 and CO2, and then provide information through visual color changes [48]. A mixed pH dye-based indicator was developed for checking their ability of changes in color at different concentrations of CO2 (10–80%) [48]. This indicator is relatively sensitive to the change of CO2 level by changing the color from blue to green when the CO2 level increased. The principle of gas indicators

was matched to the shelf life of the tested food during storage.

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

enhance the guarantee of pork safety.

*3.3.2 Time-temperature indicators*

integrated into a packaging material.

to monitor the real-time pork freshness as intelligent packaging tool and could enhance the guarantee of pork safety.

#### *3.3.2 Time-temperature indicators*

*Food Preservation and Waste Exploitation*

*3.3.1 Freshness indicators*

condition.

resolved before being used commercially.

sensors and indicators is the components; indicators do not contain receptor and transducer components as the sensor, so it provides qualitative information through directly visible color change. According to Smolander [38], changes in color of pH dye indicator can be proposed to investigate acidic and/or basic volatile compounds

Freshness indicators are devices that are printed on the packaging film or in the form of a package label and then attached inside the packaging materials. Freshness indicators have been developed with the aim of investigating the food spoilage process, degree of fermentation, or ripening stage of fruits and vegetables and then informing the users about the freshness of packaged goods through color changes that can be directly detected by the naked eye. Freshness indicators provide direct information of the packaged food quality resulting from chemical changes or microbial growth within a food product. Indicator may react to metabolites that are generated in the package as a result of metabolism or the microbial growth [34]. Freshness indicator concepts based on pH sensing film, using CO2 as the major target, have been reported [39]. Besides CO2, also other metabolites like the volatile compounds trimethylamine (TMA), dimethylamine (DMA), and ammonia, collectively known as TVB-N; biogenic amines such as histamine, putrescine, tyramine, and cadaverine; ethanol; sulfuric compounds; and organic acids have been studied as suitable target molecules for these pHsensing indicators [34]. It can sense and share information to the producer, retailer, or consumer at any time. Thus, the development of freshness indicator is based on a broad knowledge of quality-related metabolites closely related to product types, packaging material, the growth of microorganisms, and storage

Various kinds of freshness indicators have been developed [40–43]. Freshness indicators are normally comprised of food spoilage and ripeness indicators [44]. Food spoilage indicators commonly investigate the spoilage of food due to the chemical changes, microbial growth, temperature abuse, or packaging leakage. The concepts for food spoilage indicators are based on changes in color indicator which response to microbial metabolites produced during spoilage process. Ripeness indicators are mostly used in fruit and some kind of vegetable product. However, this indicator is suitable for climacteric fruit rather than non-climacteric fruit because after harvest they still continue to ripen which is easily detected by indicators. During fruit ripening, there are many changes that occur such as loss of chlorophyll; ethylene production; conversion of starch to sugar; aroma development; changes in organic acids, proteins, and fats; etc. [33]. Changes in color indicator can help the consumers to decide the product when these fruits are fully mature, ripen, and ready to eat, e.g., durian, mango, and banana [7, 40]. However, freshness indicator has a disadvantage; it provides the broad-spectrum color change, which needs to be

Chen et al. [45] developed on-package indicator labels for the determination of lean pork freshness. The indicator label was based on methylcellulose immobilized with mixed dye (bromothymol blue/methyl red, 3:2). These labels were used to monitor freshness of pork at 5°C for 8 days. The indicator label presented visual color changes due to the presence of volatile compound (TVB-N) and aerobic plate counts. The authors reported that the colorimetric freshness indicator was able to recognize fresh (0–3 days) (red), medium fresh (4–5 days) (goldenrod), and spoiled stage (6–8 days) (green). Therefore, the indicator labels could be used

and provide an irreversible color change in an appearance.

**114**

Meng et al. [6] defined time-temperature indicators (TTI) as a small device placed on a product or package that can be used to record, monitor, and indicate the time-temperature history on the quality of perishable product during the cold chain transportation and storage from the point of producer to the end consumer. Temperature is a critical factor influencing the food quality and safety during retail outlet or distribution and storage. The temperature history of packaged food is very difficult to control and monitor; thus, it is difficult to predict their shelf life. Thus, TTI can help to monitor and record the temperature condition during distribution and storage. The principle of TTI operation is based on chemical, enzymatic, mechanical, electrochemical, or microbiological change, generally expressed as a visible response in the form of a mechanical deformation, irreversible visible color development, or color change movement [46]. TTI should also be low-cost, reliable, with good stability, flexible to a wide range of temperatures, nontoxic, and easily integrated into a packaging material.

The TTI is useful because it can inform the consumers when the product has been temperature abused. If the temperature of the product is higher than the temperature recommended, the food quality can quickly deteriorate. TTI is mostly used in chilled or frozen foods, where the cold storage during distribution is important for food quality and safety. The role of developed system is to detect the quality changes by evaluating the pH alteration of the packaged foods during transportation and storage. Different kinds of food material will be stored at different temperatures; the system had the ability to detect temperature changes indirectly with the help of variation of pH of the food products, which occurred due to the improper temperature for the transportation and storage. Recently, a prototype diffusion-based TTI has been developed by Suppakul et al. [47]. A polydiacetylene (PDA)/SiO2 nanocomposite was used as the color-developing substance and loaded on the diffusion path. Tween 20 was used as a moving substance. The authors said that when Tween 20 reached the test line of the PDA/SiO2 nanocomposite, the color of the line changed from blue to red, indicating the TTI endpoint. Moreover, four TTIs were designed by matching the TTI endpoint with the deterioration time of food during storage at different temperatures (5, 10, 15, and 25°C). When diffusionbased TTI was applied on the tested food, the line of the PDA/SiO2 nanocomposite was matched to the shelf life of the tested food during storage.

#### *3.3.3 Gas indicators*

It is very difficult to assess the packaged food quality because of many factors such as the production of gas by microorganisms within the package, changing concentration of gas and gas leakage from outside or inside of the packaging materials, or continuing fruit and vegetable respiration. Thus, gas indicators have been developed to solve these problems. Gas indicators, commonly produced in the form of label, are attached inside the food package for monitoring the changes of the level of gas, such as O2 and CO2, and then provide information through visual color changes [48]. A mixed pH dye-based indicator was developed for checking their ability of changes in color at different concentrations of CO2 (10–80%) [48]. This indicator is relatively sensitive to the change of CO2 level by changing the color from blue to green when the CO2 level increased. The principle of gas indicators

(pH dye-based) was explained by Puligundla et al. [49]. CO2 generally dissolves in an aqueous solution and then forms carbonic acid (H2CO3). H2CO3 dissociates into hydrogen ions (H<sup>+</sup> ) and bicarbonate ions (HCO3 <sup>−</sup>). Then, H<sup>+</sup> , as a proton, combines with a water molecule to form a hydronium ion (H3O<sup>+</sup> ). This H3O<sup>+</sup> reacts with the basic (dissociated) form (In<sup>−</sup>) of the pH dye indicator, resulting in an acid (protonated) form (HIn) which in turn develops a color change in the indicator containing label [49].

#### **3.4 Radio-frequency identification devices**

RFID, a food traceability system, is a small device that can be attached to the product, so that the product could be identified and tracked in real time. It is commonly grouped under the form wireless automatic identification together with biometrics, magnetic inks, QR codes, barcode, etc. [32]. RFID tags mainly comprise of three components including a tag produced from a microchip linked to a small aerial, a reader capable of discharging radio signals and also accepting answers from the tag in response to the sent signals, and a network system or web server that connects the company and the RFID equipment [50]. There are three categories of RFID, which based on the power supply include passive RFID tags, semi-passive RFID tags, and active RFID tags [32]. This tool is suitable for the large-scale production network, such as food supply chains, which can control material flow and/or give information. It is typically used in order to reduce uncertainties in the food purchasing process by giving information about the whole process in terms of quality and safety.

#### **4. Sources of dye indicator**

The inclusion of dye indicator into packaging materials is a promising method for the development of smart packaging. Dyes can interact with stimulus; then the color changes are obtained, which can be observed by the naked eye. Color change of dye is cause of the electron at double bonds in the dyes able to absorb the energy at visible range wavelengths (400–700 nm). Difference structures of dye will absorb different wavelengths, which are related to their colorations. It is an organic or inorganic substance. Generally, there are two main sources of indicator: chemical dye and natural extract (**Table 2**). These components are widely used as coloring agent because they are sensitive to the condition change and are able to inform the packaged food conditions to the manufacturers and the end consumers. Food deterioration or fermentation process is mostly correlated with pH change. Thus, pH indicator dye-based colorimetric is a type of dye indicator that is widely added into materials.

#### **4.1 Chemical dye**

Most of the chemical dyes are made up of synthetic material, which may be toxic to the consumer and not suitable for use in food application. The commercially available chemical pH dye is mostly based on halochromic compound and belonged to sulfonephthalein dye and azo dye groups. Sulfonephthalein dyes include phenol red, bromophenol blue, bromocresol green, and bromothymol blue, and azo dye includes methyl red (**Figure 2**). These chemical dyes are widely used as pH dye indicator because they exhibit a clear color according to pH. Change in color of pH dyes is due to a protonation/deprotonation reaction [64]. There are two forms of pH dye: Hln (acid form) and In<sup>−</sup> (basic form). Furthermore, the chemical pH-sensitive dye is often limited in the pH range and showed very narrow color. For example,

**117**

**Table 2.**

*Example of dye indicator.*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

tion of two dyes has been widely used as chemical indicator [7, 39, 48, 52].

flavylium cation (red color) are predominantly formed; at pH between

Bromocresol green Pirsa et al. [53] Methyl orange Pirsa et al. [53]

Phenol red Kim et al. [54]

Blueberry Luchese et al. [55] Butterfly pea Rawdkuen et al. [56] Grape Ma and Wang [57] Mulberry Ma et al. [58]

Roselle Zhai et al. [9]

Bromophenol blue Zaragozá et al. [51], Chen et al. [52], Dirpan et al. [40]

[48], Chen et al. [52]

Pourjavaher et al. [63]

Purple sweet potato Liu et al. [59], Choi et al. [60], Yong et al. [61] Red cabbage Pereira et al. [8], Silva-Pereira et al. [62],

Rukchon et al. [39], Niponsak et al. [7], Baek et al.

Methyl red Niponsak et al. [7], Chen et al. [52]

**Sources Indicators References**

Mixing methyl red and bromothymol blue

bromophenol blue has only two color transitions: yellow at pH 3 and blue at pH 4.6, and phenol red also exhibits two color transitions, yellow at pH below 6.4 and pink at pH above 8.0, which is difficult to observe by the naked eye. Thus, it needs to combine with other chemical dyes to enable pH indication [65]. Baek et al. [48] studied the combination of two chemical dye indicators at different ratios (methyl red/bromothymol blue; 1:9, 3:7, 5:5, 7:3, and 9:1). The authors suggested that the mixing of two dyes exhibited various color changes in a narrow pH range, compared to the methyl red alone or bromothymol blue alone. Therefore, the combina-

Nowadays, the consumers concern about the use of the chemical compounds in foods and some chemical substances that are not generally recognized as safe compounds and may be harmful to the consumers' health. Thus, natural extract is an alternative source of indicator that can be used instead of chemical dye. Anthocyanins are natural colorants and water-soluble pigments belonging to the flavonoids family. These pigment compounds are responsible for the color (red, purple, and blue) of plant leaves, flowers, grains, fruits, and vegetables. Changes in color of anthocyanins are mostly due to the presence of phenolic or conjugated compound. The structure of anthocyanins changes when there is a difference in pH values [66]. Thus, anthocyanins are compounds that are mostly used as natural pH dye indicator because it shows a broad color change in function of pH. Color mechanism of anthocyanins can be described as illustrated in **Figure 3**, and the color chart of anthocyanins extracted from different sources of plants at different pH levels, compared to chemical dye (resazurin), is shown in **Figure 4**. Anthocyanins can be exhibited in different chemical structure forms depending on pH. In acidic condition (pH 1), intact structure forms of the

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

**4.2 Natural extract**

Chemical dye

Natural extract

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

bromophenol blue has only two color transitions: yellow at pH 3 and blue at pH 4.6, and phenol red also exhibits two color transitions, yellow at pH below 6.4 and pink at pH above 8.0, which is difficult to observe by the naked eye. Thus, it needs to combine with other chemical dyes to enable pH indication [65]. Baek et al. [48] studied the combination of two chemical dye indicators at different ratios (methyl red/bromothymol blue; 1:9, 3:7, 5:5, 7:3, and 9:1). The authors suggested that the mixing of two dyes exhibited various color changes in a narrow pH range, compared to the methyl red alone or bromothymol blue alone. Therefore, the combination of two dyes has been widely used as chemical indicator [7, 39, 48, 52].

#### **4.2 Natural extract**

*Food Preservation and Waste Exploitation*

**3.4 Radio-frequency identification devices**

into hydrogen ions (H<sup>+</sup>

containing label [49].

**4. Sources of dye indicator**

(pH dye-based) was explained by Puligundla et al. [49]. CO2 generally dissolves in an aqueous solution and then forms carbonic acid (H2CO3). H2CO3 dissociates

with the basic (dissociated) form (In<sup>−</sup>) of the pH dye indicator, resulting in an acid (protonated) form (HIn) which in turn develops a color change in the indicator

RFID, a food traceability system, is a small device that can be attached to the product, so that the product could be identified and tracked in real time. It is commonly grouped under the form wireless automatic identification together with biometrics, magnetic inks, QR codes, barcode, etc. [32]. RFID tags mainly comprise of three components including a tag produced from a microchip linked to a small aerial, a reader capable of discharging radio signals and also accepting answers from the tag in response to the sent signals, and a network system or web server that connects the company and the RFID equipment [50]. There are three categories of RFID, which based on the power supply include passive RFID tags, semi-passive RFID tags, and active RFID tags [32]. This tool is suitable for the large-scale production network, such as food supply chains, which can control material flow and/or give information. It is typically used in order to reduce uncertainties in the food purchasing process by

giving information about the whole process in terms of quality and safety.

The inclusion of dye indicator into packaging materials is a promising method for the development of smart packaging. Dyes can interact with stimulus; then the color changes are obtained, which can be observed by the naked eye. Color change of dye is cause of the electron at double bonds in the dyes able to absorb the energy at visible range wavelengths (400–700 nm). Difference structures of dye will absorb different wavelengths, which are related to their colorations. It is an organic or inorganic substance. Generally, there are two main sources of indicator: chemical dye and natural extract (**Table 2**). These components are widely used as coloring agent because they are sensitive to the condition change and are able to inform the packaged food conditions to the manufacturers and the end consumers. Food deterioration or fermentation process is mostly correlated with pH change. Thus, pH indicator dye-based colorimetric is a type of dye indicator that is widely added

Most of the chemical dyes are made up of synthetic material, which may be toxic

to the consumer and not suitable for use in food application. The commercially available chemical pH dye is mostly based on halochromic compound and belonged to sulfonephthalein dye and azo dye groups. Sulfonephthalein dyes include phenol red, bromophenol blue, bromocresol green, and bromothymol blue, and azo dye includes methyl red (**Figure 2**). These chemical dyes are widely used as pH dye indicator because they exhibit a clear color according to pH. Change in color of pH dyes is due to a protonation/deprotonation reaction [64]. There are two forms of pH dye: Hln (acid form) and In<sup>−</sup> (basic form). Furthermore, the chemical pH-sensitive dye is often limited in the pH range and showed very narrow color. For example,

<sup>−</sup>). Then, H<sup>+</sup>

, as a proton,

reacts

). This H3O<sup>+</sup>

) and bicarbonate ions (HCO3

combines with a water molecule to form a hydronium ion (H3O<sup>+</sup>

**116**

into materials.

**4.1 Chemical dye**

Nowadays, the consumers concern about the use of the chemical compounds in foods and some chemical substances that are not generally recognized as safe compounds and may be harmful to the consumers' health. Thus, natural extract is an alternative source of indicator that can be used instead of chemical dye. Anthocyanins are natural colorants and water-soluble pigments belonging to the flavonoids family. These pigment compounds are responsible for the color (red, purple, and blue) of plant leaves, flowers, grains, fruits, and vegetables. Changes in color of anthocyanins are mostly due to the presence of phenolic or conjugated compound. The structure of anthocyanins changes when there is a difference in pH values [66]. Thus, anthocyanins are compounds that are mostly used as natural pH dye indicator because it shows a broad color change in function of pH. Color mechanism of anthocyanins can be described as illustrated in **Figure 3**, and the color chart of anthocyanins extracted from different sources of plants at different pH levels, compared to chemical dye (resazurin), is shown in **Figure 4**. Anthocyanins can be exhibited in different chemical structure forms depending on pH. In acidic condition (pH 1), intact structure forms of the flavylium cation (red color) are predominantly formed; at pH between


**Table 2.** *Example of dye indicator.*

*Structural formulas of some chemical dye indicators used in indicator labels.*

2 and 4, the quinoidal blue species are formed; at pH value between 5 and 6, only two colorless structures (a chalone and a carbine pseudobase) are formed; and in basic conditions (pH > 7), the chemical structure forms are dependent on their substitution groups [67]. Therefore, anthocyanins can go through chemical changes due to pH variation. It can be successfully used as natural dye indicator for determining the food deterioration. Currently used extracted anthocyanins of some plants as natural indicator are shown in **Table 2**.

#### **5. Applications of smart packaging films**

The main purpose of packaging for fresh meat, poultry, fish, seafood, fruits and vegetables, etc. is to delay chemical, microbial, and biochemical changes, avoid contamination, reduce weight loss, and enhance overall product appearance to meet consumer expectations and preferences [34]. In general, food quality can be investigated through chemical analysis and microbiological evaluation. However, there are some quality attributes that need to alert the producers, retailers, or consumers during the whole supply chain. The qualities of the packaged food always change after processing or during distribution and

**119**

**Figure 4.**

*chemical dye (resazurin). Source: Rawdkuen et al. [56].*

**Figure 3.**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

*Anthocyanin chemical structure forms depending on pH. Source: Castaneda-Ovando et al. [67].*

*Color chart of anthocyanins extracted from different sources of plants at different pH levels, compared to* 

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

**Figure 4.**

*Food Preservation and Waste Exploitation*

2 and 4, the quinoidal blue species are formed; at pH value between 5 and 6, only two colorless structures (a chalone and a carbine pseudobase) are formed; and in basic conditions (pH > 7), the chemical structure forms are dependent on their substitution groups [67]. Therefore, anthocyanins can go through chemical changes due to pH variation. It can be successfully used as natural dye indicator for determining the food deterioration. Currently used extracted anthocyanins

The main purpose of packaging for fresh meat, poultry, fish, seafood, fruits and vegetables, etc. is to delay chemical, microbial, and biochemical changes, avoid contamination, reduce weight loss, and enhance overall product appearance to meet consumer expectations and preferences [34]. In general, food quality can be investigated through chemical analysis and microbiological evaluation. However, there are some quality attributes that need to alert the producers, retailers, or consumers during the whole supply chain. The qualities of the packaged food always change after processing or during distribution and

of some plants as natural indicator are shown in **Table 2**.

*Structural formulas of some chemical dye indicators used in indicator labels.*

**5. Applications of smart packaging films**

**118**

**Figure 2.**

*Color chart of anthocyanins extracted from different sources of plants at different pH levels, compared to chemical dye (resazurin). Source: Rawdkuen et al. [56].*

storage. Thus, these quality changes of the packaged food are difficult to evaluate by the retailers or consumers. Moreover, different types of food require a specific condition and relative humidity (RH) for their transportation and preservation. With an advantage of smart packaging, it is possible to detect the quality of the food that is packed in the package. Smart packaging tools exhibit some changes in themselves (color development) which relate to the changes in the physicochemical and biological properties of the packaged food. They are mostly placed inside or outside of the package to observe the alteration in the quality of packaged product and to inform the users about the food safety and quality through visible color changes, as illustrated in **Figure 5**.

In the recent year, the applications of smart packaging tools or devices on food product have been described [48, 53, 58]. Indicators are the most frequently used tool due to their nondestructive method, simplicity, low cost, and easy detection by the naked eye. Chemical and biological changes in food product generally occur during handling, storage, and transportation. Contamination by microorganisms is also the main spoilage of most foods. Microbes can be generated the different chemical metabolites, such as CO2, organic acids, alcohol (ethanol), and hydrogen sulfide (H2S), and nitrogen containing molecules, which have been proposed as suitable target molecules for indicators [34]. When the levels of these volatile compounds increase, pH level will also increase. As a consequence, the freshness of packaged food is decreasing. The use of colorimetric indicator film as a smart packaging can inform the real conditions of the packaged food to consumer in real-time monitoring of food quality under certain condition. Smart packaging films are widely applied on high-value products, such as meat, fish, seafood, fruits, and vegetables, for monitoring package headspace and/or perishable food spoilage. Hence, smart packaging would be very helpful in ensuring the packaged food safety and quality throughout the whole distribution chain.

#### **Figure 5.**

*Example of freshness indicator for monitoring the degree of fermentation of plaa-som, a Thai fermented fish. The indicator produced from gelatin film incorporated with anthocyanins extracted from butterfly pea (left) and gelatin film containing rezasurin (right).*

**121**

**Table 3.**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

Fresh meat is very perishable and susceptible for physicochemical changes. It generally deteriorates within 3–4 days of slaughter, even if it is kept in refrigeration. Meat products also represent excellent basic nutrients and are easily spoiled by microorganisms. The loss of meat freshness means meat has begun to spoil. The shelf life of meat is the storage time until spoilage, which are complex conditions because the combination of biological and physicochemical activities may interact and make the products unacceptable for human consumption [68]. An acceptable level of microbial, unacceptable appearance, and/or off-flavor is strictly depended on the degree of lipid oxidation, autolytic enzyme reaction, and the level of microbial contamination. Microorganism is one of the major meat spoilers. It can produce the compounds that correlate with spoilage, responsible for strong off-odors and discoloration. Slime production would constitute the major qualitative criteria for the rejection of meat. Meat itself comprises an essential nutrient (amino acids, nucleotides, and sugar). These nutrients are adequate for microbial growth, and the metabolism of these compounds leads to the formation of biogenic amines, H2S, NH3, indole, organic acids, and other substances characteristic of meat spoilage [68]. Meat industry requires rapid and simplest tool or device to determine the quality of packaged meat, to predict remaining shelf life of its product, and to provide information on the degree of spoilage. Consequently, smart packaging could be employed to detect microbial metabolites produced on packaged meat sample by reacting with volatile compounds and displaying an irreversible change in visual color, since it can be monitored directly by the naked eye. Applications of smart packaging on meat

Several freshness indicator concepts based on pH dyes, using CO2 as the main target metabolite have been proposed. An alternative method for detection of chicken breast freshness was proposed by Rukchon et al. [39]. The authors used a

**Material Indicators Type of** 

extract

of 2:3)

Pork Reverse phase silica gel Black rice extract Gas sensor Huang

Dunn. flower extract

Bromothymol bluemethyl red (ratio

amylose, and iodine

Chitosan-corn starch Hibiscus flower

Pork Chitosan *Bauhinia blakeana*

Pork A4 paper Glucoamylase,

Methylcellulosehydroxypropyl methylcellulose

*Application of smart packaging films on meat products.*

Chicken Cassava starch Blueberry residue Freshness

Pork Agar-potato starch Purple sweet potato Freshness

**intelligence**

Freshness indicator

indicator

Freshness indicator

indicator

Timetemperature indicator

Gas indicator Rukchon

**References**

Othman et al. [43]

Luchese et al. [55]

Zhang et al. [69]

Choi et al. [60]

et al. [39]

Meng et al. [6]

et al. [70]

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

products are shown in **Table 3**.

**Food product**

Chicken breast

Skinless chicken breast

**5.1 Application of smart packaging on meat products**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### **5.1 Application of smart packaging on meat products**

*Food Preservation and Waste Exploitation*

color changes, as illustrated in **Figure 5**.

distribution chain.

storage. Thus, these quality changes of the packaged food are difficult to evaluate by the retailers or consumers. Moreover, different types of food require a specific condition and relative humidity (RH) for their transportation and preservation. With an advantage of smart packaging, it is possible to detect the quality of the food that is packed in the package. Smart packaging tools exhibit some changes in themselves (color development) which relate to the changes in the physicochemical and biological properties of the packaged food. They are mostly placed inside or outside of the package to observe the alteration in the quality of packaged product and to inform the users about the food safety and quality through visible

In the recent year, the applications of smart packaging tools or devices on food product have been described [48, 53, 58]. Indicators are the most frequently used tool due to their nondestructive method, simplicity, low cost, and easy detection by the naked eye. Chemical and biological changes in food product generally occur during handling, storage, and transportation. Contamination by microorganisms is also the main spoilage of most foods. Microbes can be generated the different chemical metabolites, such as CO2, organic acids, alcohol (ethanol), and hydrogen sulfide (H2S), and nitrogen containing molecules, which have been proposed as suitable target molecules for indicators [34]. When the levels of these volatile compounds increase, pH level will also increase. As a consequence, the freshness of packaged food is decreasing. The use of colorimetric indicator film as a smart packaging can inform the real conditions of the packaged food to consumer in real-time monitoring of food quality under certain condition. Smart packaging films are widely applied on high-value products, such as meat, fish, seafood, fruits, and vegetables, for monitoring package headspace and/or perishable food spoilage. Hence, smart packaging would be very helpful in ensuring the packaged food safety and quality throughout the whole

*Example of freshness indicator for monitoring the degree of fermentation of plaa-som, a Thai fermented fish. The indicator produced from gelatin film incorporated with anthocyanins extracted from butterfly pea (left)* 

**120**

**Figure 5.**

*and gelatin film containing rezasurin (right).*

Fresh meat is very perishable and susceptible for physicochemical changes. It generally deteriorates within 3–4 days of slaughter, even if it is kept in refrigeration. Meat products also represent excellent basic nutrients and are easily spoiled by microorganisms. The loss of meat freshness means meat has begun to spoil. The shelf life of meat is the storage time until spoilage, which are complex conditions because the combination of biological and physicochemical activities may interact and make the products unacceptable for human consumption [68]. An acceptable level of microbial, unacceptable appearance, and/or off-flavor is strictly depended on the degree of lipid oxidation, autolytic enzyme reaction, and the level of microbial contamination. Microorganism is one of the major meat spoilers. It can produce the compounds that correlate with spoilage, responsible for strong off-odors and discoloration. Slime production would constitute the major qualitative criteria for the rejection of meat. Meat itself comprises an essential nutrient (amino acids, nucleotides, and sugar). These nutrients are adequate for microbial growth, and the metabolism of these compounds leads to the formation of biogenic amines, H2S, NH3, indole, organic acids, and other substances characteristic of meat spoilage [68]. Meat industry requires rapid and simplest tool or device to determine the quality of packaged meat, to predict remaining shelf life of its product, and to provide information on the degree of spoilage. Consequently, smart packaging could be employed to detect microbial metabolites produced on packaged meat sample by reacting with volatile compounds and displaying an irreversible change in visual color, since it can be monitored directly by the naked eye. Applications of smart packaging on meat products are shown in **Table 3**.

Several freshness indicator concepts based on pH dyes, using CO2 as the main target metabolite have been proposed. An alternative method for detection of chicken breast freshness was proposed by Rukchon et al. [39]. The authors used a


#### **Table 3.**

*Application of smart packaging films on meat products.*

colorimetric mixed pH dye indicator (bromothymol blue/methyl red, ratio of 2:3) based on a methylcellulose-hydroxypropyl methylcellulose film as a chemical barcode for real-time monitoring of skinless chicken breast spoilage. Changes in color indicator from green to orange-yellow were correlated with CO2 level, microbial growth patterns, and the amount of volatile compounds of skinless chicken breast. The authors also concluded that the degree of chicken spoilage was related to CO2 levels increased due to microbial growth. Zhang et al. [69] present a convenient, nondestructive, and visible method for pork freshness detection. The indicator response was correlated with pH changes in pork sample, thus enabling real-time monitoring of spoilage. The indicator was prepared by immobilizing natural pH-sensitive dye (*Bauhinia blakeana* Dunn. flower extract) in chitosan, which responded through visible color changes from red to green.

Recently, a system for monitoring chicken breast freshness was developed by Othman et al. [43] based on hibiscus flower extract. The extract was incorporated into chitosan-corn starch-based film, and changes from purplish-gray to darker gray with green color were observed when pH increased as a consequence of the spoilage of chicken breast due to the accumulation of amine and ammonia by mesophilic bacteria. Luchese et al. [55] applied the pH sensing film (anthocyanins extracted from blueberry residue added cassava starch film) on chicken meat indirectly and directly on meat surface for monitoring the spoilage of chicken during storage at 6°C for 10 days. The authors found color pigment migration from indicator to surface of chicken when the pH sensing film was placed directly on chicken meat. This phenomenon may cause the consumer to not accept the product due to changed appearance. Choi et al. [60] developed a pH-sensitive indicator for detecting pork spoilage. pH indicator was prepared by immobilizing a natural dye (anthocyanins extracted from purple sweet potato) into agar-potato starch film. Trials on pork have verified that the color indicator response (from red to green) correlates with pH values in pork sample, thus enabling the real-time detection of spoilage. Meng et al. [6] developed enzyme-based TTI for prediction of pork shelf life during cold storage. It is prepared from sodium alginate, amylose, iodine, and glucoamylase microcapsules and then was coated on A4 paper. After activation (cover with agar), PE film was used to seal the TTI. This type of indicator is based on the reaction between an enzyme and a substrate, which can cause a color change in the system to indicate the reaction degree. When this indicator was applied on pork sample, changed in color from mazarine to colorless was observed. The color change represents the spoilage of chilled pork. A gas sensor array has been proposed by Huang et al. [70] and was used for detecting the biogenic amines generated on packaged fresh pork during storage at 5°C for 7 days. The colorimetric sensor array was created by printing anthocyanins extracted from black rice extract on reverse phase silica gel plates (inorganic material). The authors found a good relationship between the gas sensor array results (i.e., color change) and biogenic amine content. The authors also demonstrated the reaction between indicator and generated volatile compound; the hydroxyl and carbonyl groups of anthocyanin molecules could be interacted with the amines generated during pork spoilage, resulting in changes in color.

#### **5.2 Application of smart packaging on fish and seafood products**

Fish and seafood products are classified as extremely perishable products. The decomposition of fish and seafood products can also be due to three mechanisms: enzymatic reactions, oxidative deterioration, and microbial spoilage [71]. Lipid oxidation is the main spoilage of chemical nature. When bacteria grow, they produce metabolic by-products, and their accumulations cause the organoleptic

**123**

**Table 4.**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

rejection. However, microbial spoilage is the major mechanism that influences the quality deterioration of fresh fish and seafood and is responsible for shelf life duration. TVB-N, trimethylamines (TMA), sulfuric compounds, alcohols, aldehydes, ketones, and esters are the most common metabolites with characteristic odor that is produced by microorganisms during fish and seafood spoilage [71]. However, the produced compounds are dependent on the metabolic activity of selected specific spoilage organisms (SSO), which is directly influenced by storage conditions. It is difficult to determine the quality of packaged fish and seafood products; thus, a variety of approaches have been developed to monitor the freshness of fish and seafood products in real time. Indicators, one form of intelligent packaging, can react to changes—usually chemical or biological—occurring within the headspace of packaging as the fish and seafood spoil. Thus, indicator generally gives characteristic change: a highly visual color change of the indicator allows for a rapid assessment of the quality of the packed fish seafood products. Considering the food quality and safety, intelligent packaging is an alternative tool that can be used to assess the shelf life and freshness status of fish and seafood products during the supply chain. Applications of smart packaging on fish and seafood products are

A real-time technique for evaluating fish freshness was prepared by Silva-Pereira et al. [62]. Chitosan-corn starch was used as starting material for making freshness indicator, and red cabbage was used as a dye indicator. The indicator film was used to monitor the fish spoilage storage at room (25°C) and refrigeration temperature (4–7°C) during 7 days. The authors found that the color of the indicator film stored at room temperature was completely changed after 72 h (from blue to yellow), indicating fish spoilage. Ma et al. [41] developed a smart film as indicator for monitoring fish freshness. Smart film was prepared based on tara gum-cellulose nanocrystals containing *Vitis amurensis* husk extract (by-product from white wine processing). The

**Material Indicators Type of** 

**intelligence**

Optoelectronic nose (sensor)

Red cabbage Freshness indicator Silva-

*Vitis amurensis* husk Freshness indicator Ma et al.

Mulberry extract Freshness indicator Ma et al.

Starch-PVA Roselle Freshness indicator Zhai et al.

Thymol blue, bromothymol blue sodium salt, bromocresol purple, dinuclear rhodium complex, and bromophenol blue

Anthraquinone and azo chromophores

Shrimp Tara gum-PVA Curcumin Sensor Ma et al.

**References**

Pereira et al. [62]

[41]

[58]

[9]

[72]

[41]

Freshness Zhang et al.

Zaragozá et al. [51]

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

shown in **Table 4**.

**Food product**

Silver carp

Cooked crabs

*PVA: polyvinyl alcohol.*

Fish Chitosan-corn starch

> cellulose nanocrystals

nanoparticles

Paper cellulose fibers

*Application of smart packaging films on fish and seafood products.*

Fish Tara gum-

Fish PVA-chitosan

Squid Aluminum oxide and silica gel

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

rejection. However, microbial spoilage is the major mechanism that influences the quality deterioration of fresh fish and seafood and is responsible for shelf life duration. TVB-N, trimethylamines (TMA), sulfuric compounds, alcohols, aldehydes, ketones, and esters are the most common metabolites with characteristic odor that is produced by microorganisms during fish and seafood spoilage [71]. However, the produced compounds are dependent on the metabolic activity of selected specific spoilage organisms (SSO), which is directly influenced by storage conditions. It is difficult to determine the quality of packaged fish and seafood products; thus, a variety of approaches have been developed to monitor the freshness of fish and seafood products in real time. Indicators, one form of intelligent packaging, can react to changes—usually chemical or biological—occurring within the headspace of packaging as the fish and seafood spoil. Thus, indicator generally gives characteristic change: a highly visual color change of the indicator allows for a rapid assessment of the quality of the packed fish seafood products. Considering the food quality and safety, intelligent packaging is an alternative tool that can be used to assess the shelf life and freshness status of fish and seafood products during the supply chain. Applications of smart packaging on fish and seafood products are shown in **Table 4**.

A real-time technique for evaluating fish freshness was prepared by Silva-Pereira et al. [62]. Chitosan-corn starch was used as starting material for making freshness indicator, and red cabbage was used as a dye indicator. The indicator film was used to monitor the fish spoilage storage at room (25°C) and refrigeration temperature (4–7°C) during 7 days. The authors found that the color of the indicator film stored at room temperature was completely changed after 72 h (from blue to yellow), indicating fish spoilage. Ma et al. [41] developed a smart film as indicator for monitoring fish freshness. Smart film was prepared based on tara gum-cellulose nanocrystals containing *Vitis amurensis* husk extract (by-product from white wine processing). The


#### **Table 4.**

*Application of smart packaging films on fish and seafood products.*

*Food Preservation and Waste Exploitation*

colorimetric mixed pH dye indicator (bromothymol blue/methyl red, ratio of 2:3) based on a methylcellulose-hydroxypropyl methylcellulose film as a chemical barcode for real-time monitoring of skinless chicken breast spoilage. Changes in color indicator from green to orange-yellow were correlated with CO2 level, microbial growth patterns, and the amount of volatile compounds of skinless chicken breast. The authors also concluded that the degree of chicken spoilage was related to CO2 levels increased due to microbial growth. Zhang et al. [69] present a convenient, nondestructive, and visible method for pork freshness detection. The indicator response was correlated with pH changes in pork sample, thus enabling real-time monitoring of spoilage. The indicator was prepared by immobilizing natural pH-sensitive dye (*Bauhinia blakeana* Dunn. flower extract) in chitosan, which

Recently, a system for monitoring chicken breast freshness was developed by Othman et al. [43] based on hibiscus flower extract. The extract was incorporated into chitosan-corn starch-based film, and changes from purplish-gray to darker gray with green color were observed when pH increased as a consequence of the spoilage of chicken breast due to the accumulation of amine and ammonia by mesophilic bacteria. Luchese et al. [55] applied the pH sensing film (anthocyanins extracted from blueberry residue added cassava starch film) on chicken meat indirectly and directly on meat surface for monitoring the spoilage of chicken during storage at 6°C for 10 days. The authors found color pigment migration from indicator to surface of chicken when the pH sensing film was placed directly on chicken meat. This phenomenon may cause the consumer to not accept the product due to changed appearance. Choi et al. [60] developed a pH-sensitive indicator for detecting pork spoilage. pH indicator was prepared by immobilizing a natural dye (anthocyanins extracted from purple sweet potato) into agar-potato starch film. Trials on pork have verified that the color indicator response (from red to green) correlates with pH values in pork sample, thus enabling the real-time detection of spoilage. Meng et al. [6] developed enzyme-based TTI for prediction of pork shelf life during cold storage. It is prepared from sodium alginate, amylose, iodine, and glucoamylase microcapsules and then was coated on A4 paper. After activation (cover with agar), PE film was used to seal the TTI. This type of indicator is based on the reaction between an enzyme and a substrate, which can cause a color change in the system to indicate the reaction degree. When this indicator was applied on pork sample, changed in color from mazarine to colorless was observed. The color change represents the spoilage of chilled pork. A gas sensor array has been proposed by Huang et al. [70] and was used for detecting the biogenic amines generated on packaged fresh pork during storage at 5°C for 7 days. The colorimetric sensor array was created by printing anthocyanins extracted from black rice extract on reverse phase silica gel plates (inorganic material). The authors found a good relationship between the gas sensor array results (i.e., color change) and biogenic amine content. The authors also demonstrated the reaction between indicator and generated volatile compound; the hydroxyl and carbonyl groups of anthocyanin molecules could be interacted with the amines generated during pork spoilage, resulting in

responded through visible color changes from red to green.

**5.2 Application of smart packaging on fish and seafood products**

Fish and seafood products are classified as extremely perishable products. The decomposition of fish and seafood products can also be due to three mechanisms: enzymatic reactions, oxidative deterioration, and microbial spoilage [71]. Lipid oxidation is the main spoilage of chemical nature. When bacteria grow, they produce metabolic by-products, and their accumulations cause the organoleptic

**122**

changes in color.

colorimetric film was adhered in a sealable bag to directly detect the color difference during fish spoilage. The color changed from pink to yellow-green due to fish spoilage. These color changes were related to the production of volatile basic nitrogen and the increase of pH. Ma et al. [58] developed a pH indicator which consisted of polyvinyl alcohol (PVA)-chitosan nanoparticles and mulberry extract. This indicator was tested for monitoring fish spoilage. The authors found that change in color indicator from red to green was correlated with the presence of volatile nitrogenous compounds, which is characteristic of fish spoilage. Anthocyanins that were extracted from roselle immobilized onto starch-PVA-based film were proposed by Zhai et al. [9] as visual colorimetric film for volatile nitrogenous compounds released in fish spoilage. The visual changes were monitored along 165 h refrigeration temperature (4°C), and the beginning purple color of colorimetric film changed over time to green (at 90 h) and finally yellow (after 135 h). These color changes indicated that the colorimetric films became more basic due to the increasing TVB-N.

The optoelectronic nose is based on the combination of pH indicator and selective chromogenic reagents supported on inorganic materials with diverse acidities and topologies [73]. A novel optoelectronic nose to monitor squid spoilage is proposed by Zaragozá et al. [51]. It is based on five pigments prepared by mixing the different corresponding dyes (thymol blue, bromothymol blue sodium salt, bromocresol purple, dinuclear rhodium complex, and bromophenol blue) with two inorganic supports (aluminum oxide and silica gel). Changes in color of sensor array were characteristic of packaged squid, which kept in cold storage for 12 days. The chromogenic array data were assessed with principal component analysis (PCA; qualitative) and partial least squares (PLS; quantitative) study tools. The PCA analysis carried out with CIE Lab showed that the colorimetric array was able to discriminate between fresh and spoiled squid. The statistical models obtained by PLS, with the optoelectronic nose, successfully predicted CO2 and O2 content in the headspace as well as microbial growth. The authors also suggested that this optoelectronic nose could help to evaluate cephalopod freshness, which is easy to use and rapid. Recently, a biosensor (tara gum-PVA-curcumin) was prepared by Ma et al. [41] for evaluation of shrimp spoilage at ambient temperature. The authors found a linear correlation between changes in total volatile basic nitrogen (TVB-N) and pH with the colorimetric response of sensor (slightly yellow to orange-red) within 1–3 min. The authors also suggested the possibility of using the developed film as a sensor for monitoring the spoilage of shrimp and other food products.

#### **5.3 Application of smart packaging on fruits and vegetables**

Fruits and vegetables are extremely perishable products and require appropriate handling and storage conditions over the distribution chain in order to preserve their quality and safety and to prolong the shelf life. These products are living products; it means they keep respiring, consuming O2, and producing CO2 after harvesting. Thus, the postharvest deterioration process is affected by intrinsic factors of the product. One of the major issues of fresh-cut products is the potential microbial spoilage. Smart packaging can be applied in fruit and vegetable product for facilitating the consumer to know the quality of packaged fruits and vegetables and to promote choosing the fruits and vegetables according to freshness or maturity without damaging the packaging. Generally, changes in color indicators represent the extent of ripening of packaged fruit and vegetable products, or in contrast the indicators represent the spoilage condition (microbial growth). According to Poças et al. [33], the packaging-specific requirements for fruits and vegetables are related to maintaining, controlling, and/ or monitoring temperature, gas composition and humidity, and mechanical damage. Applications of smart packaging on fruit and vegetable products are shown in **Table 5**.

**125**

**Table 5.**

**Food product**

Freshcut durian

Freshcut green bell pepper

Salad leaves Cassava starch-chitosan

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

The use of freshness indicator on fruit and vegetable products has been proposed. Niponsak et al. [7] described a colorimetric mixed pH dye-based indicator that responds through visible color changes to sulfur-containing volatile compounds released in durian ripening. The strip was obtained by casting method using cassava starch-chitosan, as a based film, and mixing methyl red and bromothymol blue (ratio of 3:2), as indicators. Changes in color in the strip from red to orange and finally turned to yellow indicated the ripening stages of fresh-cut durian. The authors also explained that when the volatile compounds (sulfur; diethyl disulfide, diethyl trisulfide, 3,5-dimethyl-1,2,4-trithiolane) evaporated and reacted with the strip, its changed to the basic form. It is due to the presence of moisture from durian respiration resulting changes in color. Dirpan et al. [40] developed freshness indicator from cellulose membrane and soaked it in bromophenol blue solution and then applied on mango (*Mangifera indica* L. var. *Arummanisa*). The authors found that the color indicator changed from blue to green color (over-ripening) and also suggested that this indicator could be used to determine the freshness of mango. Chen et al. [52] reported a system for freshness indicator based on methylcellulose and mixing of methyl red and bromothymol blue (ratio 3:2). The indicator was tested in the presence of fresh-cut green bell pepper sample during storage at 7 ± 1°C for 9 days. The visible change of freshness indicator was monitored for 9 days, and the color of indicator changed from yellow-green to orange when the sample was completely spoiled. The authors concluded that the deterioration of bell pepper could be detected in real time by freshness indicator. Lee et al. [74] developed a Maillard-type TTI for predicting the maturity of melon (*Cucumis melo* L.). Maillard-type TTI was based on a combination of d-xylose and glycine to create highly reactive Maillard reaction systems. The color of TTIs changed from colorless to yellow, brown, and finally dark brown. The authors concluded that

**Material Indicators Type of** 

of 3:2)

of 3:2)

PtTEPP and *α*-naphtholphthalein

of 3:7)

Mango Cellulose membrane Bromophenol blue Freshness

Methylcellulose Mixing methyl red and

Melon Transparent pouch d-xylose and glycine Time-

Kimchi Cellulose fiber Mixing chlorophenol red

Plastic [poly(isobutyl methacrylate)]

*Application of smart packaging films on fruits and vegetables.*

amide) and PET

Kimchi Poly(ether-*block*-

*PET: polyethylene terephthalate.*

Mixing methyl red and bromothymol blue (ratio

bromothymol blue (ratio

and bromothymol blue (ratio of 2:3)

Mixing methyl red and bromothymol blue (ratio **intelligence**

Freshness indicator

indicator

Freshness indicator

Freshness indicator

temperature indicator

Gas sensor Borchert

Gas indicator Baek et al.

**References**

Niponsak et al. [7]

Dirpan et al. [40]

Chen et al. [52]

Kim et al. [54]

Lee et al. [74]

et al. [75]

[48]

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### *Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

The use of freshness indicator on fruit and vegetable products has been proposed. Niponsak et al. [7] described a colorimetric mixed pH dye-based indicator that responds through visible color changes to sulfur-containing volatile compounds released in durian ripening. The strip was obtained by casting method using cassava starch-chitosan, as a based film, and mixing methyl red and bromothymol blue (ratio of 3:2), as indicators. Changes in color in the strip from red to orange and finally turned to yellow indicated the ripening stages of fresh-cut durian. The authors also explained that when the volatile compounds (sulfur; diethyl disulfide, diethyl trisulfide, 3,5-dimethyl-1,2,4-trithiolane) evaporated and reacted with the strip, its changed to the basic form. It is due to the presence of moisture from durian respiration resulting changes in color. Dirpan et al. [40] developed freshness indicator from cellulose membrane and soaked it in bromophenol blue solution and then applied on mango (*Mangifera indica* L. var. *Arummanisa*). The authors found that the color indicator changed from blue to green color (over-ripening) and also suggested that this indicator could be used to determine the freshness of mango.

Chen et al. [52] reported a system for freshness indicator based on methylcellulose and mixing of methyl red and bromothymol blue (ratio 3:2). The indicator was tested in the presence of fresh-cut green bell pepper sample during storage at 7 ± 1°C for 9 days. The visible change of freshness indicator was monitored for 9 days, and the color of indicator changed from yellow-green to orange when the sample was completely spoiled. The authors concluded that the deterioration of bell pepper could be detected in real time by freshness indicator. Lee et al. [74] developed a Maillard-type TTI for predicting the maturity of melon (*Cucumis melo* L.). Maillard-type TTI was based on a combination of d-xylose and glycine to create highly reactive Maillard reaction systems. The color of TTIs changed from colorless to yellow, brown, and finally dark brown. The authors concluded that


#### **Table 5.**

*Application of smart packaging films on fruits and vegetables.*

*Food Preservation and Waste Exploitation*

became more basic due to the increasing TVB-N.

**5.3 Application of smart packaging on fruits and vegetables**

Fruits and vegetables are extremely perishable products and require appropriate handling and storage conditions over the distribution chain in order to preserve their quality and safety and to prolong the shelf life. These products are living products; it means they keep respiring, consuming O2, and producing CO2 after harvesting. Thus, the postharvest deterioration process is affected by intrinsic factors of the product. One of the major issues of fresh-cut products is the potential microbial spoilage. Smart packaging can be applied in fruit and vegetable product for facilitating the consumer to know the quality of packaged fruits and vegetables and to promote choosing the fruits and vegetables according to freshness or maturity without damaging the packaging. Generally, changes in color indicators represent the extent of ripening of packaged fruit and vegetable products, or in contrast the indicators represent the spoilage condition (microbial growth). According to Poças et al. [33], the packaging-specific requirements for fruits and vegetables are related to maintaining, controlling, and/ or monitoring temperature, gas composition and humidity, and mechanical damage. Applications of smart packaging on fruit and vegetable products are shown in **Table 5**.

colorimetric film was adhered in a sealable bag to directly detect the color difference during fish spoilage. The color changed from pink to yellow-green due to fish spoilage. These color changes were related to the production of volatile basic nitrogen and the increase of pH. Ma et al. [58] developed a pH indicator which consisted of polyvinyl alcohol (PVA)-chitosan nanoparticles and mulberry extract. This indicator was tested for monitoring fish spoilage. The authors found that change in color indicator from red to green was correlated with the presence of volatile nitrogenous compounds, which is characteristic of fish spoilage. Anthocyanins that were extracted from roselle immobilized onto starch-PVA-based film were proposed by Zhai et al. [9] as visual colorimetric film for volatile nitrogenous compounds released in fish spoilage. The visual changes were monitored along 165 h refrigeration temperature (4°C), and the beginning purple color of colorimetric film changed over time to green (at 90 h) and finally yellow (after 135 h). These color changes indicated that the colorimetric films

The optoelectronic nose is based on the combination of pH indicator and selective chromogenic reagents supported on inorganic materials with diverse acidities and topologies [73]. A novel optoelectronic nose to monitor squid spoilage is proposed by Zaragozá et al. [51]. It is based on five pigments prepared by mixing the different corresponding dyes (thymol blue, bromothymol blue sodium salt, bromocresol purple, dinuclear rhodium complex, and bromophenol blue) with two inorganic supports (aluminum oxide and silica gel). Changes in color of sensor array were characteristic of packaged squid, which kept in cold storage for 12 days. The chromogenic array data were assessed with principal component analysis (PCA; qualitative) and partial least squares (PLS; quantitative) study tools. The PCA analysis carried out with CIE Lab showed that the colorimetric array was able to discriminate between fresh and spoiled squid. The statistical models obtained by PLS, with the optoelectronic nose, successfully predicted CO2 and O2 content in the headspace as well as microbial growth. The authors also suggested that this optoelectronic nose could help to evaluate cephalopod freshness, which is easy to use and rapid. Recently, a biosensor (tara gum-PVA-curcumin) was prepared by Ma et al. [41] for evaluation of shrimp spoilage at ambient temperature. The authors found a linear correlation between changes in total volatile basic nitrogen (TVB-N) and pH with the colorimetric response of sensor (slightly yellow to orange-red) within 1–3 min. The authors also suggested the possibility of using the developed film as a sensor for monitoring the spoilage of shrimp and other food products.

**124**

Maillard-type TTI was successfully indicated a product's accumulated temperature as color changes during melon cultivation. The authors also suggested that Maillard reaction-based TTI is not only used for predicting melon maturity but also for monitoring the chilled food distribution and cooking time and temperature.

Some studies reported the combination of device and the packaging technique (MAP or vacuum packaging). Borchert et al. [75] developed an optochemical CO2 sensor for measuring CO2 in the headspace of the package under MAP storage. This sensor is composed of phosphorescent Pt-porphyrin (PtTEPP) reporter and a colorimetric pH indicator α-naphtholphthalein bounded in a plastic [poly(isobutyl methacrylate)] combined with tetraoctyl- or cetyltrimethylammonium hydroxide, as a phase transfer reagent. The authors used this sensor to measure the CO2 levels in salad leaves stored under MAP (CO2, 6.6%; O2, 21.55%; humidity, 100%). It was demonstrated that the sensor could retain its color and sensitivity to CO2 at 4°C for 21 days. Recently, an indicator for monitoring the fermentation stage of kimchi was developed by Baek et al. [48]. It was prepared by coating poly(ether-*block*-amide) that contained chemical dye (mixing of methyl red and bromothymol blue, ratio of 3:7) on polyethylene terephthalate (PET). The determination was worked on the changes in color produced by the levels of CO2 gas in the packaged kimchi. The authors found that changes in color indicator were correlated with the CO2 levels. Kim et al. [54] prepare an accurate indicator from mixing chlorophenol red and bromothymol blue in a ratio of 2:3 and combined it with cellulose fiber to work as labeling film for the aim to develop freshness indicator. The authors found that a total color difference of indicator was correlated well with pH and titratable acidity changes, indicating the possibility of using this indicator in commercial kimchi for indicating the degree of fermentation prior to the final purchase decision during distribution and retail sale.

#### **5.4 Application of smart packaging on milk and dairy products**

Milk and other dairy products are important sources of several essential nutrients. Liquid bovine milk generally comprises approximately 87% water, 4.9% carbohydrate, 3.9% protein, 3.5% fat, and 0.7% ash such as vitamins and minerals [76]. However, the milk compositions varied depending on the species and their immediate environment. For cheese, it can generally be classified as soft, semisoft, or hard, depending on their moisture content. Soft cheese contains high levels of moisture (50–80%), such as cottage cheese and mozzarella, while semisoft and hard cheeses, such as Gorgonzola and Parmesan, respectively, have lower moisture contents and more acidic pH levels [76]. Thus, a large variety of microorganisms quickly proliferate in soft cheese rather than hard cheese due to their moisture content and pH levels (5.0–6.5). Moreover, the presence of oxygen inside the package is also the factor to control. During milk and dairy product spoilage, a wide variety of metabolic by-products are exhibited and caused off-flavor and off-odor, in addition to visible change in color and texture. Most dairy products are distributed, handled, and stored in the cold chain (<7°C) to inhibit the microbial growth. However, temperatures should be kept as low as possible (<4°C) to prolong the storage life, and it has been reported that the shelf life of processed milk increases by decreasing temperatures during storage. To know the quality of milk and dairy products and the environment condition that packaged food product is exposed to, intelligent packaging can be used as a tool or device for detecting the spoilage process in real time and informing the real status of packaged product to the manufacturers and the end consumers by changes in color indicator without opening the packaging. The most recent studies focused on the use of intelligent packaging on milk and dairy products are presented in **Table 6**.

Pereira et al. [8] prepared a time-temperature indicator (TTI) based on a chitosan-PVA film containing anthocyanins from red cabbage, as a natural dye

**127**

**6. Conclusion**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

**Material Indicators Type of** 

Chitosan-PVA Red cabbage Time-temperature

Starch-PVA Purple sweet potato Time-temperature

bromocresol green

Italian cheese RFID — RFID system Papetti et al.

**intelligence**

indicator

indicator

indicator

Freshness indicator

Grape skin extract Time-temperature

**References**

Pereira et al. [8]

Ma and Wang [57]

Liu et al. [59]

Pirsa et al. [53]

[77]

indicator, for monitoring milk spoilage. During storage at a temperature above the cooling temperature, pH lowers from 6.7 (unspoiled) to 4.6 (spoiled). This value was correlated with the color values (CIELab) of the indicator. Color of the dye (red cabbage) turned from dark gray to dark pink. Thus, color changes of the indicator represented the milk spoilage. Ma and Wang [57] prepared pH sensing film from tara gum-cellulose nanocrystal incorporated with natural dye (grape skin extract) to evaluate the pH changes of the milk at ambient temperature for 48 h. During the test, the color of indicator clearly changed from bright red (acidic) to dark green (alkaline) which correlated with microbial contamination and pH decreased (from 6.48 to 2.94). The authors suggested that the developed pH sensing film could be used as a visible color indicator and changes in color of the film provide information

Liu et al. [59] have reported the intelligent packaging made with starch-PVA added with anthocyanins extracted from purple sweet potato as an indicator for monitoring pH changes in pasteurized milk. The visual changes were monitored along 48 h storage at room temperature, and the original purple color of starch-PVA-anthocyanin film changed with time to red, which is related to milk spoilage. Recently, Pirsa et al. [53] developed a pH indicator for determination of milk spoilage. These indicators were based on starch-nanoclay incorporated with methyl orange and bromocresol green. For methyl orange indicator, the color changed from red (pH 3) to yellow (pH 4.5), while bromocresol green showed green (pH 3.8) to blue (pH 5.5). The authors suggested that the colorimetric pH indicator displayed color changes which correlated to pH changes. Thus, the use of these indicators is easily visible to the naked eye. Papetti et al. [77] developed an integrated electronic tracking system for analyzing the quality of Italian cheese. The system was able to identify the cheese products, and the con-

Food processing industry including meat, poultry, fish and seafood, fruits and vegetables, and dairy processing generates a large amount of by-products. However, these by-products still contain organic matters that can be recovered and exploited as high value-added compounds. They can be utilized in packaging applications as a starting material. Thus, it is a great potential of food processing by-products for

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

Milk Tara gum-cellulose

nanocrystal

Milk Starch-nanoclay Methyl orange and

*Application of smart packaging films on milk and dairy products.*

**Food product**

Pasteurized milk

Pasteurized milk

*PVA: polyvinyl alcohol.*

**Table 6.**

to monitor the packaged food freshness.

sumer can know information with the help of the RFID code.

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*


#### **Table 6.**

*Food Preservation and Waste Exploitation*

Maillard-type TTI was successfully indicated a product's accumulated temperature as color changes during melon cultivation. The authors also suggested that Maillard reaction-based TTI is not only used for predicting melon maturity but also for monitoring the chilled food distribution and cooking time and temperature. Some studies reported the combination of device and the packaging technique (MAP or vacuum packaging). Borchert et al. [75] developed an optochemical CO2 sensor for measuring CO2 in the headspace of the package under MAP storage. This sensor is composed of phosphorescent Pt-porphyrin (PtTEPP) reporter and a colorimetric pH indicator α-naphtholphthalein bounded in a plastic [poly(isobutyl methacrylate)] combined with tetraoctyl- or cetyltrimethylammonium hydroxide, as a phase transfer reagent. The authors used this sensor to measure the CO2 levels in salad leaves stored under MAP (CO2, 6.6%; O2, 21.55%; humidity, 100%). It was demonstrated that the sensor could retain its color and sensitivity to CO2 at 4°C for 21 days. Recently, an indicator for monitoring the fermentation stage of kimchi was developed by Baek et al. [48]. It was prepared by coating poly(ether-*block*-amide) that contained chemical dye (mixing of methyl red and bromothymol blue, ratio of 3:7) on polyethylene terephthalate (PET). The determination was worked on the changes in color produced by the levels of CO2 gas in the packaged kimchi. The authors found that changes in color indicator were correlated with the CO2 levels. Kim et al. [54] prepare an accurate indicator from mixing chlorophenol red and bromothymol blue in a ratio of 2:3 and combined it with cellulose fiber to work as labeling film for the aim to develop freshness indicator. The authors found that a total color difference of indicator was correlated well with pH and titratable acidity changes, indicating the possibility of using this indicator in commercial kimchi for indicating the degree of fermentation prior to

the final purchase decision during distribution and retail sale.

milk and dairy products are presented in **Table 6**.

**5.4 Application of smart packaging on milk and dairy products**

Milk and other dairy products are important sources of several essential nutrients. Liquid bovine milk generally comprises approximately 87% water, 4.9% carbohydrate, 3.9% protein, 3.5% fat, and 0.7% ash such as vitamins and minerals [76]. However, the milk compositions varied depending on the species and their immediate environment. For cheese, it can generally be classified as soft, semisoft, or hard, depending on their moisture content. Soft cheese contains high levels of moisture (50–80%), such as cottage cheese and mozzarella, while semisoft and hard cheeses, such as Gorgonzola and Parmesan, respectively, have lower moisture contents and more acidic pH levels [76]. Thus, a large variety of microorganisms quickly proliferate in soft cheese rather than hard cheese due to their moisture content and pH levels (5.0–6.5). Moreover, the presence of oxygen inside the package is also the factor to control. During milk and dairy product spoilage, a wide variety of metabolic by-products are exhibited and caused off-flavor and off-odor, in addition to visible change in color and texture. Most dairy products are distributed, handled, and stored in the cold chain (<7°C) to inhibit the microbial growth. However, temperatures should be kept as low as possible (<4°C) to prolong the storage life, and it has been reported that the shelf life of processed milk increases by decreasing temperatures during storage. To know the quality of milk and dairy products and the environment condition that packaged food product is exposed to, intelligent packaging can be used as a tool or device for detecting the spoilage process in real time and informing the real status of packaged product to the manufacturers and the end consumers by changes in color indicator without opening the packaging. The most recent studies focused on the use of intelligent packaging on

Pereira et al. [8] prepared a time-temperature indicator (TTI) based on a chitosan-PVA film containing anthocyanins from red cabbage, as a natural dye

**126**

*Application of smart packaging films on milk and dairy products.*

indicator, for monitoring milk spoilage. During storage at a temperature above the cooling temperature, pH lowers from 6.7 (unspoiled) to 4.6 (spoiled). This value was correlated with the color values (CIELab) of the indicator. Color of the dye (red cabbage) turned from dark gray to dark pink. Thus, color changes of the indicator represented the milk spoilage. Ma and Wang [57] prepared pH sensing film from tara gum-cellulose nanocrystal incorporated with natural dye (grape skin extract) to evaluate the pH changes of the milk at ambient temperature for 48 h. During the test, the color of indicator clearly changed from bright red (acidic) to dark green (alkaline) which correlated with microbial contamination and pH decreased (from 6.48 to 2.94). The authors suggested that the developed pH sensing film could be used as a visible color indicator and changes in color of the film provide information to monitor the packaged food freshness.

Liu et al. [59] have reported the intelligent packaging made with starch-PVA added with anthocyanins extracted from purple sweet potato as an indicator for monitoring pH changes in pasteurized milk. The visual changes were monitored along 48 h storage at room temperature, and the original purple color of starch-PVA-anthocyanin film changed with time to red, which is related to milk spoilage. Recently, Pirsa et al. [53] developed a pH indicator for determination of milk spoilage. These indicators were based on starch-nanoclay incorporated with methyl orange and bromocresol green. For methyl orange indicator, the color changed from red (pH 3) to yellow (pH 4.5), while bromocresol green showed green (pH 3.8) to blue (pH 5.5). The authors suggested that the colorimetric pH indicator displayed color changes which correlated to pH changes. Thus, the use of these indicators is easily visible to the naked eye. Papetti et al. [77] developed an integrated electronic tracking system for analyzing the quality of Italian cheese. The system was able to identify the cheese products, and the consumer can know information with the help of the RFID code.

#### **6. Conclusion**

Food processing industry including meat, poultry, fish and seafood, fruits and vegetables, and dairy processing generates a large amount of by-products. However, these by-products still contain organic matters that can be recovered and exploited as high value-added compounds. They can be utilized in packaging applications as a starting material. Thus, it is a great potential of food processing by-products for

effective utilization in the field of food packaging applications that would be more cost-effective, efficient, and sustainable. Currently, low-cost sensing packaging technologies have become increasingly interesting because they can give the real status of packaged food quality through visual indication. Thus, the use of smart packaging can be applied on various types of food-based products for facilitating the consumer to know the quality of packaged food in real time and to promote choosing the products according to its freshness without damaging the packaging. These packaging technologies are a noninvasive method, cost-effective, and rapid and can also reduce food loss and waste at the same time. Thus, the use of smart packaging is an alternative way that could reduce the food loss and waste, which is one of the world's major issues.

## **Acknowledgements**

The author would like to thank Mae Fah Luang University, College of Maritime Studies and Management, and Chiang Mai University for the financial support.

## **Author details**

Saroat Rawdkuen1 \* and Pimonpan Kaewprachu2

1 Unit of Innovative Food Packaging and Biomaterials, School of Agro-Industry, Mae Fah Luang University, Chiang Rai, Thailand

2 College of Maritime Studies and Management, Chiang Mai University, Samut Sakhon, Thailand

\*Address all correspondence to: saroat@mfu.ac.th

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**129**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

(red cabbage) as time-temperature indicators for application in intelligent food packaging. Food Hydrocolloids.

[9] Zhai X, Shi J, Zou X, Wang S, Jiang C, Zhang J, et al. Novel colorimetric films based on starch/polyvinyl alcohol incorporated with roselle anthocyanins for fish freshness monitoring. Food Hydrocolloids. 2017;**69**:308-317

[10] Ezejiofor TIN, Enebaku UE, Ogueke C. Waste to wealth-value recovery from agro-food processing wastes using biotechnology: A

review. British Biotechnology Journal.

[11] Food and Agriculture Organization of the United Nations (FAO) [Internet]. FAOSTAT database. Available from: http://www.fao.org [Accessed: 19

2015;**43**:180-188

2014;**4**:418-481

September 2018]

[12] Rathinaraj K, Sachindra NM. Meat, poultry, and eggs. In: Chandrasekaran M, editor. Valorization of Food Processing by-Products. Boca Raton, FL, USA: CRC Press; 2013. pp. 649-684

[13] Song NB, Lee JH, Al Mijan M, Song KB. Development of a chicken feather protein film containing clove oil and its application in smoked salmon packaging. LWT-Food Science and Technology. 2014;**57**:453-460

[14] Olsen RL, Toppe J, Karunasagar I. Challenges and realistic opportunities

processing of fish and shellfish. Trends in Food Science and Technology.

[15] Suresh PV, Prabhu GN. Seafoods. In: Chandrasekaran M, editor. Valorization of Food Processing by-Products. Boca Raton, FL, USA: CRC Press; 2013.

in the use of by-products from

2014;**36**:144-151

pp. 685-736

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

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[2] Yam KL, Takhistov PT, Miltz J. Intelligent packaging: Concepts and applications. Journal of Food Science.

[3] European Commission. Regulation (EC) No. 450/2009. Active and intelligent materials and articles

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[7] Niponsak A, Laohakunjit N, Kerdchoechuen O, Wongsawadee P. Development of smart colourimetric starch-based indicator for liberated volatiles during durian ripeness. Food Research International. 2016;**89**:365-372

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*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

#### **References**

*Food Preservation and Waste Exploitation*

one of the world's major issues.

**Acknowledgements**

**Author details**

Saroat Rawdkuen1

Samut Sakhon, Thailand

effective utilization in the field of food packaging applications that would be more cost-effective, efficient, and sustainable. Currently, low-cost sensing packaging technologies have become increasingly interesting because they can give the real status of packaged food quality through visual indication. Thus, the use of smart packaging can be applied on various types of food-based products for facilitating the consumer to know the quality of packaged food in real time and to promote choosing the products according to its freshness without damaging the packaging. These packaging technologies are a noninvasive method, cost-effective, and rapid and can also reduce food loss and waste at the same time. Thus, the use of smart packaging is an alternative way that could reduce the food loss and waste, which is

The author would like to thank Mae Fah Luang University, College of Maritime Studies and Management, and Chiang Mai University for the financial support.

\* and Pimonpan Kaewprachu2

Mae Fah Luang University, Chiang Rai, Thailand

\*Address all correspondence to: saroat@mfu.ac.th

provided the original work is properly cited.

1 Unit of Innovative Food Packaging and Biomaterials, School of Agro-Industry,

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

2 College of Maritime Studies and Management, Chiang Mai University,

**128**

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**133**

*Valorization of Food Processing By-Products as Smart Food Packaging Materials…*

[69] Zhang X, Lu S, Chen X. A visual pH sensing film using natural dyes from Bauhinia blakeana Dunn. Sensors and Actuators B: Chemical.

[70] Huang XW, Zou XB, Shi JY, Guo Y, Zhao JW, Zhang J, et al. Determination of pork spoilage by colorimetric gas sensor array based on natural pigments. Food Chemistry. 2014;**145**:549-554

[71] Boziaris S, Parlapani FF. Specific spoilage organisms (SSOs) in fish. In: Bevilacqua A, Corbo MR, Sinigaglia M, editors. The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing; 2017. pp. 61-98

[72] Zhang HJ, Hou AQ, Xie KL, Gao AQ. Smart color-changing paper packaging sensors with pH sensitive chromophores based on azo-anthraquinone reactive dyes. Sensor Actuatior B-Chemical.

[73] Mohebi E, Marquez L. Intelligent packaging in meat industry: An overview of existing solutions. Journal of Food Science and Technology.

[74] Lee JH, Morita A, Kuroshima M, Kawamura S, Koseki S. Development of a novel time–temperature integrator/ indicator (TTI) based on the maillard reaction for visual monitoring of melon (*Cucumis melo* L.) maturity during cultivation. Journal of Food Measurement and Characterization.

[75] Borchert NB, Kerry JP, Papkovsky

Pt-porphyrin dye and FRET scheme for food packaging applications. Sensors and Actuators B: Chemical.

[76] Lu M, Wang NS. Spoilage of Milk and dairy products. In: Bevilacqua A, Corbo MR, Sinigaglia M, editors.

2019;**286**:362-369

2015;**52**:3947-3964

2018;**12**:2899-2904

2013;**176**:157-165

DB. A CO2 sensor based on

2014;**198**:268-273

*DOI: http://dx.doi.org/10.5772/intechopen.86245*

purple-fleshed sweet potato extract into chitosan matrix. Food Hydrocolloids.

[62] Silva-Pereira MC, Teixeira JA, Pereira-Júnior VA, Stefani R. Chitosan/

corn starch blend films with extract from *Brassica oleraceae* (red cabbage) as a visual indicator of fish deterioration. LWT-Food Science and

Technology. 2015;**61**:258-262

[63] Pourjavaher S, Almasi H, Meshkini S, Pirsa S, Parandi E. Development of a colorimetric pH indicator based on bacterial cellulose nanofibers and red cabbage (*Brassica oleraceae*) extract. Carbohydrate Polymers.

[64] De Meyer T, Steyaert I, Hemelsoet K, Hoogenboom R, Van Speybroeck V, De Clerck K. Halochromic properties of sulfonphthaleine dyes in a textile environment: The influence of substituents. Dyes and Pigments.

[65] Prietto L, Pinto VZ, El Halal SLM, de Morais MG, Costa JAV, Lim LT, et al. Ultrafine fibers of zein and anthocyanins as natural pH indicator.

Journal of Science and Food Agriculture. 2018;**98**:2735-2741

[66] Miguel MG. Anthocyanins: Antioxidant and/or anti-inflammatory

ME, Rodríguez JA, Galán-Vidal

M, editors. The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing;

A review. Food Chemistry.

2009;**113**:859-871

2017. pp. 179-210

[67] Castaneda-Ovando A, de Lourdes Pacheco-Hernández M, Páez-Hernández

CA. Chemical studies of anthocyanins:

[68] Comi G. Spoilage of meat and fish. In: Bevilacqua A, Corbo MR, Sinigaglia

activities. Journal of Applied Pharmaceutical Science. 2011;**1**:7-15

2019;**90**:216-224

2017;**156**:193-201

2016;**124**:249-257

*Valorization of Food Processing By-Products as Smart Food Packaging Materials… DOI: http://dx.doi.org/10.5772/intechopen.86245*

purple-fleshed sweet potato extract into chitosan matrix. Food Hydrocolloids. 2019;**90**:216-224

*Food Preservation and Waste Exploitation*

Quality in the cold chain. In: Kerry J, Butler P, editors. Smart Packaging Technologies for Fast Moving Consumer Goods. West Sussex, England: John Wiley & Sons; 2008. pp. 61-74

[54] Kim SJ, Lee JY, Yoon SR, Lee HW,

[55] Luchese CL, Abdalla VF, Spada JC, Tessaro IC. Evaluation of blueberry residue incorporated cassava starch film as pH indicator in different simulants and foodstuffs. Food Hydrocolloids.

[56] Rawdkuen S, Faseha A, Kaewprachu

anthocyanin extract as a color indicator in gelatin films. Food Bioscience. 2019

[57] Ma Q, Wang L. Preparation of a visual pH-sensing film based on tara gum incorporating cellulose and extracts from grape skins. Sensors and Actuators B: Chemical.

[58] Ma Q, Liang T, Cao L, Wang L. Intelligent poly (vinyl alcohol) chitosan nanoparticles-mulberry extracts films capable of monitoring pH variations. International Journal of Biological Macromolecules.

[59] Liu B, Xu H, Zhao H, Liu W, Zhao L, Li Y. Preparation and characterization of intelligent starch/PVA films for simultaneous colorimetric indication and antimicrobial activity for food packaging applications. Carbohydrate

P, Benjakul S. Application of

Ha JH. Regression analysis for predicting the fermentation state of packaged Kimchi using a colorimetric indicator. Journal of Food Engineering.

2019;**240**:65-72

2018;**82**:209-218

(submitted)

2016;**235**:401-407

2018;**108**:576-584

Polymers. 2017;**157**:842-849

Chemistry. 2017;**218**:122-128

[60] Choi I, Lee JY, Lacroix M, Han J. Intelligent pH indicator film composed of agar/potato starch and anthocyanin extracts from purple sweet potato. Food

[61] Yong HM, Wang XC, Bai RY, Miao ZQ, Zhang X, Liu J. Development of antioxidant and intelligent pH-sensing packaging films by incorporating

[47] Suppakul P, Kim DY, Yang JH, Lee SB, Lee SJ. Practical design of a diffusion-type time-temperature indicator with intrinsic low temperature

[48] Baek S, Maruthupandy M, Lee K,

characterization of a poly (ether-*block*amide) film–based CO2 indicator for monitoring kimchi quality. Reactive and Functional Polymers. 2018;**131**:75-83

[49] Puligundla P, Jung J, Ko S. Carbon dioxide sensors for intelligent food packaging applications. Food Control.

[50] Kumar P, Reinitz HW, Simunovic J, Sandeep KP, Franzon PD. Overview of RFID technology and its applications in the food industry. Journal of Food

[51] Zaragozá P, Fuentes A, Ruiz-Rico M, Vivancos JL, Fernández-Segovia I, Ros-Lis JV, et al. Development of a colorimetric sensor array for squid spoilage assessment. Food Chemistry.

[52] Chen HZ, Zhang M, Bhandari B, Guo Z. Applicability of a colorimetric indicator label for monitoring freshness

[53] Pirsa S, Sani IK, Khodaeivandi S. Design and fabrication of starch-nano clay composite films loaded with methyl orange and bromocresol green for determination of spoilage in milk package. Polymers for Advanced Technologies. 2018. DOI: 10.1002/

of fresh-cut green bell pepper. Postharvest Biology and Technology.

Science. 2009;**74**:R101-R106

dependency. Journal of Food Engineering. 2018;**223**:22-31

Kim D, Seo J. Preparation and

2012;**25**:328-333

2015;**175**:315-321

2018;**140**:85-92

**132**

pat.4397

[62] Silva-Pereira MC, Teixeira JA, Pereira-Júnior VA, Stefani R. Chitosan/ corn starch blend films with extract from *Brassica oleraceae* (red cabbage) as a visual indicator of fish deterioration. LWT-Food Science and Technology. 2015;**61**:258-262

[63] Pourjavaher S, Almasi H, Meshkini S, Pirsa S, Parandi E. Development of a colorimetric pH indicator based on bacterial cellulose nanofibers and red cabbage (*Brassica oleraceae*) extract. Carbohydrate Polymers. 2017;**156**:193-201

[64] De Meyer T, Steyaert I, Hemelsoet K, Hoogenboom R, Van Speybroeck V, De Clerck K. Halochromic properties of sulfonphthaleine dyes in a textile environment: The influence of substituents. Dyes and Pigments. 2016;**124**:249-257

[65] Prietto L, Pinto VZ, El Halal SLM, de Morais MG, Costa JAV, Lim LT, et al. Ultrafine fibers of zein and anthocyanins as natural pH indicator. Journal of Science and Food Agriculture. 2018;**98**:2735-2741

[66] Miguel MG. Anthocyanins: Antioxidant and/or anti-inflammatory activities. Journal of Applied Pharmaceutical Science. 2011;**1**:7-15

[67] Castaneda-Ovando A, de Lourdes Pacheco-Hernández M, Páez-Hernández ME, Rodríguez JA, Galán-Vidal CA. Chemical studies of anthocyanins: A review. Food Chemistry. 2009;**113**:859-871

[68] Comi G. Spoilage of meat and fish. In: Bevilacqua A, Corbo MR, Sinigaglia M, editors. The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing; 2017. pp. 179-210

[69] Zhang X, Lu S, Chen X. A visual pH sensing film using natural dyes from Bauhinia blakeana Dunn. Sensors and Actuators B: Chemical. 2014;**198**:268-273

[70] Huang XW, Zou XB, Shi JY, Guo Y, Zhao JW, Zhang J, et al. Determination of pork spoilage by colorimetric gas sensor array based on natural pigments. Food Chemistry. 2014;**145**:549-554

[71] Boziaris S, Parlapani FF. Specific spoilage organisms (SSOs) in fish. In: Bevilacqua A, Corbo MR, Sinigaglia M, editors. The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing; 2017. pp. 61-98

[72] Zhang HJ, Hou AQ, Xie KL, Gao AQ. Smart color-changing paper packaging sensors with pH sensitive chromophores based on azo-anthraquinone reactive dyes. Sensor Actuatior B-Chemical. 2019;**286**:362-369

[73] Mohebi E, Marquez L. Intelligent packaging in meat industry: An overview of existing solutions. Journal of Food Science and Technology. 2015;**52**:3947-3964

[74] Lee JH, Morita A, Kuroshima M, Kawamura S, Koseki S. Development of a novel time–temperature integrator/ indicator (TTI) based on the maillard reaction for visual monitoring of melon (*Cucumis melo* L.) maturity during cultivation. Journal of Food Measurement and Characterization. 2018;**12**:2899-2904

[75] Borchert NB, Kerry JP, Papkovsky DB. A CO2 sensor based on Pt-porphyrin dye and FRET scheme for food packaging applications. Sensors and Actuators B: Chemical. 2013;**176**:157-165

[76] Lu M, Wang NS. Spoilage of Milk and dairy products. In: Bevilacqua A, Corbo MR, Sinigaglia M, editors.

The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing; 2017. pp. 151-178

Chapter 7

Abstract

Legumes

mainly in Phaseolus vulgaris.

1. Introduction

135

organic fertilizers, shrimp waste

Comparative Assessment of

Alternative Organic Fertilizers for

The global annual production of shrimp is nearly 4 million metric tons generating

almost half of this weight in waste. This study assessed the crop production of legumes fertilized with shrimp exoskeletons obtained by microwaves under greenhouse conditions. Plants were grown under the following fertilization regimes: (i) untreated shrimp waste, (ii) shrimp waste pellets, (iii) shrimp-based pellets having a hydrolysis degree of 42%, (iv) untreated cellulose pellets, (v) untreated soil, (vi) untreated cotton substrate, and (vii) two commercial fertilizers (CF1 and CF2). CF1 and CF2 showed the largest electric conductivity and ionic exchange capability, whereas the fertilizing pellets showed the lowest values. However, pH, densification and conductivity of soil were not affected by fertilization. Shrimp waste showed a high content of C, N, O, Ca and P mainly derived from chitin, proteins and minerals. All fertilizers showed typical type II isotherms, but the untreated soil and CF2 per se exhibited the largest water uptake. The soil microbiota increased during the growing cycle and then decreased as the reproductive phase started. Further, soil planted with Phaseolus vulgaris showed a larger microbial population than Pisum sativum. The best plant growth was achieved when treated with CF2, whereas the raw shrimp waste caused a beneficial plant growth and crop yield

Keywords: crop quality, fertilization, fertilizing pellets, legume development,

The global annual production of shrimp is nearly 4 million tons generating almost half of this weight in waste. This waste in turn, is composed of chitin, which forms microfibrillar arrangements embedded in a protein matrix with CaCO3. A green alternative for the use of this waste is to use it as an organic fertilizer in form of pellets or as a hydrolyzed material. The search for new organic fertilizers is important due to the limited availability of manure and compost in coast lines

John Rojas, Julian Qunitero, Yhors Ciro, Alfredo Moreno,

Javier Silva-Agredo and Ricardo A. Torres-Palma

Shrimp Hydrolyzates as

[77] Papetti P, Costa C, Antonucci F, Figorilli S, Solaini S, Menesatti P. A RFID web-based infotracing system for the artisanal Italian cheese quality traceability. Food Control. 2012;**27**:234-241

#### Chapter 7

*Food Preservation and Waste Exploitation*

The Microbiological Quality of Food: Foodborne Spoiler. Cambridge, UK: Woodhead Publishing; 2017. pp. 151-178

[77] Papetti P, Costa C, Antonucci F, Figorilli S, Solaini S, Menesatti P. A RFID web-based infotracing system for the artisanal Italian cheese quality traceability. Food Control.

2012;**27**:234-241

**134**

## Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

John Rojas, Julian Qunitero, Yhors Ciro, Alfredo Moreno, Javier Silva-Agredo and Ricardo A. Torres-Palma

#### Abstract

The global annual production of shrimp is nearly 4 million metric tons generating almost half of this weight in waste. This study assessed the crop production of legumes fertilized with shrimp exoskeletons obtained by microwaves under greenhouse conditions. Plants were grown under the following fertilization regimes: (i) untreated shrimp waste, (ii) shrimp waste pellets, (iii) shrimp-based pellets having a hydrolysis degree of 42%, (iv) untreated cellulose pellets, (v) untreated soil, (vi) untreated cotton substrate, and (vii) two commercial fertilizers (CF1 and CF2). CF1 and CF2 showed the largest electric conductivity and ionic exchange capability, whereas the fertilizing pellets showed the lowest values. However, pH, densification and conductivity of soil were not affected by fertilization. Shrimp waste showed a high content of C, N, O, Ca and P mainly derived from chitin, proteins and minerals. All fertilizers showed typical type II isotherms, but the untreated soil and CF2 per se exhibited the largest water uptake. The soil microbiota increased during the growing cycle and then decreased as the reproductive phase started. Further, soil planted with Phaseolus vulgaris showed a larger microbial population than Pisum sativum. The best plant growth was achieved when treated with CF2, whereas the raw shrimp waste caused a beneficial plant growth and crop yield mainly in Phaseolus vulgaris.

Keywords: crop quality, fertilization, fertilizing pellets, legume development, organic fertilizers, shrimp waste

#### 1. Introduction

The global annual production of shrimp is nearly 4 million tons generating almost half of this weight in waste. This waste in turn, is composed of chitin, which forms microfibrillar arrangements embedded in a protein matrix with CaCO3. A green alternative for the use of this waste is to use it as an organic fertilizer in form of pellets or as a hydrolyzed material. The search for new organic fertilizers is important due to the limited availability of manure and compost in coast lines

resulting promising the use of shrimp waste as an alternative organic fertilizer for crops. Currently, there is no information regarding the organic cultivation of legumes fertilized with shrimp-based waste.

2. Materials and methods

DOI: http://dx.doi.org/10.5772/intechopen.86914

FPE and labeled as FHPE.

thetic fertilizer, respectively.

station.

137

2.2 Treatments and cultural practices

was maintained wet in the growing medium.

2.1 Production of shrimp-based fertilizers and experimental design

Dry shrimp exoskeletons were obtained from the pacific coast of Tumaco (Colombia), milled on a cutting mill (Model 3, Willey Arthur Thomas Co., Philadelphia, USA), and passed through a # 100 mesh sieve. This material was labeled as F0. In a separate experimental set, pellets were produced using microcrystalline cellulose (MCC) as a pelletization aid. Thus, pellets made of pure MCC were made by wetting 20 g of MCC with 20 mL of distilled water and passed through a #16 mesh sieve (1190 μm size) with a force ≤11.2 N/cm<sup>2</sup> measured with a load cell (LCGD-10 K, Omega Engineering, Inc., Stamford, CT). The extruded thus obtained was put in the spheronizer chamber (Model 1LA70-4YA60, Siemens), which was operated at the spheronization rate of 15 Hz and spheronization time of 120 s producing beads, which were then oven-dried at 40°C for 24 h. These pellets were then labeled as FPC. In another experimental set, a 50:50 mixture of raw waste and MCC was wetted with 42.5 mL of water and submitted to spheronization under the same conditions as explained for the raw MCC. These pellets were labeled as FPE. On the other hand, a hydrolyzed shrimp waste was obtained using a focused microwave apparatus (Samsung, Model MW 630 WA). A 10% power was applied to ensure reproducibility. Approximately, 20 g of sample was dispersed in 200 mL of a 5% NaOH solution and submitted to a refluxing action keeping the temperature between 50 and 60°C. Radiation was continued for the selected exposure times of 0.85 h so a hydrolysis degree of 42% was obtained. The hydrolyzed product was then cooled down, neutralized with 1 N HCl, filtered and dried at 60°C for 24 h. Further, pellets of this material were made under the same conditions employed for

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

The physicochemical and functional properties of these pellets were compared to those of the untreated soil substrate (SS), untreated cotton substrate (CS) and two commercial fertilizers named as CF1 and CF2. SS was obtained from a local farm and contained a mixture of virgin soil (fine loam) and rice husk at a 3:2 ratio. CF1 and CF2 (N-P-K of 13.2-1-0) corresponded to an organic and extruded syn-

The greenhouse study was conducted in a non-temperature controlled agricultural research station near Medellin (lat. 6.12° N, long. 75.54° E, altitude 2550 m) having a 4 4 m (width length) greenhouse surrounded by a 10-mm light diffusive template glass. The growing condition in the greenhouse was a mean temperature of 23°C day/15°C night and from 65 to 85% RH as recorded during the growth season. No supplementary light or heating was applied in the greenhouse

The soil used in the study was a mixture of fine loam (taken from 0 to 30 cm of a virgin soil) and rice husk at a 3:2 ratio. The soil was put in 2 kg PVC pots (15 cm diameter). Healthy and mature legume seeds were obtained from a retail center of Medellin. Subsequently, one seed was sown in each pot randomly and irrigated uniformly with tap water. A plastic saucer was placed under each pot to prevent water loss by leaching. The plants were irrigated using one dripper per plant (at a discharging rate of 10 mL/h) and the total daily irrigation during the growing season ranged from 240 to 350 mL/plant. The irrigation volume ensured that soil

A rapid and efficient shrimp waste hydrolysis could be accomplished by microwaves, which are non-ionizing electromagnetic radiation having wavelengths from 1 mm to 1 m corresponding to frequencies from 300 GHz to 300 MHz, respectively. This radiation could provide the energy required to break the chemical bonds found in organic molecules such as C-C bonds (347 kJ/mol), and hydrogen bonds such those found in the lignocellulosic biomass of rice straw (3.9–10.1 kJ/mol) rendering a 5-fold increase in the yield of sugars [1].

Leguminous crops have been used for several centuries as a source of food for humans and animals [2]. These plants are originated from the Americas but they are now cultivated all over the world due to their high nutritional and culinary values. In fact, they contain high amounts of protein, vitamins (i.e., thiamine, pyridoxine, and folic acid), dietary fiber, complex carbohydrates (i.e., starch), and nutrients such as iron, potassium, phosphorous, selenium, molybdenum and calcium. They are highly desirable in the human diet since are low in sodium and calories [3]. Further, legumes are so important for human nutrition that 12 million tons of Phaseolus vulgaris (PV) are consumed every year worldwide. Moreover, in 2014 the U.S. produced more than 86,700 metric tons of merely kidney beans. In fact, every day 14% of the U.S. population eats dry edible beans. Legumes are a vibrant part of food security across the world, especially in many developing countries. Thus, 400 million people in the tropics eat beans as part of their daily diet. Legumes also provide income for millions of farmers, typically in Latin America and Africa.

The growth and development of legumes would require appropriate quantities of nutrients for their optimal development; otherwise, physiological deficiency symptoms could occur [4]. Nowadays, the current trend is the use of organic fertilizers for optimal vegetable development. However, the heterogeneity of the physical and chemical characteristics of the different organic fertilizers may give rise to different crop yields. Interestingly, legumes are known to be nitrogen fixers as they take nitrogen from the air by demand and release it into the soil, fulfilling their own nitrogen needs. This implies the need for an organic fertilizer which provides low levels of nitrogen accordingly [5]. For this reason, the intense use of chemical fertilizers for plant development is not advisable since it causes depletion of beneficial soil microbiota and potential pollution of soil and water [6].

Nowadays, organic fertilizers derived from worm castings, peat, manure, and poultry guano have been used to obtain an efficient organic crop production of several plant species [7]. They increase the organic matter and microorganism activity, improve porosity, water retention, and ion exchange capabilities of the soil. They also prevent root burning or destruction of soil microflora since they contain amino acids, organic matter and a variety of micronutrients that replenish the nutrient level of the soil and feeding important soil microorganisms [8]. For instance, the application of vermicompost in soil decreases root rot of beans and produces vigorous plants [9].

The main objective of the current study was to compare the physical characteristics of several shrimp-based fertilizers and their microwave-assisted hydrolyzates on the development of leguminous plants treated with these fertilizers under greenhouse conditions following an organic production. Fertility and substrate management in organic greenhouse production is important in short-term, low fertility requiring crops. Developing organic fertilizers that slowly release nutrients could improve the crop management of legumes produced organically in container production systems.

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

#### 2. Materials and methods

resulting promising the use of shrimp waste as an alternative organic fertilizer for crops. Currently, there is no information regarding the organic cultivation of

A rapid and efficient shrimp waste hydrolysis could be accomplished by microwaves, which are non-ionizing electromagnetic radiation having wavelengths from 1 mm to 1 m corresponding to frequencies from 300 GHz to 300 MHz, respectively. This radiation could provide the energy required to break the chemical bonds found in organic molecules such as C-C bonds (347 kJ/mol), and hydrogen bonds such those found in the lignocellulosic biomass of rice straw (3.9–10.1 kJ/mol) rendering

Leguminous crops have been used for several centuries as a source of food for humans and animals [2]. These plants are originated from the Americas but they are now cultivated all over the world due to their high nutritional and culinary values. In fact, they contain high amounts of protein, vitamins (i.e., thiamine, pyridoxine, and folic acid), dietary fiber, complex carbohydrates (i.e., starch), and nutrients such as iron, potassium, phosphorous, selenium, molybdenum and calcium. They are highly desirable in the human diet since are low in sodium and calories [3]. Further, legumes are so important for human nutrition that 12 million tons of Phaseolus vulgaris (PV) are consumed every year worldwide. Moreover, in 2014 the U.S. produced more than 86,700 metric tons of merely kidney beans. In fact, every day 14% of the U.S. population eats dry edible beans. Legumes are a vibrant part of food security across the world, especially in many developing countries. Thus, 400 million people in the tropics eat beans as part of their daily diet. Legumes also provide income for millions of farmers, typically in Latin

The growth and development of legumes would require appropriate quantities of nutrients for their optimal development; otherwise, physiological deficiency symptoms could occur [4]. Nowadays, the current trend is the use of organic fertilizers for optimal vegetable development. However, the heterogeneity of the physical and chemical characteristics of the different organic fertilizers may give rise to different crop yields. Interestingly, legumes are known to be nitrogen fixers as they take nitrogen from the air by demand and release it into the soil, fulfilling their own nitrogen needs. This implies the need for an organic fertilizer which provides low levels of nitrogen accordingly [5]. For this reason, the intense use of chemical fertilizers for plant development is not advisable since it causes depletion

of beneficial soil microbiota and potential pollution of soil and water [6].

Nowadays, organic fertilizers derived from worm castings, peat, manure, and poultry guano have been used to obtain an efficient organic crop production of several plant species [7]. They increase the organic matter and microorganism activity, improve porosity, water retention, and ion exchange capabilities of the soil. They also prevent root burning or destruction of soil microflora since they contain amino acids, organic matter and a variety of micronutrients that replenish the nutrient level of the soil and feeding important soil microorganisms [8]. For instance, the application of vermicompost in soil decreases root rot of beans and

The main objective of the current study was to compare the physical characteristics of several shrimp-based fertilizers and their microwave-assisted hydrolyzates on the development of leguminous plants treated with these fertilizers under greenhouse conditions following an organic production. Fertility and substrate management in organic greenhouse production is important in short-term, low fertility requiring crops. Developing organic fertilizers that slowly release nutrients could improve the crop management of legumes produced organically in container

legumes fertilized with shrimp-based waste.

Food Preservation and Waste Exploitation

a 5-fold increase in the yield of sugars [1].

America and Africa.

produces vigorous plants [9].

production systems.

136

#### 2.1 Production of shrimp-based fertilizers and experimental design

Dry shrimp exoskeletons were obtained from the pacific coast of Tumaco (Colombia), milled on a cutting mill (Model 3, Willey Arthur Thomas Co., Philadelphia, USA), and passed through a # 100 mesh sieve. This material was labeled as F0. In a separate experimental set, pellets were produced using microcrystalline cellulose (MCC) as a pelletization aid. Thus, pellets made of pure MCC were made by wetting 20 g of MCC with 20 mL of distilled water and passed through a #16 mesh sieve (1190 μm size) with a force ≤11.2 N/cm<sup>2</sup> measured with a load cell (LCGD-10 K, Omega Engineering, Inc., Stamford, CT). The extruded thus obtained was put in the spheronizer chamber (Model 1LA70-4YA60, Siemens), which was operated at the spheronization rate of 15 Hz and spheronization time of 120 s producing beads, which were then oven-dried at 40°C for 24 h. These pellets were then labeled as FPC. In another experimental set, a 50:50 mixture of raw waste and MCC was wetted with 42.5 mL of water and submitted to spheronization under the same conditions as explained for the raw MCC. These pellets were labeled as FPE. On the other hand, a hydrolyzed shrimp waste was obtained using a focused microwave apparatus (Samsung, Model MW 630 WA). A 10% power was applied to ensure reproducibility. Approximately, 20 g of sample was dispersed in 200 mL of a 5% NaOH solution and submitted to a refluxing action keeping the temperature between 50 and 60°C. Radiation was continued for the selected exposure times of 0.85 h so a hydrolysis degree of 42% was obtained. The hydrolyzed product was then cooled down, neutralized with 1 N HCl, filtered and dried at 60°C for 24 h. Further, pellets of this material were made under the same conditions employed for FPE and labeled as FHPE.

The physicochemical and functional properties of these pellets were compared to those of the untreated soil substrate (SS), untreated cotton substrate (CS) and two commercial fertilizers named as CF1 and CF2. SS was obtained from a local farm and contained a mixture of virgin soil (fine loam) and rice husk at a 3:2 ratio. CF1 and CF2 (N-P-K of 13.2-1-0) corresponded to an organic and extruded synthetic fertilizer, respectively.

#### 2.2 Treatments and cultural practices

The greenhouse study was conducted in a non-temperature controlled agricultural research station near Medellin (lat. 6.12° N, long. 75.54° E, altitude 2550 m) having a 4 4 m (width length) greenhouse surrounded by a 10-mm light diffusive template glass. The growing condition in the greenhouse was a mean temperature of 23°C day/15°C night and from 65 to 85% RH as recorded during the growth season. No supplementary light or heating was applied in the greenhouse station.

The soil used in the study was a mixture of fine loam (taken from 0 to 30 cm of a virgin soil) and rice husk at a 3:2 ratio. The soil was put in 2 kg PVC pots (15 cm diameter). Healthy and mature legume seeds were obtained from a retail center of Medellin. Subsequently, one seed was sown in each pot randomly and irrigated uniformly with tap water. A plastic saucer was placed under each pot to prevent water loss by leaching. The plants were irrigated using one dripper per plant (at a discharging rate of 10 mL/h) and the total daily irrigation during the growing season ranged from 240 to 350 mL/plant. The irrigation volume ensured that soil was maintained wet in the growing medium.

After germination, only vigorous seedlings were selected for growth in each pot. Five replications of each treatment were arranged in a completely randomized design. The germinated seeds were then treated with 4 g of the fertilizers in three amendments and these treatments were started on 1-week-old legume seedlings that emerged from direct seeding [12 d after direct seeding (DADS)]. Four and eight weeks after direct seeding, a second and third treatment was applied, whereas in the control treatments, no fertilizer was added (water only). The composition and physical properties of the fertilizers are listed in Table 1. Legume plants were trained to a single vertical pole around the main stem and fixed to a wooden stick having 1.5 m high from the ground to support the plant. There was no need to apply pesticides to control insects since plants were healthy and developed normally.

Plant height was evaluated on a monthly basis during the crop cycle. Harvesting started at 90 DADS and finished at 110 DADS. Legume plants were harvested twice a week when the pots reached maturity. Yield parameters that were measured for crop performance included pod length, pod mass, seed mass and pod number. The soil samples for chemical and microbiological analyses were collected from the surface layer (0–10 cm).

#### 2.3 Nutrient content of fertilizers and soil samples

The pH of the 1% w/v fertilizer dispersion was measured with a handheld combo electrical conductivity (EC) and pH meter (EC600, Extech Instruments, Melrose, MA, USA). The moisture content of the materials was obtained by gravimetric methods, using a moisture balance analyzer (MB200, Ohaus, Parsippany, NJ, USA) equipped with a halogen lamp at 120°C. The sensitivity of the measurements was 0.01%. The total ash content was determined following the methodology described in the AOAC [10]. Briefly, samples were heated on a muffle oven (N31R, Mueller and Krempel, Nabertherm, Germany) at 546°C for 7 h. The amount of the cooled residue was taken as the total ash content. The content of sugars was determined by the phenol-sulfuric acid colorimetric method [11].

The elemental analysis was conducted by Energy Dispersive X-ray analysis (EDX) (JEOL 6490LV, Peabody, MA). About 0.2 g of the samples were spread evenly over an aluminum stub and sputter-coated on a vacuum chamber (Desk IV, Denton Vacuum, Moorestown, NJ USA) with a 30% gold coating for 5 min and operated at 15 kV. X-ray diffraction patterns were taken using an X-ray generator with CuKα radiation and the linear surface sample scanning was conducted for 300 s, 10 mm depth of field and 50 μm diffusion. A Malvern Nano-ZS90 Zetasizer equipped with a Zetasizer Software (vs 7.11, Malvern Instruments Ltd., UK) was employed to determine the particle charge at 25°C using the principle of Laser Doppler Velocimetry (LDV). The zeta potential (PZ) measurements were performed by adding 700 μL of the sample in a polystyrene cell. Samples were analyzed between 12 and 16 cycles with a voltage of 4 mV. The ionic exchange test was carried out by weighing from 0.5 to 1 g of sample and 10 mL of 6 N HCl was added and allowed to stand for 24 h followed by centrifugation for 20 min at 1550 rpm. Subsequently, it was submitted to washing with 1% saline solution twice and titrated with 0.8 N NaOH solution. All measurements were expressed on a dry weight basis.

#### 2.4 Water sorption studies

Water sorption studies were conducted employing the static gravimetry method on chambers having several saturated salts rendering different relative humidities. Thus, K2CO3, NaBr, NaCl, KCl, KNO3 and H20 rendered constant relative

Sample MC (%) Sugars

139

F0 FPC

FPE

FHPE

SS CS CF1 CF2

p-value MC, moisture content; Prot, proteins; CHO, carbohydrates; Con, conductivity; BD, bulk density; ε, porosity; ξ, zeta potential; FPC, cellulose pellets; FPE, exoskeleton pellets; FHPE, hydrolyzed exoskeleton pellets; SS, soil substrate; CS, cotton substrate; IE, ionic

exchange; F0, raw waste; CF1 and CF2 correspond to the commercial fertilizers; A and B correspond to the fraction of adsorbed and absorbed water in the particle, respectively; E, equilibrium constant between the mono layer and liquid water; ΔH, heat of

sorption. NA, not applicable; mean values with an asterisk within the column are significantly different according to the Tukey's test at p < 0.05.

Table 1. Physical properties of

shrimp-based

 fertilizers,

 substrates and commercial

 fertilizers.

0.00

 0.00

 0.00

 0.00

 0.00

 0.00

 0.00

 0.00

 0.00

 0.00

 0.05

 0.00

 0.00

 NA NA NA NA

 NA

 5.8 0.3 0.001 0.000 6.7 0.2 \*70.3 2.1 0.0 0.0

\*8.3 0.5 0.002 0.000 6.7 0.2 58.3 3 0.0 0.0 \*42.8 0.40 \*20.2 1.2 17.8 4.6 \*0.58 0.02 10 5.4 6.9 0.2 0.41 0.12 \*459 2.8

\*8.5 0.6 0.0 0.0 7.1 0.2 \*89.8 2.1 0.0 0.0 0.05 0.01

\*44 1.3 0.002 0.000 7.2 0.4 \*83.3 0.0 \*9.41 0.43 \*45.4 1.3 \*0.6 0.1 22.1 0.3 \*0.20 0.02 16.4 8.4 6.9 0.1 0.67 0.1 40.1 3.1 3.11 0.61 46.09 9.50 0.9582

 4.2 1.3 0.002 0.000 \*8.5 0.2 66 0.0 0.0 0.0 1.5 0.4 90 0.9

 3.5 1.2

\*10.5 0.1 \*8.5 0.1 62 0.0

\*1.2 0.12 1.7 0.3

 2.5 1.1 0.0 0.0

\*5.0 0.1 \*48 0.0 0.0 0.0 0.05 0.01

\*98 1 \*94 1

11.9 1.6\* 0.57 0.02 \*27.6 2.5 7.0 0.2 0.33 0.03 \*280.7 1.6 99 0.11 5.36

9.4 0.5\* 0.51 0.02 18.4 2.7 7.1 0.2 0.34 0.01 \*142.3 0.6 4.9 0.02 0.90 0.27 0.9826

> \*98 1

> > \*5.3 0.3

> > \*10 2

> > 22.9 5.2 \*0.51 0.02 12.5 2.5 6.8 0.2 \*9.49 3.1 \*704 3.7

21 2.6 \*0.15 0.03 \*35.3 3.2 7.2 0.1 \*2.21 0.51 \*79.8 2.2 0.423 0.34 24.13

16.4 0.5 0.89 0.0 20.6 2.6 7.1 0.2 0.26 0.03 53.8 2.1 13.3 0.14 6.50

\*11.0 0.3

\*29.5 0.1 \*8.3 0.2 \*81.8 0.0 \*3.20 0.16 \*3.6 0.37 90.3 0.31 15 0.5 \*0.32 0.01 20.9 3.4 6.7 0.2 0.81 0.14 \*210 4.4 1.63 0.20 16.41 6.94 0.9668

(mg/g)

pH

ε (%)

 Prot (%) Ash (%)

 CHO (%) ξ (mV)

 BD (g/cm3) Soil con

(μS/cm)

(μS/cm)

A

B E

ΔH

r

2

DOI: http://dx.doi.org/10.5772/intechopen.86914

(kJ/

mol)

4.64 0.9593 2.70 0.9800 7.89 0.9888

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

0.81 0.28 10.69 19 0.63 4.64

3.81 0.9902

5.87 0.9941

(104

)

Nelson model)

Water sorption parameters (Young-

Soil pH IE (meq/g) Con

Physical properties of shrimp-based fertilizers, substrates and commercial fertilizers.

#### Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914


After germination, only vigorous seedlings were selected for growth in each pot.

Plant height was evaluated on a monthly basis during the crop cycle. Harvesting started at 90 DADS and finished at 110 DADS. Legume plants were harvested twice a week when the pots reached maturity. Yield parameters that were measured for crop performance included pod length, pod mass, seed mass and pod number. The soil samples for chemical and microbiological analyses were collected from the

The pH of the 1% w/v fertilizer dispersion was measured with a handheld combo electrical conductivity (EC) and pH meter (EC600, Extech Instruments, Melrose, MA, USA). The moisture content of the materials was obtained by gravimetric methods, using a moisture balance analyzer (MB200, Ohaus, Parsippany, NJ, USA) equipped with a halogen lamp at 120°C. The sensitivity of the measurements was 0.01%. The total ash content was determined following the methodology described in the AOAC [10]. Briefly, samples were heated on a muffle oven (N31R, Mueller and Krempel, Nabertherm, Germany) at 546°C for 7 h. The amount of the cooled residue was taken as the total ash content. The content of sugars was determined by

The elemental analysis was conducted by Energy Dispersive X-ray analysis (EDX) (JEOL 6490LV, Peabody, MA). About 0.2 g of the samples were spread evenly over an aluminum stub and sputter-coated on a vacuum chamber (Desk IV, Denton Vacuum, Moorestown, NJ USA) with a 30% gold coating for 5 min and operated at 15 kV. X-ray diffraction patterns were taken using an X-ray generator with CuKα radiation and the linear surface sample scanning was conducted for 300 s, 10 mm depth of field and 50 μm diffusion. A Malvern Nano-ZS90 Zetasizer equipped with a Zetasizer Software (vs 7.11, Malvern Instruments Ltd., UK) was employed to determine the particle charge at 25°C using the principle of Laser Doppler Velocimetry (LDV). The zeta potential (PZ) measurements were performed by adding 700 μL of the sample in a polystyrene cell. Samples were analyzed between 12 and 16 cycles with a voltage of 4 mV. The ionic exchange test was carried out by weighing from 0.5 to 1 g of sample and 10 mL of 6 N HCl was added and allowed to stand for 24 h followed by centrifugation for 20 min at 1550 rpm. Subsequently, it was submitted to washing with 1% saline solution twice and titrated with 0.8 N NaOH solution. All measurements were expressed on a dry

Water sorption studies were conducted employing the static gravimetry method on chambers having several saturated salts rendering different relative humidities.

Thus, K2CO3, NaBr, NaCl, KCl, KNO3 and H20 rendered constant relative

surface layer (0–10 cm).

Food Preservation and Waste Exploitation

weight basis.

138

2.4 Water sorption studies

2.3 Nutrient content of fertilizers and soil samples

the phenol-sulfuric acid colorimetric method [11].

Five replications of each treatment were arranged in a completely randomized design. The germinated seeds were then treated with 4 g of the fertilizers in three amendments and these treatments were started on 1-week-old legume seedlings that emerged from direct seeding [12 d after direct seeding (DADS)]. Four and eight weeks after direct seeding, a second and third treatment was applied, whereas in the control treatments, no fertilizer was added (water only). The composition and physical properties of the fertilizers are listed in Table 1. Legume plants were trained to a single vertical pole around the main stem and fixed to a wooden stick having 1.5 m high from the ground to support the plant. There was no need to apply pesticides to control insects since plants were healthy and developed normally.

humidities of 43, 58, 68, 75, 94 and 100%, respectively. The isotherms were built at 25°C and samples were allowed to reach equilibrium for 2 weeks when the difference between two consecutive measurements was not larger than 0.1%. Data were fitted to several sorption models, and only the one that presented the best fit was discussed in this study. The ability of the fertilizers for water sorption was studied by applying the Young and Nelson model which is expressed as:

$$m = m\_m + m\_c + m\_i \tag{1}$$

3. Results and discussion

DOI: http://dx.doi.org/10.5772/intechopen.86914

semispherical beads.

141

3.1 Preparation and physical properties of the fertilizers

organic fertilizer having a moderate hydrolysis degree.

Microwave radiation accelerated the degradation of alkaline shrimp waste forming a product having a hydrolysis degree of 42%. Thus, hydroxyl radicals of the alkaline media along with microwave radiation contributed to molecular weight reduction of waste compounds such as carbohydrates and proteins and avoided the need for a time-consuming composting of the raw waste and thus, decreased the initial microbial population avoiding further release of putrescine and other nitrous volatile compounds. Shrimp waste possesses the striated type muscle arranged into muscle fibers that are bound together by a connective tissue where the prevalent amino acid is lysine. These muscle proteins are associated to chitin and minerals such as calcium phosphate. The protein and chitin availability are important since they will eventually turn into accessible nitrogen for legumes. The magnitude of the peptide and glycosidic bonds cleavage during microwave hydrolysis rendered an

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

During the wet massing process MCC was essential as spheronization aid. Previous studies (data not shown) determined the need of at least 50% MCC as optimal in order to obtain a spherical pellet having good mechanical properties (FPE and FHPE). Thus, MCC fibers alone or combined with waste coalesced and formed larger particles which were then shaped once they passed through the screen orifices. These, in turn, were molded in the spheronizer which cut-off and rounded-off the sharply and roughly surfaces. The rotating plate operating at the 15 Hz rate and residence time of 120 s produced a denser and smoother pellet surface due to the combined action of the centrifugal force created by plate rotation, the vertical force formed by collision, and the gravitational force allowing for the formation of a toroidal or twisted rope motion having an spiral pattern. As a result, this high frequency and short residence time generated more frictional and rotational forces where the initial small, oblong and irregular particles experienced growth, folding and edge rounding which was subsequently shaped into dumb bells. These dumb bells were then twisted, broken, rounded and transformed into spherical or

On the contrary, raw waste per se failed to produce pellets or aggregates due to the lack of plasticity needed for the spheronization process, this fact also occurred by employing a very short residence time resulting in pellets of a predominantly small size, oblong shape and rougher surface. The spheronization platform usually renders bead sizes of about 1000 μm. In this case, by using a #20 screen sieves the size of the resulting beads ranged from 1.2 to 3 mm. Particle size tends to increase with residence time and this variable was kept at 120 s avoiding loss of moisture and maintaining the required plasticity for pellet growth. This high spheronization rate guarantees the formation of beads with diameters larger than 1 mm. The spherical morphology and particle size played a major role on densification and porosity. This occurrence was reflected on the resulting porosity which in turn, decreased with pelletization. On the other hand, the degree of densification decreased by the spheronization process. This is explained by the highly regularly-shaped particles that are less likely to accommodate in the powder bed under the action of an external force as compared to the non-spheronized irregular particles. Flowability is the property that reflects the way in which gravity overcomes the cohesive forces and the interlocking structure of the particles. In general, the flowability of the pellets was high ranging from 13.4 to 16.4 g/s, independent of the average bead mass. A constant plate diameter of 30 cm was employed at spheronization rates of 15 Hz which is equivalent to 900 rpm and peripheral velocity of 1415 cm/s,

$$m = \mathbf{A}(\theta + \mathfrak{B}) + \beta \mathfrak{y} \tag{2}$$

$$\Theta = \frac{a\_w}{a\_w + (1 - a\_w)E} \dots \tag{3}$$

$$
\Psi \Psi = a\_w \Theta
\tag{4}
$$

$$E = e^{-(H\_1 - H\_l)/RT} \tag{5}$$

$$\beta = -\frac{E a\_w}{E - (E - 1) a\_w} + -\frac{E^2}{(E - 1)} \text{Ln} \frac{E - (E - 1) a\_w}{E} - (E + 1) \text{Ln} (\mathbf{1} - a\_w) \tag{6}$$

where mm, mc and mi correspond to the tightly bound water, condensed external water and internally absorbed water, respectively. Further, m corresponds to the total moisture content, θ is the fraction of surface covered by a monomolecular layer, ψ is the fraction of surface covered by a water layer of two or more molecules thick, and β is the total amount of adsorbed moisture in the multilayer. Moreover, H1, Hl, k and T, correspond to the heat of adsorption of water bound to the surface, heat of condensation, the gas constant and temperature, respectively. A and B are dimensionless constants related to the fraction of adsorbed and absorbed water in the particle, respectively, and E is the equilibrium constant between the monolayer and liquid water. The product Aθ is related to the amount of monolayer moisture, A (θ + β) is the externally absorbed moisture during the sorption phase, whereas Bψ corresponds to the amount of absorbed moisture during the sorption phase [12].

#### 2.5 Total aerobic bacteria and fungi counts

These tests were conducted on samples without any previous treatment according to the National Technical Standard 4092 of microbiology. Briefly, 1 g of sample was dispersed in 10 mL of peptone water, making the pertinent dilution factors from 1�10�<sup>1</sup> to 1�10�10. Subsequently, 1 mL of the solution was poured onto a 20 mL culture plate (Merck). Samples were then incubated at 37°C between 24 and 48 h. The results were reported as colony forming units per gram of fertilizer (CFU/g).

#### 2.6 Statistical analysis

The principal component analysis (PCA) was the type of multivariate analysis used to identify and compare the relationships and patterns among the physicochemical and functional properties of the fertilizers. The software Minitab® (v. 16 Minitab, Inc., State College, PA) was used for data processing. The relationship between the different crop characteristics was assessed by the Pearson's correlation coefficient at a significance level of p < 0.05. Additional post hoc assessment was performed using the Tukey's test (p < 0.05) when significant differences between means were observed. The condition of normality was checked using the Shapiro-Wilk test.

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

#### 3. Results and discussion

humidities of 43, 58, 68, 75, 94 and 100%, respectively. The isotherms were built at 25°C and samples were allowed to reach equilibrium for 2 weeks when the difference between two consecutive measurements was not larger than 0.1%. Data were fitted to several sorption models, and only the one that presented the best fit was discussed in this study. The ability of the fertilizers for water sorption was studied

> m ¼ mm þ mc þ mi (1) m ¼ Að Þþ θ þ β βψ (2)

aw <sup>þ</sup> ð Þ <sup>1</sup> � aw <sup>E</sup> … (3)

ψ ¼ awθ (4)

�ð Þ <sup>H</sup>1�Hl <sup>=</sup>RT (5)

<sup>E</sup> � ð Þ <sup>E</sup> <sup>þ</sup> <sup>1</sup> Lnð Þ <sup>1</sup> � aw (6)

by applying the Young and Nelson model which is expressed as:

<sup>θ</sup> <sup>¼</sup> aw

E ¼ e

Ln <sup>E</sup> � ð Þ <sup>E</sup> � <sup>1</sup> aw

where mm, mc and mi correspond to the tightly bound water, condensed external water and internally absorbed water, respectively. Further, m corresponds to the total moisture content, θ is the fraction of surface covered by a monomolecular layer, ψ is the fraction of surface covered by a water layer of two or more molecules thick, and β is the total amount of adsorbed moisture in the multilayer. Moreover, H1, Hl, k and T, correspond to the heat of adsorption of water bound to the surface, heat of condensation, the gas constant and temperature, respectively. A and B are dimensionless constants related to the fraction of adsorbed and absorbed water in the particle, respectively, and E is the equilibrium constant between the monolayer and liquid water. The product Aθ is related to the amount of monolayer moisture, A (θ + β) is the externally absorbed moisture during the sorption phase, whereas Bψ corresponds to the amount of absorbed moisture during the sorption phase [12].

These tests were conducted on samples without any previous treatment according to the National Technical Standard 4092 of microbiology. Briefly, 1 g of sample was dispersed in 10 mL of peptone water, making the pertinent dilution factors from 1�10�<sup>1</sup> to 1�10�10. Subsequently, 1 mL of the solution was poured onto a 20 mL culture plate (Merck). Samples were then incubated at 37°C between 24 and 48 h. The results were reported as colony forming units per gram of fertilizer

The principal component analysis (PCA) was the type of multivariate analysis used to identify and compare the relationships and patterns among the physicochemical and functional properties of the fertilizers. The software Minitab® (v. 16 Minitab, Inc., State College, PA) was used for data processing. The

relationship between the different crop characteristics was assessed by the Pearson's correlation coefficient at a significance level of p < 0.05. Additional post hoc assessment was performed using the Tukey's test (p < 0.05) when significant differences between means were observed. The condition of normality was checked using the

E2 ð Þ E � 1

<sup>β</sup> ¼ � Eaw

(CFU/g).

2.6 Statistical analysis

Shapiro-Wilk test.

140

E � ð Þ E � 1 aw

Food Preservation and Waste Exploitation

þ �

2.5 Total aerobic bacteria and fungi counts

#### 3.1 Preparation and physical properties of the fertilizers

Microwave radiation accelerated the degradation of alkaline shrimp waste forming a product having a hydrolysis degree of 42%. Thus, hydroxyl radicals of the alkaline media along with microwave radiation contributed to molecular weight reduction of waste compounds such as carbohydrates and proteins and avoided the need for a time-consuming composting of the raw waste and thus, decreased the initial microbial population avoiding further release of putrescine and other nitrous volatile compounds. Shrimp waste possesses the striated type muscle arranged into muscle fibers that are bound together by a connective tissue where the prevalent amino acid is lysine. These muscle proteins are associated to chitin and minerals such as calcium phosphate. The protein and chitin availability are important since they will eventually turn into accessible nitrogen for legumes. The magnitude of the peptide and glycosidic bonds cleavage during microwave hydrolysis rendered an organic fertilizer having a moderate hydrolysis degree.

During the wet massing process MCC was essential as spheronization aid. Previous studies (data not shown) determined the need of at least 50% MCC as optimal in order to obtain a spherical pellet having good mechanical properties (FPE and FHPE). Thus, MCC fibers alone or combined with waste coalesced and formed larger particles which were then shaped once they passed through the screen orifices. These, in turn, were molded in the spheronizer which cut-off and rounded-off the sharply and roughly surfaces. The rotating plate operating at the 15 Hz rate and residence time of 120 s produced a denser and smoother pellet surface due to the combined action of the centrifugal force created by plate rotation, the vertical force formed by collision, and the gravitational force allowing for the formation of a toroidal or twisted rope motion having an spiral pattern. As a result, this high frequency and short residence time generated more frictional and rotational forces where the initial small, oblong and irregular particles experienced growth, folding and edge rounding which was subsequently shaped into dumb bells. These dumb bells were then twisted, broken, rounded and transformed into spherical or semispherical beads.

On the contrary, raw waste per se failed to produce pellets or aggregates due to the lack of plasticity needed for the spheronization process, this fact also occurred by employing a very short residence time resulting in pellets of a predominantly small size, oblong shape and rougher surface. The spheronization platform usually renders bead sizes of about 1000 μm. In this case, by using a #20 screen sieves the size of the resulting beads ranged from 1.2 to 3 mm. Particle size tends to increase with residence time and this variable was kept at 120 s avoiding loss of moisture and maintaining the required plasticity for pellet growth. This high spheronization rate guarantees the formation of beads with diameters larger than 1 mm. The spherical morphology and particle size played a major role on densification and porosity. This occurrence was reflected on the resulting porosity which in turn, decreased with pelletization. On the other hand, the degree of densification decreased by the spheronization process. This is explained by the highly regularly-shaped particles that are less likely to accommodate in the powder bed under the action of an external force as compared to the non-spheronized irregular particles. Flowability is the property that reflects the way in which gravity overcomes the cohesive forces and the interlocking structure of the particles. In general, the flowability of the pellets was high ranging from 13.4 to 16.4 g/s, independent of the average bead mass. A constant plate diameter of 30 cm was employed at spheronization rates of 15 Hz which is equivalent to 900 rpm and peripheral velocity of 1415 cm/s,

respectively. This rotational speed and short residence time (120 s) was suitable to obtain spherical beads.

#### 3.2 Nutritional content of the fertilizers and plant development

The nutritional content of the shrimp-based fertilizers (SBF) is listed in Table 1. The hydrolyzed product retained much of the initial nutrients contained in the raw shrimp exoskeletons. The alkaline microwave hydrolysis disrupted the inter and intra-molecular hydrogen bond pattern of complex carbohydrates and proteins initially present in the material, disturbing the regularity of the 3D packing and stereochemistry between chains, especially of the most accessible amorphous regions. As a result, the alkaline hydrolysis of the non-crystalline fraction removed monomer blocks of repeated units, especially those located at the crystallite surface and hence, NaOH accessed the β-1,4N-acetyl and peptidic linkages, simultaneously. The net result was a reduction in the crystallinity of the shrimp fertilizer. In fact, the application of high intensity waves caused chemical and mechanical degradation in the waste particles, resulting in changes in the native shrimp protein and carbohydrate structure into a molten globule state.

The pH and moisture content of these fertilizers ranged from 5.0 to 8.5 and from 2.5 to 11%, respectively. Once the fertilizers were incorporated into the soil maintained a slightly neutral ambient (6.7–7.2) and the electrical conductivity ranged from 12 to 28 μS/cm. A neutral pH ensured a good availability of the nutrients to the leguminous plants. The high moisture content eased the transformation of macromolecular N into NH4 <sup>+</sup> and NO3 by bacteria action resulting in its mineralization and easy uptake by plants as reported previously [13]. The slightly alkaline pH of F0 is attributed to the presence of peptides, and elements such as Ca2+ and Mg2+. Further, these divalent ions can then be adsorbed onto the surface of tiny clay particles of the soil which had a net negative charge. The magnesium level in the shrimp-based fertilizers (SBF) was lower than that of calcium so its effect on the soil structure was negligible. The negative surface charge of soil particles is believed to improve P availability in form of phosphates as present in shrimp waste. These phosphates along with the P2O5 of CF2 could be responsible for the large PV crop yield found in F0 and CF2, respectively. Conversely, K was virtually absent in most fertilizers and its synergistic effect on crop yield was not noticed.

The zeta potential indicates the average charge in the particles and gives a measurement of the ion activity of the fertilizers. All materials exhibited a net negative charge and CF2 had the largest ion exchange capability and electrical conductivity altogether. Conversely, FHPE exhibited the smallest value of electrical conductivity. Interestingly, CS showed a large ionic exchange capability, but a moderate electric conductivity due to the residual ionized functional groups present in this type of cellulose.

Table 2 lists the elemental composition of each type of SBF, substrates and commercial fertilizers. Alkaline microwave hydrolysis had a marked effect on the nutritional content of the shrimp waste. This had a large content of essentially C, N, Ca and P. On the other hand, Fe, Si, Al, Mg and Cl were present as the main microelements. The content of Mg, was larger in the F0 than SS, CS and pellets, whereas the K content was low in all cases except for CF1. The C/N ratio was slower than 10 for F0, FPE, FHPE, CF2, and FPC whereas CF1 (10.5) and SS (33.1) showed the largest C/N ratio due to their low content of N. Further, the SS and CF1 were poor in organic nitrogen, but rich in carbon, silicon and aluminum. On the other hand, CS had a poor content of most elements except for carbon and oxygen. The SS, FPC and CS presented low levels of essential elements such as N, P, and Ca as compared to F0, FPE and FHPE. Interestingly, CF1 and SS showed traces of other

Element

143

C O N Ca

P Si Fe Al Mg

Cl Na

K

Ti Mn C/N F0, raw waste; FPC, cellulose pellets; FPE, exoskeleton pellets; FHPE, hydrolyzed exoskeleton pellets; SS, soil substrate; CS, cotton substrate CF1 and CF2 correspond to the commercial

with an asterisk within the column are significantly

Table 2. Elemental analysis of the

shrimp-based

 fertilizers,

 substrates and commercial

 organic fertilizers (n = 3).

2.7

33.1

 different according to the Tukey's test at p < 0.05.

2.7

4.8

33.1

53.5

41

2.5

 fertilizers; mean values

NA

0 0

 0 0 0

 0

 0

 0

 0

\*0.1

0 0

 0

 0

0.03

 0.03

0 0

0.00

 0

 0

 0

0

0.5

 0.5

0.

 0.0

\*0.4

 0.4

0 0

0.06

 0

 0

0.13

 0

 0

 0

0.1

0 0

 0

 0

\*1.1

 0.2

0 0

0.00

0.2

 0.1

 0.05

 0

 0

 0

0.1

0.1

 0.1

 0.0

 0.0

\*0.8

 0.2

\*0.47

 0.13

0.00

\*0.2

 0.1

0 0

0.4

 0.1

 0.21

 0.1

 0.35 \*0.23

 0.12

0 0

 0

 0

\*0.3

 0.1

 0.03

 0.03

0.00

0.28

0.2

 0.1

0 0

\*0.6

 0.4

0.4

 0.3

0.05

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

0.1

 0.1

\*4.1

 0.5

 0

 0

\*2.1

\*4.1

 0.7

 0.5

 0.5

\*2.7

 0.5

0.0

 0.0

0.00

1.5

 1.0

0 0

 0

 0.59

1.2

 0.8

0.0

 0.0

1.8

 1.8

5.4

 5.4

0.08

 0

0.2

 0.1

\*18.2

 1

 0

 0

\*18.1

 1.6

0 0

 0

\*1.5

 1.4

0 0

1.5

0.8

0 0

 0

 0 \*11.4

 3.2

0.9

 0.4

0.00

 0

1.2

 1.2

0.00

 0

\*5.8

 2.7

0 0

\*5.4

\*2.8

0.2

 0.1

0 0

\*15.9

 5.4

0 0

\*15.9

\*7.95

0 0

 0

 0 0.9

 0.2

0.14

 0.14

0.00

 0

\*15.9

 4.9

0.00

DOI: http://dx.doi.org/10.5772/intechopen.86914

 0

33.3

 2.1

\*42.5

 3

33.3

37.9

\*42.5

 0.4

\*46.

 5.2

39

 6

37.0

 2.4

0.00

43

 3.3

33.1

 5

43

38.1

33.1

 1.1

\*53.5

 4.5

 41.0

 10.3

 39.0

 3.63

0.00

F0

FPC

FPE

 FHPE

SS

CS

CF1

CF2

p-value


Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

> Table 2.

Elemental analysis of the shrimp-based fertilizers, substrates and commercial organic fertilizers (n

= 3).

respectively. This rotational speed and short residence time (120 s) was suitable to

The nutritional content of the shrimp-based fertilizers (SBF) is listed in Table 1. The hydrolyzed product retained much of the initial nutrients contained in the raw shrimp exoskeletons. The alkaline microwave hydrolysis disrupted the inter and intra-molecular hydrogen bond pattern of complex carbohydrates and proteins initially present in the material, disturbing the regularity of the 3D packing and stereochemistry between chains, especially of the most accessible amorphous regions. As a result, the alkaline hydrolysis of the non-crystalline fraction removed monomer blocks of repeated units, especially those located at the crystallite surface and hence, NaOH accessed the β-1,4N-acetyl and peptidic linkages, simultaneously. The net result was a reduction in the crystallinity of the shrimp fertilizer. In fact, the application of high intensity waves caused chemical and mechanical degradation in the waste particles, resulting in changes in the native shrimp protein and carbohy-

The pH and moisture content of these fertilizers ranged from 5.0 to 8.5 and from

<sup>+</sup> and NO3

mineralization and easy uptake by plants as reported previously [13]. The slightly alkaline pH of F0 is attributed to the presence of peptides, and elements such as Ca2+ and Mg2+. Further, these divalent ions can then be adsorbed onto the surface of tiny clay particles of the soil which had a net negative charge. The magnesium level in the shrimp-based fertilizers (SBF) was lower than that of calcium so its effect on the soil structure was negligible. The negative surface charge of soil particles is believed to improve P availability in form of phosphates as present in shrimp waste. These phosphates along with the P2O5 of CF2 could be responsible for the large PV crop yield found in F0 and CF2, respectively. Conversely, K was virtually absent in most

The zeta potential indicates the average charge in the particles and gives a measurement of the ion activity of the fertilizers. All materials exhibited a net negative charge and CF2 had the largest ion exchange capability and electrical conductivity altogether. Conversely, FHPE exhibited the smallest value of electrical conductivity. Interestingly, CS showed a large ionic exchange capability, but a moderate electric conductivity due to the residual ionized functional groups present

Table 2 lists the elemental composition of each type of SBF, substrates and commercial fertilizers. Alkaline microwave hydrolysis had a marked effect on the nutritional content of the shrimp waste. This had a large content of essentially C, N, Ca and P. On the other hand, Fe, Si, Al, Mg and Cl were present as the main microelements. The content of Mg, was larger in the F0 than SS, CS and pellets, whereas the K content was low in all cases except for CF1. The C/N ratio was slower than 10 for F0, FPE, FHPE, CF2, and FPC whereas CF1 (10.5) and SS (33.1) showed the largest C/N ratio due to their low content of N. Further, the SS and CF1 were poor in organic nitrogen, but rich in carbon, silicon and aluminum. On the other hand, CS had a poor content of most elements except for carbon and oxygen. The SS, FPC and CS presented low levels of essential elements such as N, P, and Ca as compared to F0, FPE and FHPE. Interestingly, CF1 and SS showed traces of other

by bacteria action resulting in its

2.5 to 11%, respectively. Once the fertilizers were incorporated into the soil maintained a slightly neutral ambient (6.7–7.2) and the electrical conductivity ranged from 12 to 28 μS/cm. A neutral pH ensured a good availability of the nutrients to the leguminous plants. The high moisture content eased the transfor-

fertilizers and its synergistic effect on crop yield was not noticed.

3.2 Nutritional content of the fertilizers and plant development

obtain spherical beads.

Food Preservation and Waste Exploitation

drate structure into a molten globule state.

mation of macromolecular N into NH4

in this type of cellulose.

142

microelements such as K, Ti, and essentially CF1 was the only fertilizer which contained traces of Mn. On the other hand, CF2 contained N from urea and P from P2O5 at a 13:1 ratio.

#### 3.3 Water uptake

The water vapor sorption isotherm of a material describes the relationship between the relative vapor pressure or water activity, (aw) and water content over a range of aw values obtained at a given temperature [14]. The fitting water sorption parameters obtained from the Young-Nelson model revealed a good fitting to this model having an r2 larger than 0.9582 as compared to other models not shown in this study.

Figure 1a shows that during the first sorption stage (aw < 0.45), the isotherms exhibited a convex shape as the water molecules rapidly sorb onto the available sorption sites until a monolayer is formed. The shape of the isotherms during this first stage did not differ substantially among the different SBF, but was larger for SS and CF2. Thereafter, there was a gradual increase in water content with aw up to 0.80 where an abrupt increase of water content was observed possibly due to capillary condensation phenomena. Interestingly, most fertilizers showed a steady increase in monolayer and multilayer formation up to aw of 0.45, afterwards the water molecules although still in vapor form, begin to diffuse within the particle core except for SS, FPE and FPC in which this process started at a very low aw (Figure 1b). Therefore, in these materials isotherms proved that water did not form a continuous monolayer because the multilayer and particle water absorption occurred simultaneously. This phenomenon has been attributed to the tendency of water molecules to cluster around exchangeable cations found in different soils [14]. As a result, water molecules bind as succeeding layers of water molecules rather to empty sites on the surface of the particle. Thus, the formation of a second layer probably started at lower concentration than those corresponding to the monolayer formation. Clustering was expected to occur in most cases since the amount of water molecules on the particle was higher than the quantity that can be bound within the particle. Further, SS and CF2 per se had an innate ability to uptake and keep water within the particles and were able to preserve the wet environment for the optimal root and microbiota development.

CF2 at all aw showed the lowest tendency for clustering, but the largest sorption within the particle core. The deconvoluted curves showed that the monolayer formation presented a type III Langmuir isotherm, whereas the curves for the multilayer sorption showed a type II isotherm. Interestingly, CF2 also showed the largest cation exchange capability and ionic conductivity. This agrees with previous studies that reported a relationship between the high water sorption and the ion exchange capability of the soil [15].

The raw soil substrate (SS) showed the largest E parameter and hence, presented the largest heat of endothermic sorption (ΔH). Further, SS and CF2 showed the largest intrinsic absorbed water (B parameter), whereas CS showed the largest adsorption ability forming multilayers. CF2 and SS showed the largest hygroscopicity, especially at a water activity larger than 0.4. Further, these two samples had the largest ability to absorb water intrinsically, whereas SS and CS per se were able to form large water multilayers around the particles. In addition, the water sorption behavior of SBF was comparable to that of CF1.

#### 3.4 Soil microstructure and microbial activity

The ionic exchange capability of the SBF decreased upon hydrolysis as compared to F0 due to leakage of some ions such as calcium and phosphates. Further, the

incorporation of these fertilizers into the soil did not have a marked effect on the physicochemical properties of the topsoil due to a dilution effect. Thus, the electrical conductivity of the soil was low (10–28 μS/cm) as compared to the pure fertilizers, but outside the range recommended for other horticultural plants

Water sorption isotherms fitted to the Young-Nelson model. (a) Fitted isotherms, (b) deconvoluted sorption behavior for the monolayer and multilayers, and (c) deconvoluted sorption behavior for the intrinsic absorbed

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

DOI: http://dx.doi.org/10.5772/intechopen.86914

Figure 1.

145

water (n = 3).

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

Figure 1.

microelements such as K, Ti, and essentially CF1 was the only fertilizer which contained traces of Mn. On the other hand, CF2 contained N from urea and P from

The water vapor sorption isotherm of a material describes the relationship between the relative vapor pressure or water activity, (aw) and water content over a range of aw values obtained at a given temperature [14]. The fitting water sorption parameters obtained from the Young-Nelson model revealed a good fitting to this model having an r2 larger than 0.9582 as compared to other models not shown in this study.

Figure 1a shows that during the first sorption stage (aw < 0.45), the isotherms exhibited a convex shape as the water molecules rapidly sorb onto the available sorption sites until a monolayer is formed. The shape of the isotherms during this first stage did not differ substantially among the different SBF, but was larger for SS and CF2. Thereafter, there was a gradual increase in water content with aw up to 0.80 where an abrupt increase of water content was observed possibly due to capillary condensation phenomena. Interestingly, most fertilizers showed a steady increase in monolayer and multilayer formation up to aw of 0.45, afterwards the water molecules although still in vapor form, begin to diffuse within the particle core except for SS, FPE and FPC in which this process started at a very low aw (Figure 1b). Therefore, in these materials isotherms proved that water did not form a continuous monolayer because the multilayer and particle water absorption occurred simultaneously. This phenomenon has been attributed to the tendency of water molecules to cluster around exchangeable cations found in different soils [14]. As a result, water molecules bind as succeeding layers of water molecules rather to empty sites on the surface of the particle. Thus, the formation of a second layer probably started at lower concentration than those corresponding to the monolayer formation. Clustering was expected to occur in most cases since the amount of water molecules on the particle was higher than the quantity that can be bound within the particle. Further, SS and CF2 per se had an innate ability to uptake and keep water within the particles and were able to preserve the wet environment

CF2 at all aw showed the lowest tendency for clustering, but the largest sorption

The raw soil substrate (SS) showed the largest E parameter and hence, presented the largest heat of endothermic sorption (ΔH). Further, SS and CF2 showed the largest intrinsic absorbed water (B parameter), whereas CS showed the largest adsorption ability forming multilayers. CF2 and SS showed the largest hygroscopicity, especially at a water activity larger than 0.4. Further, these two samples had the largest ability to absorb water intrinsically, whereas SS and CS per se were able to form large water multilayers around the particles. In addition, the water sorption

The ionic exchange capability of the SBF decreased upon hydrolysis as compared

to F0 due to leakage of some ions such as calcium and phosphates. Further, the

within the particle core. The deconvoluted curves showed that the monolayer formation presented a type III Langmuir isotherm, whereas the curves for the multilayer sorption showed a type II isotherm. Interestingly, CF2 also showed the largest cation exchange capability and ionic conductivity. This agrees with previous studies that reported a relationship between the high water sorption and the ion

for the optimal root and microbiota development.

behavior of SBF was comparable to that of CF1.

3.4 Soil microstructure and microbial activity

exchange capability of the soil [15].

144

P2O5 at a 13:1 ratio.

Food Preservation and Waste Exploitation

3.3 Water uptake

Water sorption isotherms fitted to the Young-Nelson model. (a) Fitted isotherms, (b) deconvoluted sorption behavior for the monolayer and multilayers, and (c) deconvoluted sorption behavior for the intrinsic absorbed water (n = 3).

incorporation of these fertilizers into the soil did not have a marked effect on the physicochemical properties of the topsoil due to a dilution effect. Thus, the electrical conductivity of the soil was low (10–28 μS/cm) as compared to the pure fertilizers, but outside the range recommended for other horticultural plants

(0.76–4.0 mS cm<sup>1</sup> ) [16]. Further, the negative charge of the SBF is due to the residual amine groups of chitin and amino acids. The ash content of the SS (45.4%) and CF1 (42.8%) were larger than most fertilizers (<5.3%) mainly due to their high silicate and carbonate content. The content of carbohydrates of FPE and FHPE (90–94%) was lower than that of CS and FPC; whereas the content of proteins was relatively low and tended to disappear upon hydrolysis as happened for sugars. Moreover, densification (0.51–0.89 g/cm<sup>3</sup> ) and porosity (48–66%) increased upon pelletization, whereas CS and SS as expected showed the lowest bulk density, but the largest total porosity.

It was estimated that complex carbohydrates present in SBF such as chitin could act as a cementing agents bonding soil particles together improving soil structure and stability. Further, it is reported that calcium ions could act as a cementing agents, bonding soil particles into aggregates resulting in the formation of strong, water-stable aggregates [17]. However, the net postharvest bulk density of the soil did not vary significantly upon treatment with fertilizers probably due to the low applied rate, and density remained in the range generally considered suitable for the normal growth of crops. This low bulk density made root growth and penetration easier and improved the size and system of voids in the soil matrix enabling aeration and water movement. Moreover, the particle size of the powdered fertilizers ranged from 50 to 150 μm and that of the soil and pellets were about 300 and 2 mm, respectively being able to decompose slowly matching the particle size of the soil.

Figure 2 depicts legume growth as a function of time. The largest and fastest growing period of both legumes occurred within the first 2 months of the crop cycle. Both plants followed a sigmoid or S-shaped curve during the growing season corresponding to the period of rapid nutrient uptake. Further, both legumes showed the best growing phase upon fertilization with CF2. Conversely, a slow growth profile for both plants was observed once fertilized with FPE and FHPE. This phenomenon is explained by the reduction of essential nutrients different from C and O.

On the other hand, the pod length, pod mass, and seed mass of PV were outstanding when treated with CF2 and comparable to those of F0 (Table 3). Conversely, crop quality of Pisum sativum (PS) as described by these parameters was superior for SS and only FHPE showed good characteristics among the fertilizing pellets. Further, FPC had the worst crop quality an in this particular case plants were not able to render any kind of grain. Likewise, the fact of having a large pod number was not necessary translated into a large crop yield, but pod length, pod mass and seed mass were all good indicatives of crop yield for both legumes (r > 0.859).

The SBF were applied at a rate of 4 g/kg soil in three monthly amendments. SBF having 8–20% N had a variable effect on legume growth characteristics depending on the composition. As a result, they showed distinctive quantitative and qualitative

Sample

147

Pod length (cm)

> F0

FPC FPE FHPE

SS CS CF1 CF2 p-value

FPC, cellulose pellets; FPE, exoskeletons

significantly

Table 3. Effect of

shrimp-based

 fertilizers,

 substrates and commercial

 fertilizers on plant

development

 for Phaseolus vulgaris and Pisum sativum.

 different according to the Tukey's test at p < 0.05.

0.00

 pellets; FHPE, hydrolyzed exoskeleton pellets; SS, soil substrate; CS, cotton substrate; CF, commercial

0.00

0.00

0.00

0.00

0.00

 fertilizers; mean values with an asterisk within the column are

0.00

0.00

\*10.1

 0.1

\*4.7

 0.1

\*1.2

 0.1

1.1

 0.2

5.5

 0.6

1.5

 0.6

0.6

 0.2

2 0.5

\*7.7

 1.1

2.13

 0.8

\*0.73

 0.1

4.3

 1.3

0.26

 0.1

0.1

 0.0

2 0.1

\*

3 1.0

6.0

 0.8

0.74

 0.1

 0.46

 0.1

2 1

5 0.5

1.1

 0.5

0.43

 0.1

2 0.1

4.9

 1.3

0.62

 0.2

 0.35

 0.1

1 0.0

5 1.6

0.82

 0.2

 0.41

 0.1

1.5

 0.5

4.4

\*6.5

 1.2

\*3.9

 0.9

\*1.43

 0.1

1 0

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

 0.5

0.4

 0.1

0.3

 0.1

4.1

 1.3

0.46

 0.1

 0.22

 0.1

7 0

\*10

 1.2

\*4.56

 2.0

0.77

0.1

 0.0

1 0.0

\*

4 0.5

5 0

 1.83

 0.3\*

2 0.3

5.5

\*

0 0

 0 0.6

 0

\*0.28

 0

 1

\*

3 0

 0

 0

 1.1

1.23

 0.8

\*0.7

\*

0 0

 0.1

 Pod mass (g)

 Seed mass (g)

 Pod number

 Pod length (cm)

 Pod mass (g)

 Seed mass (g)

 Pod number

DOI: http://dx.doi.org/10.5772/intechopen.86914

\*

3 1

\*

0 0

Phaseolus vulgaris

Pisum sativum

#### Figure 2.

Growth profiles given by shrimp-based fertilizers, substrates and commercial fertilizers: (A) Phaseolus vulgaris and (B) Pisum sativum.



Table

Effect

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

(0.76–4.0 mS cm<sup>1</sup>

the largest total porosity.

(r > 0.859).

Figure 2.

146

vulgaris and (B) Pisum sativum.

Moreover, densification (0.51–0.89 g/cm<sup>3</sup>

Food Preservation and Waste Exploitation

) [16]. Further, the negative charge of the SBF is due to the

) and porosity (48–66%) increased upon

residual amine groups of chitin and amino acids. The ash content of the SS (45.4%) and CF1 (42.8%) were larger than most fertilizers (<5.3%) mainly due to their high silicate and carbonate content. The content of carbohydrates of FPE and FHPE (90–94%) was lower than that of CS and FPC; whereas the content of proteins was relatively low and tended to disappear upon hydrolysis as happened for sugars.

pelletization, whereas CS and SS as expected showed the lowest bulk density, but

Both plants followed a sigmoid or S-shaped curve during the growing season

explained by the reduction of essential nutrients different from C and O.

corresponding to the period of rapid nutrient uptake. Further, both legumes showed the best growing phase upon fertilization with CF2. Conversely, a slow growth profile for both plants was observed once fertilized with FPE and FHPE. This phenomenon is

On the other hand, the pod length, pod mass, and seed mass of PV were outstanding when treated with CF2 and comparable to those of F0 (Table 3). Conversely, crop quality of Pisum sativum (PS) as described by these parameters was superior for SS and only FHPE showed good characteristics among the fertilizing pellets. Further, FPC had the worst crop quality an in this particular case plants were not able to render any kind of grain. Likewise, the fact of having a large pod number was not necessary translated into a large crop yield, but pod length, pod mass and seed mass were all good indicatives of crop yield for both legumes

The SBF were applied at a rate of 4 g/kg soil in three monthly amendments. SBF having 8–20% N had a variable effect on legume growth characteristics depending on the composition. As a result, they showed distinctive quantitative and qualitative

Growth profiles given by shrimp-based fertilizers, substrates and commercial fertilizers: (A) Phaseolus

It was estimated that complex carbohydrates present in SBF such as chitin could act as a cementing agents bonding soil particles together improving soil structure and stability. Further, it is reported that calcium ions could act as a cementing agents, bonding soil particles into aggregates resulting in the formation of strong, water-stable aggregates [17]. However, the net postharvest bulk density of the soil did not vary significantly upon treatment with fertilizers probably due to the low applied rate, and density remained in the range generally considered suitable for the normal growth of crops. This low bulk density made root growth and penetration easier and improved the size and system of voids in the soil matrix enabling aeration and water movement. Moreover, the particle size of the powdered fertilizers ranged from 50 to 150 μm and that of the soil and pellets were about 300 and 2 mm, respectively being able to decompose slowly matching the particle size of the soil. Figure 2 depicts legume growth as a function of time. The largest and fastest growing period of both legumes occurred within the first 2 months of the crop cycle.

traits of grain yield of legumes, especially for PV. It has been reported that a large amendment of 20% organic fertilizer (vermicompost) was needed to get the highest pod weight, pod number, pod dry weight and pod length of legumes [5]. In this study, there was a remarkable mismatch between plant growth and plant yield. For instance, CF2 and F0 rendered plants with a good growth and crop yield especially for PV, whereas CP2 only led to a good plant growth rather than crop yield in PS. This is explained by the content of urea:P2O5 (N/P ratio of 13.2), which is recommended by the supplier for the rapid plant growth. In all cases, the N uptake and growth rate were prominent within 30 and 60 days after sowing. In other words, the growth rate progressively increased over time during the vegetative growth up to 4–8 weeks after which growth slowed down as the reproductive phase initiated. Legume growth was not significantly improved with most SBF despite of having a considerable content of available N due to the slow release of this element. However, macroelements such as N, C, P, and Ca were available 45 days after sowing for the appropriate blooming and protein development. Interestingly, the unfertilized CS showed a slow development and crop quality for both legumes, especially for PS and thus these plants were not very efficient as atmospheric N fixers to compensate for the lack of N in the CS. In this case, the branched root hair systems of the legumes were not sufficient to ease N mineralization during the growing phase and as a result, they showed the poorest crop yield.

The soil amended with the fertilizers had pH values between 6.7 and 7.1, which are considered optimum for the rapid development of most ubiquitous microorganisms. At this pH range N loss due to ammonia volatilization is prevented since this phenomenon only occurs at acid pH (<6.0) [18]. Soil porosity was 83% and moisture at saturation was >40% and these levels were not affected by fertilization. The lower water content of SBF was attributed to the presence of insoluble carbohydrates, proteins and of calcium ions. The high moisture content in the soil near to field capacity was responsible for the high diversity of viable microbial during the legume developing phase. These in turn, promoted mineralization and increased available N. The high population of aerobic bacteria found during the whole crop cycle eased nitrogen fixation from the fertilizers and the atmosphere. Interestingly, PV was able to modify its own root environment to maximize nutrient uptake. Thus, the inherent absence of N of the unfertilized substrate forced the plant to increase the root pattern so the nitrogen demand could be obtained by microbial (especially fungi) N2 fixation, as reported previously [19]. However, this N uptake was not sufficient to achieve an optimum plant growth of PS since the unfertilized substrates showed the poorest growth rate in the CS. Conversely, SS showed better crop quality than CS due to the higher content of Si, Mg, Fe and Ca which were absent in CS.

It is accepted that during the decomposition of an organic fertilizer the microbial population requires an optimal diet with a C:N ratio of 15:1 to meet their needs for nutrients. Since the F0, FPE, FHPE and CF2 had a C:N ratio of less than 15:1 they had more N than the microflora require for their own growth in the initial crop cycle and are likely to provide significant plant available N leading to an increased mineral N levels through mineralization carried out by microbial metabolism (production of NH4 <sup>+</sup> and NO3 ) [20]. This phenomenon was reflected on a large microbial population in the soil within the first month (>50,000 cfu/g of bacteria and > 100 cfu/g for fungi). Conversely, the SS, FPC, CS CF1 had a C:N ratio of more than 25:1 and thus, it is assumed a rapid immobilization of the scarce N by microorganisms in this growing phase [21]. Since those fertilizers had N content above 2.5%, they are expected to release nutrients once decomposed by the soil microbiota. The N, P and K ratio of the SBF, and SS were 1–0.1–0.0, and 0–0–0.1, respectively. These ratios are different from other reported for fertilizers such as cow manure (0.97–0.69–1.66) and compost of raw straw (0.81–0.18–0.68).

Time (month)

149

 F0 PV

Mesoaerobic

1 2 3

Fungi (cfu 103/g). Basal count: 100/g

1 2 3 Bacteria/fungi

1 2 3 FPC, cellulose pellets; FPE, exoskeleton pellets; FHPE, hydrolyzed exoeskeleton

Table 4. Total aerobic bacteria and fungi of the soil fertilized with the

10,000

1030

56

 4

 5

 890

 3400

 pellets; SS, soil substrate; CS: cotton substrate; CF, commercial

shrimp-based

 fertilizers and commercial

 fertilizers.

 10

 325

 593

 14

 11

 20

 fertilizers; PV, Phaseolus vulgaris; PS, Pisum sativum.

 2

 540

 77

 11

 6

 43

 36

 49

 891

 60

 1050

 714

 90

 68

 30

 2

 3140

 160

 6

 9

 200

 440

 127

 51

 200

 45

 6

 102

 16

 40

 4

 744

 617

 7

 7

 ratio

0.1

1

10

 12

 0.6

 0.1

 0.2

 5

 1.6

 0.81

 23.6

 28

 1

 0.5

 1

 3

 18

 47

 6

 0.1

 1.7

 1.1

 1

 1.2

 1.4

 14.5

 15

 1

 0.5

 2.5

 4

 27

 37

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

 2

 2

 3

 14

 2

 20

 36

 10

 23

 0.25

 0.5

 7.8

 6

 18

 48

100

103

56

 4.9

 0.3

 8.9

 68

 4.9

 52

 48

 33

 30

 2

 0.1

 54

 23

 19

 28

 26

 0.36

 8.25

 98

 6

 126

 100

 130

 102

 3

 0.1

 785

 64

 17

 33

 40

 88

 38

 72

 40

 90

 20

 102

 36

 1

 0.2

 580

 370

 12

 32

 bacteria (cfu 

 PS 104/g). Basal count: 5104/g

 PV

 PS

 PV

 PS

 PV

 PS

 PV

 PS

 PV

 PS

 PV

 PS

 PV

 PS

DOI: http://dx.doi.org/10.5772/intechopen.86914

FPC

FPE

FHPE

SS

CS

CF1

CF2


Total aerobic bacteria and fungi of the soil fertilized with the

shrimp-based

 fertilizers and commercial

 fertilizers.

#### Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

traits of grain yield of legumes, especially for PV. It has been reported that a large amendment of 20% organic fertilizer (vermicompost) was needed to get the highest pod weight, pod number, pod dry weight and pod length of legumes [5]. In this study, there was a remarkable mismatch between plant growth and plant yield. For instance, CF2 and F0 rendered plants with a good growth and crop yield especially for PV, whereas CP2 only led to a good plant growth rather than crop yield in PS.

recommended by the supplier for the rapid plant growth. In all cases, the N uptake and growth rate were prominent within 30 and 60 days after sowing. In other words, the growth rate progressively increased over time during the vegetative growth up to 4–8 weeks after which growth slowed down as the reproductive phase initiated. Legume growth was not significantly improved with most SBF despite of having a considerable content of available N due to the slow release of this element. However, macroelements such as N, C, P, and Ca were available 45 days after sowing for the appropriate blooming and protein development. Interestingly, the unfertilized CS showed a slow development and crop quality for both legumes, especially for PS and thus these plants were not very efficient as atmospheric N fixers to compensate for the lack of N in the CS. In this case, the branched root hair systems of the legumes were not sufficient to ease N mineralization during the

The soil amended with the fertilizers had pH values between 6.7 and 7.1, which are considered optimum for the rapid development of most ubiquitous microorganisms. At this pH range N loss due to ammonia volatilization is prevented since this phenomenon only occurs at acid pH (<6.0) [18]. Soil porosity was 83% and moisture at saturation was >40% and these levels were not affected by fertilization. The lower water content of SBF was attributed to the presence of insoluble carbohydrates, proteins and of calcium ions. The high moisture content in the soil near to field capacity was responsible for the high diversity of viable microbial during the legume developing phase. These in turn, promoted mineralization and increased available N. The high population of aerobic bacteria found during the whole crop cycle eased nitrogen fixation from the fertilizers and the atmosphere. Interestingly, PV was able to modify its own root environment to maximize nutrient uptake. Thus, the inherent absence of N of the unfertilized substrate forced the plant to increase the root pattern so the nitrogen demand could be obtained by microbial (especially fungi) N2 fixation, as reported previously [19]. However, this N uptake was not sufficient to achieve an optimum plant growth of PS since the unfertilized substrates showed the poorest growth rate in the CS. Conversely, SS showed better crop quality than CS due to the

It is accepted that during the decomposition of an organic fertilizer the microbial population requires an optimal diet with a C:N ratio of 15:1 to meet their needs for nutrients. Since the F0, FPE, FHPE and CF2 had a C:N ratio of less than 15:1 they had more N than the microflora require for their own growth in the initial crop cycle and are likely to provide significant plant available N leading to an increased mineral N levels through mineralization carried out by microbial metabolism (pro-

microbial population in the soil within the first month (>50,000 cfu/g of bacteria and > 100 cfu/g for fungi). Conversely, the SS, FPC, CS CF1 had a C:N ratio of more than 25:1 and thus, it is assumed a rapid immobilization of the scarce N by microorganisms in this growing phase [21]. Since those fertilizers had N content above

microbiota. The N, P and K ratio of the SBF, and SS were 1–0.1–0.0, and 0–0–0.1, respectively. These ratios are different from other reported for fertilizers such as cow manure (0.97–0.69–1.66) and compost of raw straw (0.81–0.18–0.68).

2.5%, they are expected to release nutrients once decomposed by the soil

) [20]. This phenomenon was reflected on a large

This is explained by the content of urea:P2O5 (N/P ratio of 13.2), which is

Food Preservation and Waste Exploitation

growing phase and as a result, they showed the poorest crop yield.

higher content of Si, Mg, Fe and Ca which were absent in CS.

duction of NH4

148

<sup>+</sup> and NO3

absence of N, Ca and P in the unfertilized substrates limited legume growth, and microbial activity. This suggested that nutrient sufficiency ranges may require minor adjustment for plant development. Further, viable microorganism population increased in the beginning of the crop cycle and then declined possibly due to depletion of nutrients, but provided short-term fertility benefits for the legumes productivity. These fertilizers are considered more ecofriendly, more efficient, and accessible to marginal and small farmers located in the coast lines. Shrimp-based fertilizers were found to be an alternative soil amendment for legume crops grown

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

The authors are grateful to Colciencias for providing the financial resources for the execution of this study through the Grant No. 111571551545 and contract no. 036-2016. Authors thank CODI for their sustainability strategy 2018–2019 of Uni-

using organic methods.

DOI: http://dx.doi.org/10.5772/intechopen.86914

Acknowledgements

versity of Antioquia.

Conflict of interest

Author details

John Rojas<sup>1</sup>

151

The authors declare no conflict of interest.

\*, Julian Qunitero<sup>1</sup>

and Ricardo A. Torres-Palma<sup>2</sup>

Antioquia, Medellín, Colombia

Antioquia UdeA, Medellín, Colombia

provided the original work is properly cited.

\*Address all correspondence to: jrojasca@gmail.com

, Yhors Ciro1

1 Department of Food, College of Pharmaceutical and Food Sciences, University of

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

2 Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Facultad de Ciencias Exactas y Naturales, Instituto de Química, Universidad de

, Alfredo Moreno<sup>1</sup>

, Javier Silva-Agredo<sup>2</sup>

Figure 3. Principal component plot for key properties of fertilizers.

The fertilizers once incorporated into the soil showed a variable microbial population which decreased over time, possibly due to depletion of soil nutrients that share with plants in a symbiotic way. In fact, the bacteria population was larger in soils containing PV than PS (Table 4). Conversely, the latter favored the proliferation of fungi in the soil. Further, fertilizer type also influenced the bacterial proliferation; for instance, CF1 rendered the largest bacterial population in the soil, whereas CF2 maintained a virtually constant bacterial count. On the contrary, the soil population of fungi tends to increase over time except for soils treated with CF1 and fertilizing pellets where tended to decrease. This fact was reflected on the bacteria to fungi ratio which decreased over time except for the fertilizing pellets and commercial products which increased and remained unchanged, respectively. The high microbial content of the fertilizers mingled with those of the soil microflora favoring the rapid development of bacteria and fungi, which in turn decreased during the crop cycle.

The multivariate analysis rendered interesting facts about this study. The first three components explained 73.3% of data variability (Figure 3). In the PCA plot four great clusters are observed apart from the center. The first one depicts the influence of Mg and Na on crop quality of PV and the second cluster relates the pod number of PV with the content of Na, P, N, and sugars. The third cluster is related to the crop quality of PS and soil pH; whereas the fourth cluster relates Si, Al with the C/N ratio. Moreover, a correlation analysis confirmed that fertilizers having a high content of Si also had high Al (r > 0.920). Likewise, fertilizers having a high level of N also showed low levels of O and C/N (r > 0.874). Further, high levels of Mg were correlated with those of Na (r = 0.806) and fertilizers having a high content of N also showed high levels of P (r = 0.999).

#### 4. Conclusions

The raw waste rendered an optimal crop quality, especially for PV, but showed a lower growth as compared to CF2. Conversely, the pelletization of raw shrimp waste had a deleterious effect on the crop quality of both legumes. Further, the

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

absence of N, Ca and P in the unfertilized substrates limited legume growth, and microbial activity. This suggested that nutrient sufficiency ranges may require minor adjustment for plant development. Further, viable microorganism population increased in the beginning of the crop cycle and then declined possibly due to depletion of nutrients, but provided short-term fertility benefits for the legumes productivity. These fertilizers are considered more ecofriendly, more efficient, and accessible to marginal and small farmers located in the coast lines. Shrimp-based fertilizers were found to be an alternative soil amendment for legume crops grown using organic methods.

#### Acknowledgements

The authors are grateful to Colciencias for providing the financial resources for the execution of this study through the Grant No. 111571551545 and contract no. 036-2016. Authors thank CODI for their sustainability strategy 2018–2019 of University of Antioquia.

#### Conflict of interest

The fertilizers once incorporated into the soil showed a variable microbial population which decreased over time, possibly due to depletion of soil nutrients that share with plants in a symbiotic way. In fact, the bacteria population was larger in soils containing PV than PS (Table 4). Conversely, the latter favored the proliferation of fungi in the soil. Further, fertilizer type also influenced the bacterial proliferation; for instance, CF1 rendered the largest bacterial population in the soil, whereas CF2 maintained a virtually constant bacterial count. On the contrary, the soil population of fungi tends to increase over time except for soils treated with CF1 and fertilizing pellets where tended to decrease. This fact was reflected on the bacteria to fungi ratio which decreased over time except for the fertilizing pellets and commercial products which increased and remained unchanged, respectively. The high microbial content of the fertilizers mingled with those of the soil microflora favoring the rapid development of bacteria and fungi, which in turn decreased

The multivariate analysis rendered interesting facts about this study. The first three components explained 73.3% of data variability (Figure 3). In the PCA plot four great clusters are observed apart from the center. The first one depicts the influence of Mg and Na on crop quality of PV and the second cluster relates the pod number of PV with the content of Na, P, N, and sugars. The third cluster is related to the crop quality of PS and soil pH; whereas the fourth cluster relates Si, Al with the C/N ratio. Moreover, a correlation analysis confirmed that fertilizers having a high content of Si also had high Al (r > 0.920). Likewise, fertilizers having a high level of N also showed low levels of O and C/N (r > 0.874). Further, high levels of Mg were correlated with those of Na (r = 0.806) and fertilizers having a high

The raw waste rendered an optimal crop quality, especially for PV, but showed a

lower growth as compared to CF2. Conversely, the pelletization of raw shrimp waste had a deleterious effect on the crop quality of both legumes. Further, the

content of N also showed high levels of P (r = 0.999).

during the crop cycle.

Figure 3.

Principal component plot for key properties of fertilizers.

Food Preservation and Waste Exploitation

4. Conclusions

150

The authors declare no conflict of interest.

#### Author details

John Rojas<sup>1</sup> \*, Julian Qunitero<sup>1</sup> , Yhors Ciro1 , Alfredo Moreno<sup>1</sup> , Javier Silva-Agredo<sup>2</sup> and Ricardo A. Torres-Palma<sup>2</sup>

1 Department of Food, College of Pharmaceutical and Food Sciences, University of Antioquia, Medellín, Colombia

2 Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Facultad de Ciencias Exactas y Naturales, Instituto de Química, Universidad de Antioquia UdeA, Medellín, Colombia

\*Address all correspondence to: jrojasca@gmail.com

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

## References

[1] Bassoyouni FA, Abu-Bakr SM, Rehim MA. Evolution of microwave irradiation and its application in green chemistry and biosciences. Research on Chemical Intermediates. 2012;38:283-322. DOI: 10.1007/s11164-011-0348-1

[2] Brink M, Belay GE. Plant resources of tropical Africa: Conclusions and recommendations based on PROTA 1. In: Cereals and Pulses. Leiden: Backhuys; 2006

[3] Valdez-Perez MA, Fernandez-Luqueno F, Franco-Hernandez O. Cultivation of beans (Phaseolus vulgaris) in limed or unlimed wastewater, sludge, vermicompost or inorganic amended soil. Scientia Horticulturae. 2011;128: 380-387. DOI: 10.1016/j.scienta.2011. 01.016

[4] Takahashi K. Physiological disorders in Chinese cabbage. In: Talekar NS, Griggs TD, editors. Chinese Cabbage. Shan Hua, Taiwan: AVRDC; 1981. pp. 225-233

[5] Aminul M, Nasrulhaq A, Motior R, Sofian M, Aqeel M. Effects of organic fertilizers on the growth and yield of bush bean, winged bean and yard long bean. Brazilian Archives of Biology and Technology. 2016;59:1-9. DOI: 10.1590/ 1678-4324-2016160586

[6] Derkowska E, Paszt L, Trzcinsky P, Przibyl M, Weszczak K. Influence of biofertilizers on plant growth and rhizosphere microbiology of greenhouse-grown strawberry cultivars. Acta Scientiarum Polonorum-Hortorum Cultus. 2015;14:83-96

[7] Aluko OA, Olanipekun TO, Olasoji JO, Abiola IO, Adeniyan ON, Olanipekun SO, et al. Effect of organic and inorganic fertilizer on the yield and nutrient composition of jute mallow. Global Journal of Agricultural Research. 2014;2:1-9

[8] Ghimire A. A Review of Organic Farming for Sustainable Agriculture. Tribhuvan University; 2002

crops. Journal of Plant Nutrition. 2010;

DOI: http://dx.doi.org/10.5772/intechopen.86914

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes

[17] Yang R, Su YZ, Wang T, Yang Q. Effect of chemical and organic

fertilization on soil carbon and nitrogen accumulation in a newly cultivated farmland. Journal of Integrative Agriculture. 2016;15:658-666. DOI: 10.1016/S2095-3119(15)61107-8

[18] Swisher ME. An Investigation of the

[19] Celestin NP. Effects of Inorganic and Organic Fertilizers on Nutrient Uptake, Soil Chemical Properties and Crops Performance in Maize Based Cropping Systems in Eastern Province of Rwanda. Kenyatta University; 2013

Potential for the Use of Organic Fertilizer on Small, Mixed Farms in Costa Rica. University of Florida; 1948

[20] Eroa MG. Production and characterization of organic fertilizer from Tubang-Bakod (Jatrophacurcas) seed cake and chicken manure. Asia Pacific Journal of Multidisciplinary

[21] Chavan BL, Vedpathak MM, Pirgonde BR. Effects of organic and chemical fertilizers on cluster bean (Cyamopsis tetragonolobus). European Journal of Experimental Biology. 2015;5:

Research. 2015;3:9-13

34-38

153

33:351-361. DOI: 10.1080/ 01904160903470406

[9] Cespedes L, Stone MC, Dick RP. Organic soil amendments; impacts on snap bean common root rot and soil quality. Applied Soil Ecology. 2006;31: 199-210. DOI: 10.1016/j.apsoil.2005. 05.008

[10] Association of Official Agricultural Chemists. Method 923.03: Ash of Flour (Direct Method). 2005

[11] Albalasmeh AA, Berhe AA, Ghezzehei TA. A new method for rapid determination of carbohydrate and total carbon concentrations using UV spectrophotometry. Carbohydrate Polymers. 2013;97:253-261. DOI: 10.1016/j.carbpol.2013.04.072

[12] Young JH, Nelson GL. Research of hysteresis between sorption and desorption isotherms of wheat. Transactions of ASAE. 1967;10:756-761

[13] Tucker LC. Comparison of Two Different Organic Fertilizer Sources for Flue-Cured Tobacco. Virginia Polytechnic Institute and State University; 2015

[14] Arthur EM, Tuller PM, de Jonge LW. Evaluation of theoretical and empirical water vapor sorption isotherm models for soils. Water Resources Research. 2016;52:190-205. DOI: 10.1002/2015WR017681

[15] Woodruff WF, Revil A. CECnormalized clay-water sorption isotherm. Water Resources Research. 2011;47:1-15. DOI: 10.1029/ 2011WR010919

[16] Nelson PV, Pitchay DS, Niedziela CE, Mingis NC. Efficacy of soybeanbaseliquid fertilizer for greenhouse

Comparative Assessment of Shrimp Hydrolyzates as Alternative Organic Fertilizers for Legumes DOI: http://dx.doi.org/10.5772/intechopen.86914

crops. Journal of Plant Nutrition. 2010; 33:351-361. DOI: 10.1080/ 01904160903470406

References

[1] Bassoyouni FA, Abu-Bakr SM, Rehim MA. Evolution of microwave irradiation and its application in green chemistry and biosciences. Research on Chemical Intermediates. 2012;38:283-322. DOI:

Food Preservation and Waste Exploitation

[8] Ghimire A. A Review of Organic Farming for Sustainable Agriculture.

[9] Cespedes L, Stone MC, Dick RP. Organic soil amendments; impacts on snap bean common root rot and soil quality. Applied Soil Ecology. 2006;31: 199-210. DOI: 10.1016/j.apsoil.2005.

[10] Association of Official Agricultural Chemists. Method 923.03: Ash of Flour

Ghezzehei TA. A new method for rapid determination of carbohydrate and total

[12] Young JH, Nelson GL. Research of hysteresis between sorption and desorption isotherms of wheat.

Transactions of ASAE. 1967;10:756-761

[13] Tucker LC. Comparison of Two Different Organic Fertilizer Sources for

[14] Arthur EM, Tuller PM, de Jonge LW. Evaluation of theoretical and empirical water vapor sorption isotherm models for soils. Water Resources Research. 2016;52:190-205. DOI:

[15] Woodruff WF, Revil A. CECnormalized clay-water sorption isotherm. Water Resources Research.

[16] Nelson PV, Pitchay DS, Niedziela CE, Mingis NC. Efficacy of soybeanbaseliquid fertilizer for greenhouse

Flue-Cured Tobacco. Virginia Polytechnic Institute and State

10.1002/2015WR017681

2011;47:1-15. DOI: 10.1029/

2011WR010919

University; 2015

Tribhuvan University; 2002

(Direct Method). 2005

[11] Albalasmeh AA, Berhe AA,

carbon concentrations using UV spectrophotometry. Carbohydrate Polymers. 2013;97:253-261. DOI: 10.1016/j.carbpol.2013.04.072

05.008

[2] Brink M, Belay GE. Plant resources of

10.1007/s11164-011-0348-1

tropical Africa: Conclusions and recommendations based on PROTA 1.

In: Cereals and Pulses. Leiden:

[3] Valdez-Perez MA, Fernandez-Luqueno F, Franco-Hernandez O. Cultivation of beans (Phaseolus vulgaris) in limed or unlimed wastewater, sludge, vermicompost or inorganic amended soil. Scientia Horticulturae. 2011;128: 380-387. DOI: 10.1016/j.scienta.2011.

[4] Takahashi K. Physiological disorders in Chinese cabbage. In: Talekar NS, Griggs TD, editors. Chinese Cabbage. Shan Hua, Taiwan: AVRDC; 1981.

[5] Aminul M, Nasrulhaq A, Motior R, Sofian M, Aqeel M. Effects of organic fertilizers on the growth and yield of bush bean, winged bean and yard long bean. Brazilian Archives of Biology and Technology. 2016;59:1-9. DOI: 10.1590/

[6] Derkowska E, Paszt L, Trzcinsky P, Przibyl M, Weszczak K. Influence of biofertilizers on plant growth and rhizosphere microbiology of

greenhouse-grown strawberry cultivars. Acta Scientiarum Polonorum-Hortorum

[7] Aluko OA, Olanipekun TO, Olasoji

Olanipekun SO, et al. Effect of organic and inorganic fertilizer on the yield and nutrient composition of jute mallow. Global Journal of Agricultural Research.

JO, Abiola IO, Adeniyan ON,

Backhuys; 2006

01.016

pp. 225-233

1678-4324-2016160586

Cultus. 2015;14:83-96

2014;2:1-9

152

[17] Yang R, Su YZ, Wang T, Yang Q. Effect of chemical and organic fertilization on soil carbon and nitrogen accumulation in a newly cultivated farmland. Journal of Integrative Agriculture. 2016;15:658-666. DOI: 10.1016/S2095-3119(15)61107-8

[18] Swisher ME. An Investigation of the Potential for the Use of Organic Fertilizer on Small, Mixed Farms in Costa Rica. University of Florida; 1948

[19] Celestin NP. Effects of Inorganic and Organic Fertilizers on Nutrient Uptake, Soil Chemical Properties and Crops Performance in Maize Based Cropping Systems in Eastern Province of Rwanda. Kenyatta University; 2013

[20] Eroa MG. Production and characterization of organic fertilizer from Tubang-Bakod (Jatrophacurcas) seed cake and chicken manure. Asia Pacific Journal of Multidisciplinary Research. 2015;3:9-13

[21] Chavan BL, Vedpathak MM, Pirgonde BR. Effects of organic and chemical fertilizers on cluster bean (Cyamopsis tetragonolobus). European Journal of Experimental Biology. 2015;5: 34-38

**155**

**Chapter 8**

**Abstract**

*and Younes Moussaoui*

made from soda-HP pulping process.

fibrous suspension, pulping

**1. Introduction**

Cellulosic Fibers from

Lignocellulosic Biomass for

This chapter gives a brief overview of the cellulose extraction from Opuntia (Cactaceae) fibers. The suitability of this food waste for pulp and paper production was investigated by the determination of the chemical composition and testing two procedures of delignification: chemical and semichemical pulping processes. Chemical pulping procedure was carried out by using soda-anthraquinone (soda-AQ ) mixture, and semichemical pulping process was performed by softening the raw material using soda-hydrogen peroxide (soda-HP) mixture; this operation was followed by mechanical grinding. The obtained fibrous suspensions were characterized by measuring their dimension parameters (fiber length, fiber width, and fine elements), polymerization degree, and their retention water capacity. The effect of pulping process on yield and fiber characteristics in each pulp was studied. The surface morphologies of the produced papers were studied using scanning electron microscope (SEM), and results show the good distribution and individuality of fibers. The structural and mechanical properties of the prepared paper were presented and discussed. Mechanical strength results show the good tenacity of papers

**Keywords:** *Opuntia ficus-indica*, food waste, lignocellulosic fibers, deliberate fibers,

*Opuntia ficus-indica* is a xerophyte plant belonging to the Cactaceae family, well adapted to drought conditions thanks to its succulent nature that allows it to store extraordinary quantities of water [1]. *Opuntia ficus-indica* was used in traditional medicine for therapeutic, cosmetic, anticarcinogenic, anti-inflammatory, antioxidant, antiviral, and antidiabetic goods [2–4]. Thereby, *Opuntia ficus-indica* waste has received significant attention from numerous researches and was investigated because of its important chemical composition which has a high nutritional value, mainly due to their mineral, protein, dietary fiber, and phytochemical contents [4–9]. By-products of *Opuntia ficus-indica* were used by Bensadon et al. [4] as a source of good-quality antioxidant dietary fiber. Furthermore, *Opuntia ficusindica* cladodes have interesting medical antioxidant activity [10, 11]. Likewise, methanol extract of *Opuntia ficus-indica* flowers has an anti-inflammatory effect on

Papermaking Applications

*Faten Mannai, Hanedi Elhleli, Ramzi Khiari* 

#### **Chapter 8**
