**Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil – A Case Study**

Humberto J. José, Regina F. P. M. Moreira, Danielle B. Luiz, Elaine Virmond, Aziza K. Genena, Silvia L. F. Andersen, Rennio F. de Sena and Horst Fr. Schröder

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/53163

**1. Introduction**

A commitment to sustainability and an understanding of the concepts of "cleaner produc‐ tion" are current requirements for achieving environmentally-friendly industrial practices. Such concepts promote the minimization of fresh water consumption, a reduction in waste‐ water production and the recycling of wastes. Hence, in a world where water scarcity and climate change are a reality, actions to protect fresh water resources and enhance renewable energy capacity are mandatory for any type and size of industry. With reference to solid wastes, social and environmental responsibility goes beyond the obligations determined by law and relies on substantial technical research to establish a strict environmental manage‐ ment policy.

Meat processing plants worldwide use approximately 62 Mm³ per year of water. Only a small amount of this quantity becomes a component of the final product. The remaining part becomes wastewater with high biological and chemical oxygen demands, high fat con‐ tent and high concentrations of dry residue, sedimentary and total suspended matter as well as nitrogen and chloride compounds (Sroka et al., 2004). Of the components usually found in these effluents, blood can be considered as the most problematic due to its capacity to in‐ hibit floc formation during physicochemical wastewater treatment and its high biochemical (BOD5, biochemical oxygen demand during decomposition over a 5-day period) and chemi‐

© 2013 J. José et al.; licensee InTech. This is an open access article 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. © 2013 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

cal oxygen demand (COD). In fact, even with correct handling during meat processing, this activity generates 2.0 and 0.5 liters of blood as effluent for each bovine animal and pig, re‐ spectively (Tritt & Schuchardt, 1992). The treatment of both the solid wastes and the waste‐ water from the meat processing industry represents one of the greatest concerns associated with the agro-industrial sector globally, mainly due to the restrictions that international trade regulations have imposed over their use and the related environmental issues.

their own biomass generated and other urban and agro-industrial organic wastes, providing

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

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703

The use of the biosolids originating from the physicochemical treatment of meat processing wastewater can reduce the costs associated with its disposal (which has been prohibited in many locations by strict regulations) as it can directly and significantly reduce the mass and volume of such wastes, allowing energy recovery and generally lower toxic gas emissions when compared to fossil fuels. As long as emissions are below the specified legislative lim‐ its, changing energy policies lend support to the use of this type of biomass as a fuel source,

The EIA Annual Energy Outlook 2011 reported that the global marketed energy consump‐ tion is expected to rise by nearly 50 percent from 2009 through 2035 (US EIA, 2011). Unless

The requirement to reduce carbon dioxide emissions has sparked interest in the use of many types of biomass as alternative energy sources. Since biomass is produced by the photosynthetic reduction of carbon dioxide, its utilization as biofuel can essentially be car‐ bon neutral with respect to the build-up of atmospheric greenhouse gases, increasing both the demand for the characterization of alternative fuels and encouraging the proliferation of scientific papers concerned with this subject (Demirbas, 2004, 2005; de Sena et al., 2008, 2009; Floriani et al., 2010; Obernberger et al., 2006; Virmond et al., 2010, 2011 2012a, 2012b;

Brazil is currently implementing advanced programs aimed at the use of biomass energy, and several experimental and commercial projects are being implemented, such as those presented by Lora and Andrade (2009), to provide important information in order to over‐ come the technical and commercial barriers which inhibit the extensive implementation of bioenergy. The solid wastes produced by the meat industry have been applied mostly to the production of animal feed, which include the slaughter wastes and the wastewater treat‐ ment solids as main ingredients (Johns, 1995; Tritt and Schuchardt, 1992). However, diseases such as BSE (Bovine Spongiform Encephalopathy) have led to restrictions over the use of

The first actions taken by the case study meat processing company, between the years 2003 and 2004, as shown by de Sena et al. (2008), were related to the in-depth investigation of the physicochemical treatment carried out at the wastewater plant with regard to its solids re‐ moval, mainly to achieve an increase in the chlorine-free biomass obtainment with a view to its utilization as a biomass fuel for steam generation. The data obtained indicate that the raw wastewater has a high organic load comprised basically of blood and organic materials that cause the red color, the greater part of the turbidity, the high concentration of total solids, oils and greases, the BOD5 and the COD. The combustion of these wastes, especially the sludge from the wastewater treatment plants, might be a nobler utilization for economic rea‐ sons, however, many parameters related to the combustion must be monitored due to the formation of pollutants such as polychlorinated dibenzodioxins (PCDD), polychlorinated di‐ benzofurans (PCDF), volatile organic compounds (VOCs), NOx, and SO2. The authors

the world energy matrix is altered, fossil fuels will account for 90% of this increase.

power for the neighborhood and improvements in the agrarian economy.

as part of a move towards achieving low carbon economies.

Werther et al., 2000).

these wastes for feed production.

In order to meet this challenge, one of the largest meat processing companies in Brazilian initiated a series of investments in scientific research to improve its environmental perform‐ ance. Biomass as an energy source, air pollution control, and water and wastewater manage‐ ment were the main issues addressed in research projects carried out from 2003 to 2010.

The Brazilian agro-industrial sector consumes large amounts of fresh water and produces large amounts of residues and by-products, which can potentially be used as energy sour‐ ces. The Brazilian legislation itself admits the need for water management in industrial plants to implement cleaner production techniques, which include the conscious uses of wa‐ ter. There are several legal documents that promote the recognition of water as public prop‐ erty and a finite resource with economic value. These legal norms and legislation are gathered in a single official document called "Set of legal regulations: water resources" (Bra‐ zil, 2011) and promote: (1) the rationalization of water use and its conservation, recondition‐ ing and sustainable management; (2) investment in pollution control, reuse, protection and conservation as well as the use of clean technologies to protect water resources; (3) the prac‐ tice of water reuse to reduce discharges of pollutants into receiving waters, conserving wa‐ ter resources for public supply and other uses which demand high quality water; (4) the practice of water reuse to reduce the costs associated with pollution, contributing to the pro‐ tection of the environment and public health; and (5) the creation of guidelines to regulate and encourage the practice of direct reuse of non-potable water. Official Brazilian reports highlight that the costs of water treatment have been raised by the contamination of water resources and water shortages (aspects of quality and quantity) in certain regions of the country. Consequently, they emphasize that high quality water should not be used in activi‐ ties that tolerate water of lower quality (Brazil, 2011).

Regarding the solid waste materials generated in agro-industries, these are commonly gen‐ erated during the processing of crops, but are also produced by all sectors of the food indus‐ try including everything from meat production to confectionery, such as peelings and scraps from fruit and vegetables, food that does not meet quality control standards, pulp and fiber from sugar and starch extraction, sludge from physicochemical and biological wastewater treatment and filter sludge. The co-digestion of energy crops and a variety of residual bio‐ masses may be a good integrated solution for energy recovery from such waste materials, particularly with wastes that are unsuitable for direct disposal on land, as proposed by Schievano et al. (2009). These authors evaluated the suitability and the costs associated with many substitutes for energy crops in biogas production such as: swine manure, municipal solid waste, olive oil sludge, glycerine from biodiesel production and other agro-industrial by-products and residues. They concluded that farms could implant biogas plants to treat their own biomass generated and other urban and agro-industrial organic wastes, providing power for the neighborhood and improvements in the agrarian economy.

cal oxygen demand (COD). In fact, even with correct handling during meat processing, this activity generates 2.0 and 0.5 liters of blood as effluent for each bovine animal and pig, re‐ spectively (Tritt & Schuchardt, 1992). The treatment of both the solid wastes and the waste‐ water from the meat processing industry represents one of the greatest concerns associated with the agro-industrial sector globally, mainly due to the restrictions that international

In order to meet this challenge, one of the largest meat processing companies in Brazilian initiated a series of investments in scientific research to improve its environmental perform‐ ance. Biomass as an energy source, air pollution control, and water and wastewater manage‐ ment were the main issues addressed in research projects carried out from 2003 to 2010.

The Brazilian agro-industrial sector consumes large amounts of fresh water and produces large amounts of residues and by-products, which can potentially be used as energy sour‐ ces. The Brazilian legislation itself admits the need for water management in industrial plants to implement cleaner production techniques, which include the conscious uses of wa‐ ter. There are several legal documents that promote the recognition of water as public prop‐ erty and a finite resource with economic value. These legal norms and legislation are gathered in a single official document called "Set of legal regulations: water resources" (Bra‐ zil, 2011) and promote: (1) the rationalization of water use and its conservation, recondition‐ ing and sustainable management; (2) investment in pollution control, reuse, protection and conservation as well as the use of clean technologies to protect water resources; (3) the prac‐ tice of water reuse to reduce discharges of pollutants into receiving waters, conserving wa‐ ter resources for public supply and other uses which demand high quality water; (4) the practice of water reuse to reduce the costs associated with pollution, contributing to the pro‐ tection of the environment and public health; and (5) the creation of guidelines to regulate and encourage the practice of direct reuse of non-potable water. Official Brazilian reports highlight that the costs of water treatment have been raised by the contamination of water resources and water shortages (aspects of quality and quantity) in certain regions of the country. Consequently, they emphasize that high quality water should not be used in activi‐

Regarding the solid waste materials generated in agro-industries, these are commonly gen‐ erated during the processing of crops, but are also produced by all sectors of the food indus‐ try including everything from meat production to confectionery, such as peelings and scraps from fruit and vegetables, food that does not meet quality control standards, pulp and fiber from sugar and starch extraction, sludge from physicochemical and biological wastewater treatment and filter sludge. The co-digestion of energy crops and a variety of residual bio‐ masses may be a good integrated solution for energy recovery from such waste materials, particularly with wastes that are unsuitable for direct disposal on land, as proposed by Schievano et al. (2009). These authors evaluated the suitability and the costs associated with many substitutes for energy crops in biogas production such as: swine manure, municipal solid waste, olive oil sludge, glycerine from biodiesel production and other agro-industrial by-products and residues. They concluded that farms could implant biogas plants to treat

trade regulations have imposed over their use and the related environmental issues.

ties that tolerate water of lower quality (Brazil, 2011).

702 Food Industry

The use of the biosolids originating from the physicochemical treatment of meat processing wastewater can reduce the costs associated with its disposal (which has been prohibited in many locations by strict regulations) as it can directly and significantly reduce the mass and volume of such wastes, allowing energy recovery and generally lower toxic gas emissions when compared to fossil fuels. As long as emissions are below the specified legislative lim‐ its, changing energy policies lend support to the use of this type of biomass as a fuel source, as part of a move towards achieving low carbon economies.

The EIA Annual Energy Outlook 2011 reported that the global marketed energy consump‐ tion is expected to rise by nearly 50 percent from 2009 through 2035 (US EIA, 2011). Unless the world energy matrix is altered, fossil fuels will account for 90% of this increase.

The requirement to reduce carbon dioxide emissions has sparked interest in the use of many types of biomass as alternative energy sources. Since biomass is produced by the photosynthetic reduction of carbon dioxide, its utilization as biofuel can essentially be car‐ bon neutral with respect to the build-up of atmospheric greenhouse gases, increasing both the demand for the characterization of alternative fuels and encouraging the proliferation of scientific papers concerned with this subject (Demirbas, 2004, 2005; de Sena et al., 2008, 2009; Floriani et al., 2010; Obernberger et al., 2006; Virmond et al., 2010, 2011 2012a, 2012b; Werther et al., 2000).

Brazil is currently implementing advanced programs aimed at the use of biomass energy, and several experimental and commercial projects are being implemented, such as those presented by Lora and Andrade (2009), to provide important information in order to over‐ come the technical and commercial barriers which inhibit the extensive implementation of bioenergy. The solid wastes produced by the meat industry have been applied mostly to the production of animal feed, which include the slaughter wastes and the wastewater treat‐ ment solids as main ingredients (Johns, 1995; Tritt and Schuchardt, 1992). However, diseases such as BSE (Bovine Spongiform Encephalopathy) have led to restrictions over the use of these wastes for feed production.

The first actions taken by the case study meat processing company, between the years 2003 and 2004, as shown by de Sena et al. (2008), were related to the in-depth investigation of the physicochemical treatment carried out at the wastewater plant with regard to its solids re‐ moval, mainly to achieve an increase in the chlorine-free biomass obtainment with a view to its utilization as a biomass fuel for steam generation. The data obtained indicate that the raw wastewater has a high organic load comprised basically of blood and organic materials that cause the red color, the greater part of the turbidity, the high concentration of total solids, oils and greases, the BOD5 and the COD. The combustion of these wastes, especially the sludge from the wastewater treatment plants, might be a nobler utilization for economic rea‐ sons, however, many parameters related to the combustion must be monitored due to the formation of pollutants such as polychlorinated dibenzodioxins (PCDD), polychlorinated di‐ benzofurans (PCDF), volatile organic compounds (VOCs), NOx, and SO2. The authors showed that the physicochemical treatment carried out at the meat processing wastewater plant provides around 20% of sludge, an organic solid residue, using the chlorine-free coag‐ ulant ferric sulfate (instead of aluminum or ferric chloride). In order to avoid discharge and subsequent environmental problems, the authors performed a preliminary combustion test with a mixture of biosolids and sawdust in a mass ratio of 4:1. The results suggested that the use of the biosolids as an alternative energy source would offer a favorable solution, reduc‐ ing disposal and processing costs, as well as avoiding environmental and health problems for staff and the community close to these processing plants, thus establishing a cheaper and cleaner energy source for the meat industry segment (de Sena et al., 2008).

The meat processing plant has its own drinking water treatment plant (DWTP) and waste‐ water treatment plant (WWTP). The major water resource of this unit is from a river called Rio do Peixe. Its DWTP produces around 8,600 m3 d-1 of drinking water, and the WWTP treats around 7,900 m3 d-1 of wastewater. As described by de Sena et al. (2008), after the flo‐

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

logical treatment, while the biosolids are transported by pumps to a three-phase centrifugal system, which separates oil, water and solid parts (biomass). Afterwards, the biomass is dried in an industrial rotating granulator drier with an operating capacity of 400 kg h-1 (model Bruthus, Albrecht, Brazil), where the moisture content was reduced from approxi‐

Figure 1 shows the wastewater treatment process of the case study meat processing plant.

**Wastewater**

Coagulation

Equalization

Flocculation

Flotation

**Figure 1.** Processes involved in the wastewater treatment plant and obtainment of biofuel (de Sena et al., 2008)

The wastewater treatment plants of meat processing units in Brazil usually undergo the same type of treatment process, where a flotation system is the most commonly used solidliquid separation step, due to the natural characteristics of these effluents, which possess high oil and grease contents. To increase the flotation performance the use of coagulants and coagulation aids are mandatory. Dissolved air flotation (DAF) has become an attractive sep‐ aration process because of its well-known higher efficiency in terms of organic matter abate‐ ment, although the increase in costs associated with the production of micro-bubbles and

Liquid

**Biofuel**

Sludge

Aeration

Centrifugation

Oil

**Biomass**

Drying

mately from 80 wt% to 10-20 wt% in order to make the burning process feasible.

h-1, the treated effluent undergoes a bio‐

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705

tation process with a continuous capacity of 350 m3

Biological Treatment

Liquid

Coagulant

Polymer

Another point related to sustainability in the meat processing industry is the associated farm residues, like pig and chicken manure. A reasonable solution for these wastes is their anae‐ robic digestion to produce biogas and/or fertilizers. Many farms in Brazil are implementing biodigestors in order to obtain biogas to produce electrical or thermal energy. Boersma et al. (1981), for example, studied the energy recovery from biogas produced from pig waste and verified an economy of 86%, showing a very good potential for this kind of solution. Also, carbon credits could be sold when the biodigestion process together with the energy recov‐ ery are applied to the farms.

Biogas is composed basically of methane, carbon dioxide, hydrogen sulfide, and other com‐ ponents in lower concentration. The gas production and the proportion of each compound are dependent on the biodigestor parameters and the chemical composition of the substrates (Lucas Jr., 1994).

A typical composition of a biogas is 55-65% of CH4, 35-45% of CO2 and a low concentration of H2S. The presence of H2S can cause corrosion problems when using the biogas as a fuel and also, when it is emitted to the atmosphere, its greenhouse potential is 21 times higher than that of CO2. A high concentration of methane is desirable, as its presence increases the calorific value of the gas, making it more attractive for energy production.

In this context, this chapter was designed to highlight complementary research projects that have been carried out between 2005 and 2010 to implement actions to reduce the fresh water consumption, promoting water recycling and reuse, and to further investigate the applica‐ tion of biomass residues as energy sources and gaseous emissions in combustion processes.

## **2. Case study – Meat processing plant**

The industrial plant which formed the basis of this case study is located in the west of Santa Catarina State (southern Brazil), where water pollution and overexploitation, the uneven distribution of rainfall over the seasons and long periods of drought, especially in summer, have become a significant problem. The activities of the meat processing plant of this case study include the slaughtering and processing of poultry and swine, while the poultry hatchery plant includes all activities involved in poultry growth: breeding, hatching, rear‐ ing, food production and waste handling.

The meat processing plant has its own drinking water treatment plant (DWTP) and waste‐ water treatment plant (WWTP). The major water resource of this unit is from a river called Rio do Peixe. Its DWTP produces around 8,600 m3 d-1 of drinking water, and the WWTP treats around 7,900 m3 d-1 of wastewater. As described by de Sena et al. (2008), after the flo‐ tation process with a continuous capacity of 350 m3 h-1, the treated effluent undergoes a bio‐ logical treatment, while the biosolids are transported by pumps to a three-phase centrifugal system, which separates oil, water and solid parts (biomass). Afterwards, the biomass is dried in an industrial rotating granulator drier with an operating capacity of 400 kg h-1 (model Bruthus, Albrecht, Brazil), where the moisture content was reduced from approxi‐ mately from 80 wt% to 10-20 wt% in order to make the burning process feasible.

showed that the physicochemical treatment carried out at the meat processing wastewater plant provides around 20% of sludge, an organic solid residue, using the chlorine-free coag‐ ulant ferric sulfate (instead of aluminum or ferric chloride). In order to avoid discharge and subsequent environmental problems, the authors performed a preliminary combustion test with a mixture of biosolids and sawdust in a mass ratio of 4:1. The results suggested that the use of the biosolids as an alternative energy source would offer a favorable solution, reduc‐ ing disposal and processing costs, as well as avoiding environmental and health problems for staff and the community close to these processing plants, thus establishing a cheaper and

Another point related to sustainability in the meat processing industry is the associated farm residues, like pig and chicken manure. A reasonable solution for these wastes is their anae‐ robic digestion to produce biogas and/or fertilizers. Many farms in Brazil are implementing biodigestors in order to obtain biogas to produce electrical or thermal energy. Boersma et al. (1981), for example, studied the energy recovery from biogas produced from pig waste and verified an economy of 86%, showing a very good potential for this kind of solution. Also, carbon credits could be sold when the biodigestion process together with the energy recov‐

Biogas is composed basically of methane, carbon dioxide, hydrogen sulfide, and other com‐ ponents in lower concentration. The gas production and the proportion of each compound are dependent on the biodigestor parameters and the chemical composition of the substrates

A typical composition of a biogas is 55-65% of CH4, 35-45% of CO2 and a low concentration of H2S. The presence of H2S can cause corrosion problems when using the biogas as a fuel and also, when it is emitted to the atmosphere, its greenhouse potential is 21 times higher than that of CO2. A high concentration of methane is desirable, as its presence increases the

In this context, this chapter was designed to highlight complementary research projects that have been carried out between 2005 and 2010 to implement actions to reduce the fresh water consumption, promoting water recycling and reuse, and to further investigate the applica‐ tion of biomass residues as energy sources and gaseous emissions in combustion processes.

The industrial plant which formed the basis of this case study is located in the west of Santa Catarina State (southern Brazil), where water pollution and overexploitation, the uneven distribution of rainfall over the seasons and long periods of drought, especially in summer, have become a significant problem. The activities of the meat processing plant of this case study include the slaughtering and processing of poultry and swine, while the poultry hatchery plant includes all activities involved in poultry growth: breeding, hatching, rear‐

cleaner energy source for the meat industry segment (de Sena et al., 2008).

calorific value of the gas, making it more attractive for energy production.

**2. Case study – Meat processing plant**

ing, food production and waste handling.

ery are applied to the farms.

(Lucas Jr., 1994).

704 Food Industry

Figure 1 shows the wastewater treatment process of the case study meat processing plant.

**Figure 1.** Processes involved in the wastewater treatment plant and obtainment of biofuel (de Sena et al., 2008)

The wastewater treatment plants of meat processing units in Brazil usually undergo the same type of treatment process, where a flotation system is the most commonly used solidliquid separation step, due to the natural characteristics of these effluents, which possess high oil and grease contents. To increase the flotation performance the use of coagulants and coagulation aids are mandatory. Dissolved air flotation (DAF) has become an attractive sep‐ aration process because of its well-known higher efficiency in terms of organic matter abate‐ ment, although the increase in costs associated with the production of micro-bubbles and system maintenance must be considered. Flotation processes are preferred in relation to sed‐ imentation considering their faster solids separation, the lower moisture content of the sludge produced and the smaller area requirements. Coagulants themselves are very effi‐ cient for floc formation during the coagulation process, but the use of coagulation aids (*e.g.*, anionic polyacrylamide polymers) after the rapid mixing of the coagulant-wastewater to dis‐ perse the coagulant, have been shown to increase of floc size and to provide higher floc sta‐ bility and high solid separation rates. Since the coagulation and flocculation (addition of coagulation aids during gentle dispersion) are successive steps applied to neutralize the sus‐ pended particles and achieve strong flocs, the addition of these reagents must be carefully and precisely controlled to enhance solid-liquid separation. If some variables related to the process efficiency are not properly controlled, such as pH, reagent concentrations, mixing speed and contact time, the whole process will be unsuccessful. During the increase in floc size air bubbles of different diameters are incorporated into the flocs and this is responsible for the flotation phenomenon. Flotation efficiencies may vary from 60 to 95% of organic mat‐ ter removal, according to the technology applied.

**3. Water and wastewater management**

**1.** Collection and analysis of documents;

**7.** Maintenance of water management.

four process steps was approximately 806 m3

considered as direct wastewater reuse.

**3.** Verification of the points of greatest water consumption;

water production.

sumption;

seven stages:

The water and wastewater management (W2M) proposed for the pilot plant aimed to mini‐ mize the water consumption and evaluate the possibilities for water and wastewater reuse in the food industry. The W2M, described in a previous publication (Luiz et al., 2012a), pro‐ posed strategies for water management in slaughterhouses considering the restrictions im‐ posed by Brazilian legislation and hygiene concerns particular to the food industry. The objective was to present alternatives for the minimization of water consumption and waste‐

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

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707

The proposed W2M is a practical model of industrial water management, which consists of

**4.** Minimization of water consumption with emphasis on the points of greatest water con‐

The points identified as being associated with major water consumption were: (1) pre-cool‐ ing of giblets, (2) washing of poultry carcass before pre-chilling, (3) transportation of giblets, poultry necks and feet, and (4) washing of swine carcass after buckling. The potential for re‐ ducing the fresh water consumption in-line with the current Brazilian legislation in these

After the minimization of water use, the most important action is the evaluation of direct recycling and reuse of wastewater without reconditioning or treatment (direct reuse). The direct reuse could be "in processes without direct contact with food products, that is, in non-potable uses (*e.g.*, as cooling water, for flushing toilets or as irrigation around the plant), thus saving fresh potable water" (Luiz et al., 2012a). Hence, according to the water balance carried out, "the wastewater with the possibility for direct or indirect recycling or reuse was evaluated physically, chemically and microbiologically to verify if and where it could be recycled and reused" (Luiz et al., 2012a). The four types of wastewaters which offered the possibility of reuse originated from: (1) the defrosting of refrigerating and freezing chambers, (2) the purging of condensers, (3) the cooling of smoke fumigator chimneys, and (4) the sealing and cooling of vacuum pumps. These residues had similar water quality parameters; hence they could be mixed before reuse, totaling approximately 1,383 m3 d-1 of wastewater. Depending on the final use, this mixed wastewater could be reused without major treatment or following simple filtration; thus, this approach can be

d-1 (Luiz et al., 2012a).

**2.** Measurement of water consumption and wastewater production (water balance);

**5.** Evaluation of the potential for water reuse and recycling without reconditioning; **6.** Evaluation of the potential for water reuse and recycling after reconditioning; and

When the flotation of the solids is complete, the froth on the surface is separated from the water and skimmed off. It is collected in chambers and is pumped to a three-phase centri‐ fuge where another polymer, a cationic polyacrylamide, is added to improve the oil-watersludge separation. The water undergoes biological treatment and the oil is collected and sold as a raw material for the soap and detergent manufacturing industries. The remaining solid fraction is the sludge which was formerly used as an ingredient for animal food and feeds, especially the pet segment. However, due to the above-mentioned restrictions regard‐ ing its use in feeds, there are currently two other available options for the correct discharge of this so-called waste: combustion/incineration or land disposal. The combustion of the sludge for steam generation was the option chosen in this case study due to both economic and environmental aspects, since the use of an existing waste as part of the fuel content will decrease the fuel costs for internal energy supply, and the amount of sludge added to the fuel used (wood chips) could be properly controlled with regard to the gaseous emissions. On the other hand, land disposal might bring extra costs associated with transportation and long-term storage. All of the results obtained, as well as their pros and cons, are discussed in detail in the following sections.

The importance of the Brazilian poultry industry can be verified by its strong presence in the rural regions, mainly in the southern and south-eastern states. In many cities, poultry pro‐ duction is the main economic activity. The poultry hatchery unit of this case study, as in the case of the meat processing unit, also has its own WWTP. The wastewater originated from the processes of this unit is characterized by a high organic content, with the presence of nu‐ trients such as nitrogen and phosphorus, as well as persistent organic compounds such as the residues of sanitizing products (*e.g.* pesticides) and veterinary drugs (Genena, 2009). The treatment system for the poultry hatchery wastewater comprises a screening stage (primary treatment), followed by equalization and finally biological treatment (secondary treatment: stabilization ponds). The treated wastewater is then discharged into a river (surface water).

## **3. Water and wastewater management**

system maintenance must be considered. Flotation processes are preferred in relation to sed‐ imentation considering their faster solids separation, the lower moisture content of the sludge produced and the smaller area requirements. Coagulants themselves are very effi‐ cient for floc formation during the coagulation process, but the use of coagulation aids (*e.g.*, anionic polyacrylamide polymers) after the rapid mixing of the coagulant-wastewater to dis‐ perse the coagulant, have been shown to increase of floc size and to provide higher floc sta‐ bility and high solid separation rates. Since the coagulation and flocculation (addition of coagulation aids during gentle dispersion) are successive steps applied to neutralize the sus‐ pended particles and achieve strong flocs, the addition of these reagents must be carefully and precisely controlled to enhance solid-liquid separation. If some variables related to the process efficiency are not properly controlled, such as pH, reagent concentrations, mixing speed and contact time, the whole process will be unsuccessful. During the increase in floc size air bubbles of different diameters are incorporated into the flocs and this is responsible for the flotation phenomenon. Flotation efficiencies may vary from 60 to 95% of organic mat‐

When the flotation of the solids is complete, the froth on the surface is separated from the water and skimmed off. It is collected in chambers and is pumped to a three-phase centri‐ fuge where another polymer, a cationic polyacrylamide, is added to improve the oil-watersludge separation. The water undergoes biological treatment and the oil is collected and sold as a raw material for the soap and detergent manufacturing industries. The remaining solid fraction is the sludge which was formerly used as an ingredient for animal food and feeds, especially the pet segment. However, due to the above-mentioned restrictions regard‐ ing its use in feeds, there are currently two other available options for the correct discharge of this so-called waste: combustion/incineration or land disposal. The combustion of the sludge for steam generation was the option chosen in this case study due to both economic and environmental aspects, since the use of an existing waste as part of the fuel content will decrease the fuel costs for internal energy supply, and the amount of sludge added to the fuel used (wood chips) could be properly controlled with regard to the gaseous emissions. On the other hand, land disposal might bring extra costs associated with transportation and long-term storage. All of the results obtained, as well as their pros and cons, are discussed in

The importance of the Brazilian poultry industry can be verified by its strong presence in the rural regions, mainly in the southern and south-eastern states. In many cities, poultry pro‐ duction is the main economic activity. The poultry hatchery unit of this case study, as in the case of the meat processing unit, also has its own WWTP. The wastewater originated from the processes of this unit is characterized by a high organic content, with the presence of nu‐ trients such as nitrogen and phosphorus, as well as persistent organic compounds such as the residues of sanitizing products (*e.g.* pesticides) and veterinary drugs (Genena, 2009). The treatment system for the poultry hatchery wastewater comprises a screening stage (primary treatment), followed by equalization and finally biological treatment (secondary treatment: stabilization ponds). The treated wastewater is then discharged into a river (surface water).

ter removal, according to the technology applied.

706 Food Industry

detail in the following sections.

The water and wastewater management (W2M) proposed for the pilot plant aimed to mini‐ mize the water consumption and evaluate the possibilities for water and wastewater reuse in the food industry. The W2M, described in a previous publication (Luiz et al., 2012a), pro‐ posed strategies for water management in slaughterhouses considering the restrictions im‐ posed by Brazilian legislation and hygiene concerns particular to the food industry. The objective was to present alternatives for the minimization of water consumption and waste‐ water production.

The proposed W2M is a practical model of industrial water management, which consists of seven stages:


The points identified as being associated with major water consumption were: (1) pre-cool‐ ing of giblets, (2) washing of poultry carcass before pre-chilling, (3) transportation of giblets, poultry necks and feet, and (4) washing of swine carcass after buckling. The potential for re‐ ducing the fresh water consumption in-line with the current Brazilian legislation in these four process steps was approximately 806 m3 d-1 (Luiz et al., 2012a).

After the minimization of water use, the most important action is the evaluation of direct recycling and reuse of wastewater without reconditioning or treatment (direct reuse). The direct reuse could be "in processes without direct contact with food products, that is, in non-potable uses (*e.g.*, as cooling water, for flushing toilets or as irrigation around the plant), thus saving fresh potable water" (Luiz et al., 2012a). Hence, according to the water balance carried out, "the wastewater with the possibility for direct or indirect recycling or reuse was evaluated physically, chemically and microbiologically to verify if and where it could be recycled and reused" (Luiz et al., 2012a). The four types of wastewaters which offered the possibility of reuse originated from: (1) the defrosting of refrigerating and freezing chambers, (2) the purging of condensers, (3) the cooling of smoke fumigator chimneys, and (4) the sealing and cooling of vacuum pumps. These residues had similar water quality parameters; hence they could be mixed before reuse, totaling approximately 1,383 m3 d-1 of wastewater. Depending on the final use, this mixed wastewater could be reused without major treatment or following simple filtration; thus, this approach can be considered as direct wastewater reuse.

The theoretical reduction in water consumption, after applying the principles of water minimization and wastewater reuse, was 25.6%, representing a financial saving of around \$434,000 per year (Table 1). However, new regulations need to be elaborated together with national environmental, sanitary and water supply agencies, processing industries and research institutions aiming at the legalization and promotion of water reuse in the food industry.

treatments are inefficient in removing these pollutants (Luiz et al., 2009). These compounds are present in municipal wastewaters primarily as pharmaceuticals and personal care prod‐ ucts (PPCPs) (Esplugas et al., 2007), and also in industrial wastewaters which contain a large number of synthetic and toxic compounds, mainly polar and non-polar hazardous com‐ pounds, pharmaceuticals, phenols, pesticides, endocrine disruptor compounds (EDCs), and non-biodegradable and toxic chlorinated solvents (Esplugas et al., 2007; Liu et al., 2009; Luiz

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

Due to the large variety of recalcitrant organic contaminants, the tertiary treatment applied to produce water for reuse must be exceptionally efficient. The advanced oxidation process‐ es (AOPs) are an excellent alternative. During AOPs, highly reactive oxidizing radicals are formed, mainly hydroxyl radicals (•OH) (Koning et al., 2008). These radicals are non-selec‐ tive, promoting the oxidation of all organic and inorganic contaminants and, in the presence of a sufficient amount of oxidant and optimized reaction conditions, complete mineraliza‐ tion can be reached, the final products being CO2, H2O and inorganic anions. Thus, AOPs are applied to totally or partially remove recalcitrant organic compounds, increasing the bio‐

In previous studies carried out by our group we evaluated the different options of tertiary treatments to produce high quality reuse water to be used in processes without contact with food products, that is, non-potable uses (*e.g*. as cooling water, boiler feed water, toilet flush‐ ing water or for irrigation around the plant) (Cornel et al., 2011; Luiz et al., 2009, 2011, 2012a). However, since Brazilian legislation only allows the use of fresh potable water in the food industry, our research, using real wastewater and aiming to obtain reclaimed water with drinking water quality which adhered to Brazilian legislation, was carried out in

The tertiary treatments evaluated for the slaughterhouse secondary wastewater included: UV, H2O2, O3, and AOPs (H2O2/UV, O3/UV; O3/H2O2/UV; TiO2/UV; and H2O2/TiO2/UV). Ad‐ ditionally, for the best combinations, the kinetics of the photo-induced degradation of color, UV254, total organic carbon (TOC) and/or total coliforms were evaluated (Luiz et al., 2009,

Two main problems were encountered during this research. The first issue was the variation in the quality of the target slaughterhouse wastewater over time, which affected the treat‐ ment efficiency and the determination of the best treatment (Luiz et al., 2011). The second



http://dx.doi.org/10.5772/53163

709



issue was the high concentration of nitrate and nitrite: 45.9(±17.7) mg NO<sup>3</sup>

ard (Brazilian Ministry of Health Administrative Ruling 518/2004) allows 10 mg NO3

In order to remove the recalcitrant organic compounds and the nitrate/nitrite, to reduce the color and turbidity, and to disinfect the secondary wastewater in a single treatment, micro-

et al., 2009, 2010, 2011, 2012a; Petrović et al., 2003).

degradability of wastewater (Rizzo, 2011).

bench-scale and pilot-scale.

2010, 2011, 2012a,b).

3.74-3.77 mg NO<sup>2</sup>

and 1 mg NO2




*3.1.1. Proposed tertiary treatments of slaughterhouse secondary wastewater*


1Considering costs in 2007: \$0.10 and \$0.42 per m3 to treat water (DWTP) and wastewater (WWTP), respectively, in the case study meat processing plant. Data reproduced from Luiz et al., 2012a.

**Table 1.** Water and financial savings

#### **3.1. Tertiary and advanced treatment for indirect wastewater reuse**

Additionally, tertiary treatments are a good alternative to produce high quality indirect re‐ use water, reducing the percent of fresh water consumption. Tertiary treatments can be ap‐ plied to recondition secondary effluents (*i.e*., after secondary activated-sludge treatment), further increasing the possibilities for indirect wastewater reuse inside or outside the build‐ ing. For example, an industrial wastewater treatment plant can produce high quality tertiary wastewater to be used as reuse water in its processes that do not involve contact with the food product, without the risk of adverse effects in terms of the product quality and human health. Alternatively, it can provide this high quality reuse water for another industrial ac‐ tivity, which does not require fresh potable water for all of its processes.

To improve the quality of the wastewater to be reused, it is necessary to disinfect it and to decrease or eliminate the concentration of biologically persistent organic compounds. The inefficient removal of these organic compounds from the wastewater before reuse or dis‐ charge into natural watercourse is promoting their accumulation in fresh water bodies and causing environmental and human health problems and, especially, harming the aquatic an‐ imals (Esplugas et al, 2007; Liu et al., 2009; Luiz et al., 2009, 2010, 2011; Oller et al., 2011).

Biologically resistant pollutants or persistent organic pollutants (POPs) are compounds which are not eliminated through the metabolic activity of living organisms (mainly bacteria and fungi) in natural waters and soils (Oller et al., 2011). Thus, conventional primary (re‐ moval of suspended compounds) and secondary (such as activated sludge) wastewater treatments are inefficient in removing these pollutants (Luiz et al., 2009). These compounds are present in municipal wastewaters primarily as pharmaceuticals and personal care prod‐ ucts (PPCPs) (Esplugas et al., 2007), and also in industrial wastewaters which contain a large number of synthetic and toxic compounds, mainly polar and non-polar hazardous com‐ pounds, pharmaceuticals, phenols, pesticides, endocrine disruptor compounds (EDCs), and non-biodegradable and toxic chlorinated solvents (Esplugas et al., 2007; Liu et al., 2009; Luiz et al., 2009, 2010, 2011, 2012a; Petrović et al., 2003).

Due to the large variety of recalcitrant organic contaminants, the tertiary treatment applied to produce water for reuse must be exceptionally efficient. The advanced oxidation process‐ es (AOPs) are an excellent alternative. During AOPs, highly reactive oxidizing radicals are formed, mainly hydroxyl radicals (•OH) (Koning et al., 2008). These radicals are non-selec‐ tive, promoting the oxidation of all organic and inorganic contaminants and, in the presence of a sufficient amount of oxidant and optimized reaction conditions, complete mineraliza‐ tion can be reached, the final products being CO2, H2O and inorganic anions. Thus, AOPs are applied to totally or partially remove recalcitrant organic compounds, increasing the bio‐ degradability of wastewater (Rizzo, 2011).

### *3.1.1. Proposed tertiary treatments of slaughterhouse secondary wastewater*

The theoretical reduction in water consumption, after applying the principles of water minimization and wastewater reuse, was 25.6%, representing a financial saving of around \$434,000 per year (Table 1). However, new regulations need to be elaborated together with national environmental, sanitary and water supply agencies, processing industries and research institutions aiming at the legalization and promotion of water reuse in the

Production in 2007 8616.0 - 1,539,353 Theoretical production after water minimization 7810.0 9.4 1,366,000 Theoretical production after wastewater reuse 7216.8 16.0 1,256,996

1Considering costs in 2007: \$0.10 and \$0.42 per m3 to treat water (DWTP) and wastewater (WWTP), respectively, in

Additionally, tertiary treatments are a good alternative to produce high quality indirect re‐ use water, reducing the percent of fresh water consumption. Tertiary treatments can be ap‐ plied to recondition secondary effluents (*i.e*., after secondary activated-sludge treatment), further increasing the possibilities for indirect wastewater reuse inside or outside the build‐ ing. For example, an industrial wastewater treatment plant can produce high quality tertiary wastewater to be used as reuse water in its processes that do not involve contact with the food product, without the risk of adverse effects in terms of the product quality and human health. Alternatively, it can provide this high quality reuse water for another industrial ac‐

To improve the quality of the wastewater to be reused, it is necessary to disinfect it and to decrease or eliminate the concentration of biologically persistent organic compounds. The inefficient removal of these organic compounds from the wastewater before reuse or dis‐ charge into natural watercourse is promoting their accumulation in fresh water bodies and causing environmental and human health problems and, especially, harming the aquatic an‐ imals (Esplugas et al, 2007; Liu et al., 2009; Luiz et al., 2009, 2010, 2011; Oller et al., 2011).

Biologically resistant pollutants or persistent organic pollutants (POPs) are compounds which are not eliminated through the metabolic activity of living organisms (mainly bacteria and fungi) in natural waters and soils (Oller et al., 2011). Thus, conventional primary (re‐ moval of suspended compounds) and secondary (such as activated sludge) wastewater

**Water flow (m3 day-1)**

**Water saving (%)**

6410.0 25.4 1,104,731

**Annual Costs1 (\$)**

food industry.

708 Food Industry

wastewater reuse

**Condition**

the case study meat processing plant. Data reproduced from Luiz et al., 2012a.

**3.1. Tertiary and advanced treatment for indirect wastewater reuse**

tivity, which does not require fresh potable water for all of its processes.

Theoretical production after water minimization and

**Table 1.** Water and financial savings

In previous studies carried out by our group we evaluated the different options of tertiary treatments to produce high quality reuse water to be used in processes without contact with food products, that is, non-potable uses (*e.g*. as cooling water, boiler feed water, toilet flush‐ ing water or for irrigation around the plant) (Cornel et al., 2011; Luiz et al., 2009, 2011, 2012a). However, since Brazilian legislation only allows the use of fresh potable water in the food industry, our research, using real wastewater and aiming to obtain reclaimed water with drinking water quality which adhered to Brazilian legislation, was carried out in bench-scale and pilot-scale.

The tertiary treatments evaluated for the slaughterhouse secondary wastewater included: UV, H2O2, O3, and AOPs (H2O2/UV, O3/UV; O3/H2O2/UV; TiO2/UV; and H2O2/TiO2/UV). Ad‐ ditionally, for the best combinations, the kinetics of the photo-induced degradation of color, UV254, total organic carbon (TOC) and/or total coliforms were evaluated (Luiz et al., 2009, 2010, 2011, 2012a,b).

Two main problems were encountered during this research. The first issue was the variation in the quality of the target slaughterhouse wastewater over time, which affected the treat‐ ment efficiency and the determination of the best treatment (Luiz et al., 2011). The second issue was the high concentration of nitrate and nitrite: 45.9(±17.7) mg NO<sup>3</sup> - -N L-1 and 3.74-3.77 mg NO<sup>2</sup> - -N L-1, respectively (Luiz et al., 2012). The Brazilian drinking water stand‐ ard (Brazilian Ministry of Health Administrative Ruling 518/2004) allows 10 mg NO3 - -N L-1 and 1 mg NO2 - -N L-1, respectively.

In order to remove the recalcitrant organic compounds and the nitrate/nitrite, to reduce the color and turbidity, and to disinfect the secondary wastewater in a single treatment, microfiltration followed by an AOP employing H2O2/TiO2/UV was identified as the best combina‐ tion evaluated (Figure 2).

found was the macrolide antibiotic erythromycin A and its removal and degradation prod‐ ucts resulting from direct ozone attack and hydroxyl radical attack (AOPs O3/UV, O3/H2O2 and UV/H2O2) were evaluated. However, the research indicated that the degradation of or‐ ganic micropollutants, such as erythromycin, in the AOP may be faster than under ozone treatment, because the hydroxyl radical attack (AOP treatments) is not selective and is usu‐ ally diffusion-controlled. On the other hand, the direct attack of ozone is selective and is typ‐ ically targeted toward functional groups with a lone valence electron pair where the electrophilic addition of ozone occurs (unsaturated compounds with carbon-carbon double or triple bonds - π bonds, aromatic rings, amines and sulfides) (Luiz et al., 2010, 2012a).

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Industrial wastewater is generally comprised of various effluent streams generated at differ‐ ent points in a particular process. Its physicochemical characteristics can present considera‐ ble variation over time due to, for instance, changes in operating procedures and cleaning activities. Therefore, the complexity and variation of its composition are typical attributes of

The poultry hatchery wastewater of this case study was collected and passed through the stages of screening and equalization. The wastewater variability was investigated over a pe‐ riod of 48 h and its quality was evaluated by chemical oxygen demand (COD) analysis, which is an overall pollution indicator and represents the amount of organic matter present in the sample. The COD values ranged from 218±2 to 997±5 mg O<sup>2</sup> L-1, which confirms the

Wastewater in the poultry hatcheries originates mainly from the washing of equipment and utensils. Therefore, a series of diverse compounds may be present, such as veterinary drugs administered to the animals through feed and excreted by them in urine, and sanitizer agents and pesticides used in the cleaning and disinfection of the work environment (Gene‐ na, 2009). These compounds, which are persistent compounds, are very harmful to the envi‐ ronment, presenting high toxicity and bioaccumulation (Almeida et al., 2004). They are complex and often difficult to degrade in the biological treatment systems commonly

The food industry is constantly seeking ways to improve the quality of its wastewater through changes in treatment systems. The growing concern regarding emerging and per‐ sistent compounds has resulted in researchers focusing their attention on alternative meth‐ ods of wastewater treatment to minimize or avoid the discharge of these pollutants into water resources, since the biological treatment processes typically used by the food industry are not able to destroy these types of compounds (Genena et al., 2011). The application of oxidative elimination methods, *e.g.*, direct oxidation with ozone or hydrogen peroxide and AOP have been highlighted as strong alternatives for the treatment of wastewater contain‐ ing compounds which do not degrade easily (de Sena et al., 2009; Genena, 2009, Genena et

high variability in the nature of the poultry hatchery wastewater (Genena, 2009).

*3.1.2. Poultry hatchery wastewater treatment*

industrial wastewater (Genena, 2009).

present in industrial wastewater treatment plants.

al., 2011; Luiz et al., 2009, 2010; Tambosi et al., 2009).

**Figure 2.** Process proposed for the treatment of secondary wastewaters with high concentration of nitrate/nitrite and recalcitrant organic compounds.

The photocatalytic removal of nitrate/nitrite is more effective in the absence of dissolved oxygen, because if O2 is present this oxidant agent will be a better final electron acceptor than nitrate or nitrite. The catalyst is activated by the absorption of high energy photons, promoting the excitation of the electrons from the valence band (VB) to the conduction band (CB), and consequently an electron (e- ) and a positive hole (h+ ) are formed in the CB and VB, respectively (Luiz et al., 2012b). The electron reduces the oxidizing agent adsorbed on the catalyst, and the hole oxidizes the organic compound or H2O. In the latter case, the oxidation of H2O produces •OH radicals, which will also oxidize organic matter (Ahmed et al., 2010).

Therefore, during the photocatalytic removal of nitrate/nitrite by UV/TiO2, nitrate and nitrite ions will be the final electron acceptor and they will be reduced to N2 gas. The natural or‐ ganic compounds or residual, biologically persistent, organic pollutants (in the case of in‐ dustrial wastewaters) will be the hole scavengers (electron donors, reducing agent). In cases where the natural concentration of organic compounds in the aquatic medium is not suffi‐ cient to promote the reduction of nitrate/nitrite to below the desired concentration, a carbon source should be added. Formic acid is a good alternative since its residue can be complete‐ ly decomposed into the harmless compounds CO2 and H2O (Luiz et al., 2012b; Rengaraj and Li, 2007; Sá et al., 2009; Wehbe et al., 2009; Zhang et al, 2005). Finally, the heterogeneous AOP system UV/TiO2/H2O2 was applied in the presence of O2 to remove residual organic matter and achieve the required standard of drinking water quality (Luiz et al., 2012b).

The proposed treatment was also successful in removing recalcitrant organic compounds present in the secondary treated slaughterhouse wastewater, which include antibiotics, pharmaceuticals and personal care products which are commonly found in industrial, but predominantly in sanitary and domestic, wastewater (Luiz et al., 2009). One such compound found was the macrolide antibiotic erythromycin A and its removal and degradation prod‐ ucts resulting from direct ozone attack and hydroxyl radical attack (AOPs O3/UV, O3/H2O2 and UV/H2O2) were evaluated. However, the research indicated that the degradation of or‐ ganic micropollutants, such as erythromycin, in the AOP may be faster than under ozone treatment, because the hydroxyl radical attack (AOP treatments) is not selective and is usu‐ ally diffusion-controlled. On the other hand, the direct attack of ozone is selective and is typ‐ ically targeted toward functional groups with a lone valence electron pair where the electrophilic addition of ozone occurs (unsaturated compounds with carbon-carbon double or triple bonds - π bonds, aromatic rings, amines and sulfides) (Luiz et al., 2010, 2012a).

#### *3.1.2. Poultry hatchery wastewater treatment*

filtration followed by an AOP employing H2O2/TiO2/UV was identified as the best combina‐

Microfiltration - Removal of suspended solids

UV/TiO2 in absence of O2 - Removal of nitrate and natural organic compounds at the same time

AOP UV/TiO2/H2O2 heterogeneous system in presence of O2 - Removal of residual organic matter

**Figure 2.** Process proposed for the treatment of secondary wastewaters with high concentration of nitrate/nitrite and

The photocatalytic removal of nitrate/nitrite is more effective in the absence of dissolved oxygen, because if O2 is present this oxidant agent will be a better final electron acceptor than nitrate or nitrite. The catalyst is activated by the absorption of high energy photons, promoting the excitation of the electrons from the valence band (VB) to the conduction band

respectively (Luiz et al., 2012b). The electron reduces the oxidizing agent adsorbed on the catalyst, and the hole oxidizes the organic compound or H2O. In the latter case, the oxidation of H2O produces •OH radicals, which will also oxidize organic matter (Ahmed et al., 2010).

Therefore, during the photocatalytic removal of nitrate/nitrite by UV/TiO2, nitrate and nitrite ions will be the final electron acceptor and they will be reduced to N2 gas. The natural or‐ ganic compounds or residual, biologically persistent, organic pollutants (in the case of in‐ dustrial wastewaters) will be the hole scavengers (electron donors, reducing agent). In cases where the natural concentration of organic compounds in the aquatic medium is not suffi‐ cient to promote the reduction of nitrate/nitrite to below the desired concentration, a carbon source should be added. Formic acid is a good alternative since its residue can be complete‐ ly decomposed into the harmless compounds CO2 and H2O (Luiz et al., 2012b; Rengaraj and Li, 2007; Sá et al., 2009; Wehbe et al., 2009; Zhang et al, 2005). Finally, the heterogeneous AOP system UV/TiO2/H2O2 was applied in the presence of O2 to remove residual organic matter and achieve the required standard of drinking water quality (Luiz et al., 2012b).

The proposed treatment was also successful in removing recalcitrant organic compounds present in the secondary treated slaughterhouse wastewater, which include antibiotics, pharmaceuticals and personal care products which are commonly found in industrial, but predominantly in sanitary and domestic, wastewater (Luiz et al., 2009). One such compound

) and a positive hole (h+

) are formed in the CB and VB,

tion evaluated (Figure 2).

710 Food Industry

recalcitrant organic compounds.

(CB), and consequently an electron (e-

Industrial wastewater is generally comprised of various effluent streams generated at differ‐ ent points in a particular process. Its physicochemical characteristics can present considera‐ ble variation over time due to, for instance, changes in operating procedures and cleaning activities. Therefore, the complexity and variation of its composition are typical attributes of industrial wastewater (Genena, 2009).

The poultry hatchery wastewater of this case study was collected and passed through the stages of screening and equalization. The wastewater variability was investigated over a pe‐ riod of 48 h and its quality was evaluated by chemical oxygen demand (COD) analysis, which is an overall pollution indicator and represents the amount of organic matter present in the sample. The COD values ranged from 218±2 to 997±5 mg O<sup>2</sup> L-1, which confirms the high variability in the nature of the poultry hatchery wastewater (Genena, 2009).

Wastewater in the poultry hatcheries originates mainly from the washing of equipment and utensils. Therefore, a series of diverse compounds may be present, such as veterinary drugs administered to the animals through feed and excreted by them in urine, and sanitizer agents and pesticides used in the cleaning and disinfection of the work environment (Gene‐ na, 2009). These compounds, which are persistent compounds, are very harmful to the envi‐ ronment, presenting high toxicity and bioaccumulation (Almeida et al., 2004). They are complex and often difficult to degrade in the biological treatment systems commonly present in industrial wastewater treatment plants.

The food industry is constantly seeking ways to improve the quality of its wastewater through changes in treatment systems. The growing concern regarding emerging and per‐ sistent compounds has resulted in researchers focusing their attention on alternative meth‐ ods of wastewater treatment to minimize or avoid the discharge of these pollutants into water resources, since the biological treatment processes typically used by the food industry are not able to destroy these types of compounds (Genena et al., 2011). The application of oxidative elimination methods, *e.g.*, direct oxidation with ozone or hydrogen peroxide and AOP have been highlighted as strong alternatives for the treatment of wastewater contain‐ ing compounds which do not degrade easily (de Sena et al., 2009; Genena, 2009, Genena et al., 2011; Luiz et al., 2009, 2010; Tambosi et al., 2009).

The proposal for the use of physicochemical processes for the treatment of the poultry hatchery wastewater of this case study was based on the value of 4.6 for the COD/BOD5 ratio (low biodegradability) and the presence of persistent compounds. Therefore, the appli‐ cation of different AOPs (H2O2/Fe2+ – Fenton, H2O2/Fe2+/UV – photo-Fenton and H2O2/UV) for the poultry hatchery wastewater treatment was investigated. The wastewater treatment process by photo-Fenton reaction was found to be the most appropriate, resulting in better organic matter removal efficiency (approximately 91.9% of COD and 66.3% of TOC). Addi‐ tionally, the COD/BOD5 ratio obtained for the treated wastewater indicates that all physico‐ chemical treatments applied improved the biodegradability, *i.e.*, there was an increase in the amount of material susceptible to degradation by biological processes, reaching a value of 1.5 in the photo-Fenton process. Thus, the biological process can be considered as a posttreatment stage, which would reduce the total costs of the wastewater treatment process (Genena, 2009).

in toxicity over time for both treatments, indicating that the by-products were not more toxic

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The biosolids originating from the wastewater treatment system of the meat processing plant, sawdust and their mixture in a mass ratio of 1:9 (w/w) were characterized as fuels. The correlations between the fuel properties, the operating parameters for the combustion and the gaseous emissions were then investigated in order to evaluate the feasibility of ap‐

The fuel properties often form the basis for the selection of the most appropriate technol‐ ogy for the biomass-to-energy conversion process. Depending on these properties, a bio‐ mass fuel may not be suitable for specific conversion options, partially for technical and sometimes for environmental reasons. The characteristics of the biomass are influenced by its origin and also by the entire processing system preceding any conversion step. Bi‐ omass presents a wide variation in its physical and chemical properties. Many publica‐ tions have investigated the effects of the biomass properties on thermal conversion processes (Demirbas, 2004; Jenkins et al., 1998; Obernberger et al., 2006; van Paasen et al., 2006; Werther et al., 2000; Werther, 2007). The use of biomass as a fuel in combustion processes is frequently desirable in the agro-industry sector because the residues, such as wastewater sludge, usually present high calorific value. However, burning biomass con‐ taining different mineral matter compositions may create various problems which can af‐ fect the boiler operation or make the firing of the biomass in conventional combustion

Wood and wood-based materials are extensively used as fuel for thermal energy generation

In order to evaluate the potential for the utilization of the biosolids originating from the case study plant for co-combustion with sawdust, a sample of the biosolids obtained from the physicochemical treatment (LFP) was chemically and physically characterized, and its com‐ position was compared to that of sawdust (SD), taken as a reference fuel. Additionally, a sample of a mixture of LFP and SD in a mass ratio of 1:9 w/w (LFPSD1:9) was also character‐

The methodology applied for the biomass characterization and the results obtained for LFP, SD and LFPSD1:9 were reported by Floriani et al. (2010) and Virmond et al. (2008, 2011), and

Carbon (C), hydrogen (H) and oxygen (O) are the main components of solid biofuels. Car‐ bon and hydrogen contribute positively to the HHV (higher heating value). The content of hydrogen also influences the LHV (lower heating value) due to the formation of water. The

particularly in the Brazilian food industry, which requires large amounts of steam.

ized and the results compared to SD and LFP properties.

plying this organic residue as a substitute fuel for thermal energy generation.

than their parent molecules (Genena, 2009, Genena et al., 2011).

**4. Biomass-to-energy actions**

**4.1. Biomass properties**

systems unprofitable.

are summarized in Table 2.

An important consideration in the degradation processes is the potential for the generation of toxic intermediates or compounds which are even more toxic than their parent molecule, and thus it is necessary to monitor the process using toxicity assays (Bila et al., 2005). The *Daphnia magna* acute toxicity evaluation showed that all treatments promoted a significant reduction in the wastewater toxicity effects, and a 94% reduction was reached in photo-Fen‐ ton process (Genena, 2009).

Photo-Fenton and Fenton processes result in the formation of a sludge, which is usually de‐ posited in landfills. Thus, better alternatives are being proposed and among them is sludge combustion for power generation. However, in this case study the amount of sludge ob‐ tained was insufficient for the determination of its calorific power (Genena, 2009).

The poultry hatchery wastewater was submitted to analysis by liquid chromatography cou‐ pled to mass spectrometry (LC/MS) with the objective of investigating the presence of per‐ sistent compounds. The presence of imazalil (pesticide) was confirmed among the investigated compounds. Imazalil is an organochloride compound used as a fungicide in the industry for sanitization (Genena, 2009, Genena et al., 2011). Organochlorine pesticides are typical persistent organic pollutants and are the subject of worldwide concern due to their persistence, bioaccumulation and potential negative impacts on humans and animals (Guan et al., 2009; Zhang et al., 2007). The biological treatment of wastewater containing micropol‐ lutants, like pesticides, is often very complicated or even impossible, because many pesti‐ cides are highly toxic to wastewater biocoenosis (Genena et al., 2011).

The treatment of ultrapure water to remove imazalil has been investigated applying the photo-Fenton (AOP) and ozonation processes. *Tert*-butanol (t-BuOH) was used in the ozona‐ tion process as an •OH scavenger to ensure that the study was focused only on the direct attack of imazalil by molecular ozone. For both processes the detection and identification of by-products were carried out, applying sophisticated analytical techniques such as LC/MS and LC/MSn (liquid chromatography coupled to mass or multiple tandem mass spectrome‐ try). The toxicity induced by these by-products was also investigated. For each process of oxidative treatment, four degradation products not yet known were detected and their structures were elucidated. The toxicity analysis (*Daphnia magna* assays) revealed a decrease in toxicity over time for both treatments, indicating that the by-products were not more toxic than their parent molecules (Genena, 2009, Genena et al., 2011).

## **4. Biomass-to-energy actions**

The biosolids originating from the wastewater treatment system of the meat processing plant, sawdust and their mixture in a mass ratio of 1:9 (w/w) were characterized as fuels. The correlations between the fuel properties, the operating parameters for the combustion and the gaseous emissions were then investigated in order to evaluate the feasibility of ap‐ plying this organic residue as a substitute fuel for thermal energy generation.

#### **4.1. Biomass properties**

The proposal for the use of physicochemical processes for the treatment of the poultry hatchery wastewater of this case study was based on the value of 4.6 for the COD/BOD5 ratio (low biodegradability) and the presence of persistent compounds. Therefore, the appli‐ cation of different AOPs (H2O2/Fe2+ – Fenton, H2O2/Fe2+/UV – photo-Fenton and H2O2/UV) for the poultry hatchery wastewater treatment was investigated. The wastewater treatment process by photo-Fenton reaction was found to be the most appropriate, resulting in better organic matter removal efficiency (approximately 91.9% of COD and 66.3% of TOC). Addi‐ tionally, the COD/BOD5 ratio obtained for the treated wastewater indicates that all physico‐ chemical treatments applied improved the biodegradability, *i.e.*, there was an increase in the amount of material susceptible to degradation by biological processes, reaching a value of 1.5 in the photo-Fenton process. Thus, the biological process can be considered as a posttreatment stage, which would reduce the total costs of the wastewater treatment process

An important consideration in the degradation processes is the potential for the generation of toxic intermediates or compounds which are even more toxic than their parent molecule, and thus it is necessary to monitor the process using toxicity assays (Bila et al., 2005). The *Daphnia magna* acute toxicity evaluation showed that all treatments promoted a significant reduction in the wastewater toxicity effects, and a 94% reduction was reached in photo-Fen‐

Photo-Fenton and Fenton processes result in the formation of a sludge, which is usually de‐ posited in landfills. Thus, better alternatives are being proposed and among them is sludge combustion for power generation. However, in this case study the amount of sludge ob‐

The poultry hatchery wastewater was submitted to analysis by liquid chromatography cou‐ pled to mass spectrometry (LC/MS) with the objective of investigating the presence of per‐ sistent compounds. The presence of imazalil (pesticide) was confirmed among the investigated compounds. Imazalil is an organochloride compound used as a fungicide in the industry for sanitization (Genena, 2009, Genena et al., 2011). Organochlorine pesticides are typical persistent organic pollutants and are the subject of worldwide concern due to their persistence, bioaccumulation and potential negative impacts on humans and animals (Guan et al., 2009; Zhang et al., 2007). The biological treatment of wastewater containing micropol‐ lutants, like pesticides, is often very complicated or even impossible, because many pesti‐

The treatment of ultrapure water to remove imazalil has been investigated applying the photo-Fenton (AOP) and ozonation processes. *Tert*-butanol (t-BuOH) was used in the ozona‐ tion process as an •OH scavenger to ensure that the study was focused only on the direct attack of imazalil by molecular ozone. For both processes the detection and identification of by-products were carried out, applying sophisticated analytical techniques such as LC/MS and LC/MSn (liquid chromatography coupled to mass or multiple tandem mass spectrome‐ try). The toxicity induced by these by-products was also investigated. For each process of oxidative treatment, four degradation products not yet known were detected and their structures were elucidated. The toxicity analysis (*Daphnia magna* assays) revealed a decrease

tained was insufficient for the determination of its calorific power (Genena, 2009).

cides are highly toxic to wastewater biocoenosis (Genena et al., 2011).

(Genena, 2009).

712 Food Industry

ton process (Genena, 2009).

The fuel properties often form the basis for the selection of the most appropriate technol‐ ogy for the biomass-to-energy conversion process. Depending on these properties, a bio‐ mass fuel may not be suitable for specific conversion options, partially for technical and sometimes for environmental reasons. The characteristics of the biomass are influenced by its origin and also by the entire processing system preceding any conversion step. Bi‐ omass presents a wide variation in its physical and chemical properties. Many publica‐ tions have investigated the effects of the biomass properties on thermal conversion processes (Demirbas, 2004; Jenkins et al., 1998; Obernberger et al., 2006; van Paasen et al., 2006; Werther et al., 2000; Werther, 2007). The use of biomass as a fuel in combustion processes is frequently desirable in the agro-industry sector because the residues, such as wastewater sludge, usually present high calorific value. However, burning biomass con‐ taining different mineral matter compositions may create various problems which can af‐ fect the boiler operation or make the firing of the biomass in conventional combustion systems unprofitable.

Wood and wood-based materials are extensively used as fuel for thermal energy generation particularly in the Brazilian food industry, which requires large amounts of steam.

In order to evaluate the potential for the utilization of the biosolids originating from the case study plant for co-combustion with sawdust, a sample of the biosolids obtained from the physicochemical treatment (LFP) was chemically and physically characterized, and its com‐ position was compared to that of sawdust (SD), taken as a reference fuel. Additionally, a sample of a mixture of LFP and SD in a mass ratio of 1:9 w/w (LFPSD1:9) was also character‐ ized and the results compared to SD and LFP properties.

The methodology applied for the biomass characterization and the results obtained for LFP, SD and LFPSD1:9 were reported by Floriani et al. (2010) and Virmond et al. (2008, 2011), and are summarized in Table 2.

Carbon (C), hydrogen (H) and oxygen (O) are the main components of solid biofuels. Car‐ bon and hydrogen contribute positively to the HHV (higher heating value). The content of hydrogen also influences the LHV (lower heating value) due to the formation of water. The content of greases was also measured in the LFP composition (34.39 wt%, raw) and it con‐ tributes considerably to the high energy content of the LFP (LHV of 25.77 MJ kg-1, daf). The presence of chlorine in the biomass (0.18 wt%) occurs due to the utilization of chlorine-based products for hygiene purposes at the plant and is incorporated into the wastewater as well as into the remaining biosolids (LFP). The nitrogen content of the fuel mixture LFPSD1:9 (1.36 wt%), even though much lower than the concentration found in LFP, can still cause problems in terms of NOx emission during its combustion. The variability of components present in the biomass is mainly due to the chemical compounds used as ingredients during meat processing operations, especially salts and additives. The sulfur content in LFP is mainly due to the conversion of sulfur-containing proteins, but some may remain from the precipitation agent used in the wastewater treatment (ferric sulfate).

In previous publications (Floriani et al., 2010; Virmond et al., 2008, 2011), the authors have addressed the effects of the LFP ash composition on the fouling and slagging tendency in the combustion systems, showing that the occurrence of this problem can be reduced when burning a mixture of the biosolids with wood residues such as SD compared to LFP alone.

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

As shown in Table 3, the ash melting temperatures of LFP are much lower than the values estimated for LFPSD1:9 through mass balance analysis considering a homogeneous mixture,

Fe2O3 (wt%, db) 4.44 32.40 9.34 CaO (wt%, db) 31.27 17.40 22.77 MgO (wt%, db) 11.64 1.30 4.59 Na2O (wt%, db) 1.67 1.70 1.14 K2O (wt%, db) 10.44 1.70 8.77 SiO2 (wt%, db) 15.69 4.90 17.84 Al2O3 (wt%, db) 12.30 1.70 8.22 TiO2 (wt%, db) 3.94 0.00 3.07 P2O5 (wt%, db) 2.74 36.30 8.50 MnO (wt%, db) 2.06 n.d. n.d. SO4 (wt%, db) 3.02 n.d. n.d.

Deformation temperature (°C) >1150\* 750 1335 Softening temperature (°C) >1170\* 990 1359 Hemispherical temperature (°C) >1190\* 1010 1361 Fluid temperature (°C) >1230\* 1040 1364

1Data reproduced from Virmond et al. (2011); 2Data reproduced from Floriani et al. (2010); 3Maximum experimental uncertainties equal to 0.30%; db is on a dry basis; n.d. is not determined; 4Data reproduced from Llorente & García

It was observed that the main element found in the sludge ash was phosphorus, followed by iron. This is considered a problem because P forms compounds with lower melting tempera‐ ture, which may have influenced the results presented in Table 3. As expected, the mixture

**Units SD1 LFP1 LFPSD1:92**

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715

and its utilization is recommended in low blending proportions.

Ash composition3

Ash melting temperatures

(2005) for eucalyptus sample

**Table 3.** Biomass ash properties


1Data reproduced from Virmond et al. (2011); 2Data reproduced from Floriani et al. (2010); 3Maximum experimental uncertainties equal to 0.30%; db is on a Dry Basis; daf is on a Dry and Ash Free basis; \*Value previously presented by Floriani et al. (2010) corrected; n.d. is Not Determined; LHV is Lower Heating Value

**Table 2.** Biomass properties

In previous publications (Floriani et al., 2010; Virmond et al., 2008, 2011), the authors have addressed the effects of the LFP ash composition on the fouling and slagging tendency in the combustion systems, showing that the occurrence of this problem can be reduced when burning a mixture of the biosolids with wood residues such as SD compared to LFP alone.

As shown in Table 3, the ash melting temperatures of LFP are much lower than the values estimated for LFPSD1:9 through mass balance analysis considering a homogeneous mixture, and its utilization is recommended in low blending proportions.


1Data reproduced from Virmond et al. (2011); 2Data reproduced from Floriani et al. (2010); 3Maximum experimental uncertainties equal to 0.30%; db is on a dry basis; n.d. is not determined; 4Data reproduced from Llorente & García (2005) for eucalyptus sample

**Table 3.** Biomass ash properties

content of greases was also measured in the LFP composition (34.39 wt%, raw) and it con‐ tributes considerably to the high energy content of the LFP (LHV of 25.77 MJ kg-1, daf). The presence of chlorine in the biomass (0.18 wt%) occurs due to the utilization of chlorine-based products for hygiene purposes at the plant and is incorporated into the wastewater as well as into the remaining biosolids (LFP). The nitrogen content of the fuel mixture LFPSD1:9 (1.36 wt%), even though much lower than the concentration found in LFP, can still cause problems in terms of NOx emission during its combustion. The variability of components present in the biomass is mainly due to the chemical compounds used as ingredients during meat processing operations, especially salts and additives. The sulfur content in LFP is mainly due to the conversion of sulfur-containing proteins, but some may remain from the

Ash (wt%, db) 0.43 12.30 1.75 Moisture (wt%, raw) 19.97 15.00 50.23 Volatiles (wt%, daf) 79.78 85.29 83.08 Fixed carbon (wt%, daf) 20.22 9.58 17.01

Carbon (wt%, daf) 55.30 58.04 51.06 Hydrogen (wt%, daf) 7.14 9.01 6.64 Nitrogen (wt%, daf) 0.21 9.24 1.36 Sulfur (wt%, daf) < 0.01 0.34 0.03\* Oxygen (wt%, daf) 37.34 22.68 40.94 Chlorine (wt%, daf) < 0.01 0.18 < 0.01 Fluorine (wt%, daf) < 0.20 < 0.20 n.d. Phosphorus (wt%, daf) 0.01 1.03 n.d.

LHV (MJ kg-1, daf) 16.62 25.77 20.31 LHV (MJ kg-1, raw) 16.55 22.60 19.76

1Data reproduced from Virmond et al. (2011); 2Data reproduced from Floriani et al. (2010); 3Maximum experimental uncertainties equal to 0.30%; db is on a Dry Basis; daf is on a Dry and Ash Free basis; \*Value previously presented by

Floriani et al. (2010) corrected; n.d. is Not Determined; LHV is Lower Heating Value

**Units SD1 LFP1 LFPSD1:92**

precipitation agent used in the wastewater treatment (ferric sulfate).

Proximate analysis3

714 Food Industry

Ultimate analysis3

Lower Heating Value3

**Table 2.** Biomass properties

It was observed that the main element found in the sludge ash was phosphorus, followed by iron. This is considered a problem because P forms compounds with lower melting tempera‐ ture, which may have influenced the results presented in Table 3. As expected, the mixture of biomasses maintained a relatively high ash melting temperature, which is a desirable as‐ pect when considering the combustion of solid fuels. Additionally, the design of the equip‐ ment and the definition of the operating conditions are extremely important to control, or even avoid, the occurrence of such problems.

transfer of contaminants into the food chain. Inorganic and organic pollutants not removed during physicochemical wastewater treatment processes are either bio-chemically degraded or adsorbed by the sludge. The characterization of the sludge was reported by de Sena et al. (2009), where the trace metal, PAH, PCB and PCDD/PCDF concentrations in the WWTP sludge were determined. Trace metals might end up in the effluent from the meat process‐ ing plant through sources like equipment, sanitizers and cleaning agents, as well as equip‐ ment and pumps used in the wastewater treatment plant itself. Also, some metals such as arsenic, copper and zinc are occasionally added to animal feed as mineral food supplements and/or as growth promoters (US EPA, 2004). The group of PAHs, generated undesirably mostly during manifold incomplete incineration processes, includes numerous compounds with three or more condensed aromatic rings. PCBs synthesized for specific applications as non-inflammable insulators, hydrolic liquids and plasticizers are pollutants which today are ubiquitously found in the environment, although they were phased out from production worldwide at the end of the 1970s. PCDDs/PCDFs are not intentionally produced by hu‐ mans but they are released into the atmosphere as sub-products of incineration and combus‐ tion processes, both domestic and industrial, when carbon, hydrogen, chlorine and oxygen together with copper as a catalyst are present. The incineration of municipal or clinical wastes, iron ore sinter plants and non-ferrous metal industries (Quass et al., 2000) as well as the chemical synthesis of chlorophenols and electrolysis of sodium chloride are sources of PCDDs/PCDFs. These compounds accumulate in sludge due to their extreme lipophilicity, and it is very difficult to assess the various sources of these compounds and their pathways into the environment and into the food chain (Klöpffer, 1996). Tables 4, 5 and 6 show the results of the biomass characterization, including 3 (three) types of sludge (BS) collected at different points in the WWTP. BSFlot refers to the sludge remaining after the flotation proc‐ ess, BSCent to the sludge remaining after the three-phase centrifugation, and BSBiol to the sludge collected from the activated sludge bioreactor (not primarily intended for combus‐

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**Compounds Concentration (µg kg-1, db)**

Naphthalene (Nap) - 110.0 < 40.0 < 30.0

Acenaphthylene (Acy) - 84.0 < 30.0 < 30.0

Acenaphtene (Ace) - < 7.0 < 7.0 < 6.0

Fluorene (Flu) 0.001 20.0 < 7.0 < 6.0

Phenanthrene (Phe) 0.001 84.0 < 8.0 < 7.0

Anthracene (Ant) - < 2.0 8.0 8.0

**TEF1 Limit2 BSFlot BSCent BSBiol**

tion purposes).

Polycyclic Aromatic Hydrocarbons (PAHs)


db is Dry Basis; 1Upper limit of pollution for the disposal of sewage sludge in the environment (EU, 2000); \* Trace ele‐ ments, biologically essential in small quantities. Reproduced from de Sena et al. (2009)

**Table 4.** Results for the determination of trace metals and nutrients in the sludge samples

Besides the determination of the biomass properties for biofuel applications, the organic and inorganic contents of the sludge generated from the WWTP were characterized, since it is necessary to assure that sludge containing high pollutant loads is not applied as fertilizer, in order to avoid contamination of agricultural soil and cultivated plants, *i.e.*, to avoid the of biomasses maintained a relatively high ash melting temperature, which is a desirable as‐ pect when considering the combustion of solid fuels. Additionally, the design of the equip‐ ment and the definition of the operating conditions are extremely important to control, or

**Concentration (mg kg-1, db)**

Hg 5 < 0.50 < 0.50 < 0.50 Cd 5 < 0.50 < 0.50 0.64 Cr 800 6.7 28.4 26.7 Cu\* 800 16.2 29.8 182.1 Ni 200 1.9 9.9 22.0 Pb 500 1.3 3.4 6.1 Zn\* 2000 88.2 183.8 1090.3 As 75 0.57 < 0.50 < 0.50 Mo\* 75 0.50 1.7 4.4 Co\* 5 < 0.50 < 0.50 4.1

K - 427 599 6903 Fe - 9360 25600 20900 Al - 1750 498 3420 P - 6350 15900 28400

Ca - 1520 5080 18600 Mg - 148 259 7185 S - 3140 6630 9810

Besides the determination of the biomass properties for biofuel applications, the organic and inorganic contents of the sludge generated from the WWTP were characterized, since it is necessary to assure that sludge containing high pollutant loads is not applied as fertilizer, in order to avoid contamination of agricultural soil and cultivated plants, *i.e.*, to avoid the

db is Dry Basis; 1Upper limit of pollution for the disposal of sewage sludge in the environment (EU, 2000); \*

ments, biologically essential in small quantities. Reproduced from de Sena et al. (2009)

**Table 4.** Results for the determination of trace metals and nutrients in the sludge samples

**Limit1 BSFlot BSCent BSBiol**

Trace ele‐

even avoid, the occurrence of such problems.

Trace metal

716 Food Industry

Micronutrient

Secondary nutrients

transfer of contaminants into the food chain. Inorganic and organic pollutants not removed during physicochemical wastewater treatment processes are either bio-chemically degraded or adsorbed by the sludge. The characterization of the sludge was reported by de Sena et al. (2009), where the trace metal, PAH, PCB and PCDD/PCDF concentrations in the WWTP sludge were determined. Trace metals might end up in the effluent from the meat process‐ ing plant through sources like equipment, sanitizers and cleaning agents, as well as equip‐ ment and pumps used in the wastewater treatment plant itself. Also, some metals such as arsenic, copper and zinc are occasionally added to animal feed as mineral food supplements and/or as growth promoters (US EPA, 2004). The group of PAHs, generated undesirably mostly during manifold incomplete incineration processes, includes numerous compounds with three or more condensed aromatic rings. PCBs synthesized for specific applications as non-inflammable insulators, hydrolic liquids and plasticizers are pollutants which today are ubiquitously found in the environment, although they were phased out from production worldwide at the end of the 1970s. PCDDs/PCDFs are not intentionally produced by hu‐ mans but they are released into the atmosphere as sub-products of incineration and combus‐ tion processes, both domestic and industrial, when carbon, hydrogen, chlorine and oxygen together with copper as a catalyst are present. The incineration of municipal or clinical wastes, iron ore sinter plants and non-ferrous metal industries (Quass et al., 2000) as well as the chemical synthesis of chlorophenols and electrolysis of sodium chloride are sources of PCDDs/PCDFs. These compounds accumulate in sludge due to their extreme lipophilicity, and it is very difficult to assess the various sources of these compounds and their pathways into the environment and into the food chain (Klöpffer, 1996). Tables 4, 5 and 6 show the results of the biomass characterization, including 3 (three) types of sludge (BS) collected at different points in the WWTP. BSFlot refers to the sludge remaining after the flotation proc‐ ess, BSCent to the sludge remaining after the three-phase centrifugation, and BSBiol to the sludge collected from the activated sludge bioreactor (not primarily intended for combus‐ tion purposes).


#### 718 Food Industry


**Concentration (ng kg-1, db)**

2,3,7,8 – TCDD2 1.0 0.1 0.4 0.4

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

1,2,3,7,8 - PeCDD 1.0 0.6 1.3 2.2 1,2,3,4,7,8 - HxCDD 0.1 0.3 1.5 1.7 1,2,3,7,8,9 - HxCDD 0.1 0.2 1.9 3.3 1,2,3,6,7,8 - HxCDD 0.1 0.7 1.3 1.8 1,2,3,4,6,7,8 - HpCDD 0.01 0.8 4.2 4.6 OCDD 0.0003 2.1 21.1 23.1 ∑ PCDD - 4.8 31.7 37.1

2,3,7,8 – TCDF 0.1 0.2 0.3 1.3 2,3,4,7,8 – PeCDF 0.3 0.5 2.1 2.1 1,2,3,7,8 – PeCDF 0.03 0.7 1.5 3.8 1,2,3,4,7,8 – HxCDF 0.1 0.6 1.2 2.0 1,2,3,6,7,8 – HxCDF 0.1 0.6 1.6 2.3 1,2,3,7,8,9 – HxCDF 0.1 1.7 2.9 3.1 2,3,4,6,7,8 - HxCDF 0.1 0.7 1.9 3.8 1,2,3,4,6,7,8 - HpCDF 0.01 2.6 4.2 5.3 1,2,3,4,7,8,9 – HpCDF 0.01 1.4 3.1 3.6 OCDF 0.0003 2.1 4.4 10.2 ∑ PCDF - 11.1 23.2 37.3 PCDD:PCDF Ratio - 0.43 1.37 0.98

∑ TEF PCDD/PCDF 100\* 1.4 3.8 5.4

db is Dry Basis; 1TEF for dioxins and dioxin-like compounds (van den Berg et al., 2006; WHO, 2005); <sup>2</sup>Isomer with high‐

**Table 6.** TEF and concentrations of PCDDs/PCDFs in the sludge samples

TEF (ng kg-1) limit for solid disposal onto soil (EU, 2001). Reproduced from de Sena et al. (2009)

Polychlorinated dibenzo-p-dioxins (PCDD)

Polychlorinated dibenzofurans (PCDF)

est acute toxicity; \*

**TEF1 BSFlot BSCent BSBiol**

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db is Dry Basis; 1TEF for dioxin and dioxin-like compounds (Nisbet et al., 1992; van den Berg et al., 2006); 2Limit for solid disposal onto soil (EU, 2001); 3Carcinogenic isomers; 4Isomers of PAH with TEF comparable to the most toxic poly‐ chlorinated dibenzo-dioxins and -furans; \* Isomer of PCB with highest TEF; LOQ is Limit of Quantification. Reproduced from de Sena et al. (2009)

**Table 5.** Results for the determination of PAHs and PCBs in the sludge samples


db is Dry Basis; 1TEF for dioxins and dioxin-like compounds (van den Berg et al., 2006; WHO, 2005); <sup>2</sup>Isomer with high‐ est acute toxicity; \* TEF (ng kg-1) limit for solid disposal onto soil (EU, 2001). Reproduced from de Sena et al. (2009)

**Table 6.** TEF and concentrations of PCDDs/PCDFs in the sludge samples

**Compounds Concentration (µg kg-1, db)**

Fluoranthene (Fla) 0.001 320.0 510.0 < 10.0

Pyrene (Pyr) 0.001 97.0 72.0 11.0

Chrysene (Cry)3 0.01 92.0 < 1.0 5.0

∑ PAHLMW - 816.0 616.0 113.0

Benzo[a]anthracene (BaA)<sup>3</sup> 0.1 24.0 < 1.0 4.0

Benzo[b]fluoranthene (BbF)3 0.1 38.0 25.0 < 3.0

Benzo[k]fluoranthene (BkF)3 0.1 11.0 < 1.0 < 1.0

Benzo[a]pyrene (BaP)3,4 1.0 2.0 < 1.0 5.0

Dibenzo[a,h]anthracene (DbA)3,4 5.0 < 4.0 < 4.0 < 4.0

Benzo[g,h,i]perylene (BgP) 0.1 12.0 < 6.0 < 6.0

Indeno[1,2,3-cd]pyrene (InD)3 0.1 < 10.0 < 10.0 < 10.0

∑ PAHHMW - 101.0 48.0 33.0

∑ PAH ≤ 6000 917.0 664.0 146.0

∑ TEFPAH - 11.0 3.0 6.0

PCB 105, 114, 118, 123, 156, 167, 189 < 0.005 < LOQ < LOQ < LOQ

∑ PCB - ≤ 800 < LOQ < LOQ < LOQ

db is Dry Basis; 1TEF for dioxin and dioxin-like compounds (Nisbet et al., 1992; van den Berg et al., 2006); 2Limit for solid disposal onto soil (EU, 2001); 3Carcinogenic isomers; 4Isomers of PAH with TEF comparable to the most toxic poly‐

, 169 < 0.1 < LOQ < LOQ < LOQ

Isomer of PCB with highest TEF; LOQ is Limit of Quantification. Reproduced

Polychlorinated Biphenyls (PCB)

chlorinated dibenzo-dioxins and -furans; \*

**Table 5.** Results for the determination of PAHs and PCBs in the sludge samples

from de Sena et al. (2009)

PCB non-ortho

718 Food Industry

PCB 77, 81, 126\*

PCB mono-ortho

**TEF1 Limit2 BSFlot BSCent BSBiol**

A study by de Sena et al. (2009) verified low pollution loads for the sludge (BS) originating from the WWTP, with respect to the most relevant inorganic and organic priority pollutants as monitored by the US EPA, at the case study meat processing plant located in the south of Brazil. Although other pollutants such as veterinary drugs, pesticides and surfactants were not investigated in this first analytical approach, they are of high concern. However, this study was a preliminary report for future monitoring of other food processing segments lo‐ cated in different regions of Brazil.

rocating-grate coupled to a boiler at the meat processing plant with the capacity to process

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Grate firing is one of the main technologies that are currently used for biomass combustion aiming at heat and power production. Grate-fired boilers can fire a wide range of fuels with varying moisture content and show great potential in biomass combustion (Goërner, 2003). The plant-scale furnace was operated at a fuel feed rate of 2604 kg h-1 (moisture content of approximately 50 wt%) at 900 °C, with 59% excess air and without gas recirculation. The combustion test lasted for approximately 2 h after the system had reached steady state.

In the pilot-scale plant the combustion of SD was carried out at a fuel feed rate of 32 kg h-1 (moisture content of 9.16 wt%), with gas recirculation of 20% at an average temperature of 642 °C in a cyclone combustor (Drako, Albrecht, Brazil), which has been described by Vir‐ mond et al. (2011). The average temperature at the front stage of the combustor was 1052 °C and at the outlet it was 1024 °C, and an air-to-fuel (A/F) ratio of 9.08 (theoretical A/F ratio of 7.23 based on the fuel composition) was used. For the LFP combustion test, the conditions applied to the cyclone combustor were: fuel feed rate of 43 kg h-1 (moisture content of 11.44 wt%), with gas recirculation of 20% at an average temperature of 800 °C. The average tem‐ perature at the front stage of the combustor was 868 °C, at the outlet of the combustor it was 1080 °C, and the A/F ratio was 11.82 (theoretical A/F ratio of 7.76 based on the fuel composi‐ tion). CO, O2, SO2, CxHy (measured as CH4), NO, and NO2 emissions were measured using a Greenline MK2 (Eurotron) analyzer and BTEX emission measurements were based on the adsorption and desorption of gases which were analyzed by gas chromatography. Emis‐ sions of BTEX were expressed as Total Organic Carbon (TOC). The detailed methodology for emissions sampling and analysis during the combustion tests, as well as the complete set of results, have been previously reported by Floriani et al. (2010) and Virmond et al. (2007, 2008) for LFPSD1:9 combustion, and by Virmond et al. (2011) for SD and LFP. Thus, only the main points are highlighted herein. The gaseous emissions observed in the combustion tests and the respective regulation limits were corrected to the reference oxygen content (O2ref) of

Since no data on the combustion of meat processing or slaughterhouse wastes had been previ‐ ously published, no comparison was possible. However, the results for the contaminants re‐ ported were compared with the emission limits established by national and international environmental agencies, such as the Brazilian guidelines issued by The National Council of the Environment (CONAMA, 2002) for gaseous emissions in the thermal treatment of wastes; the American guidelines issued by the US Environmental Protection Agency (US EPA, 2002) for emissions from commercial and industrial solid waste incineration units; and the German Guidelines 17.BlmSchV (17.BlmSchV, 2003) for emissions from biomass combustion and from biomass co-combustion. Concerning the combustion tests performed in the pilot-scale cyclone combustor with SD and LFP as fuels, the emissions of CO, CO2, CxHy and TOC were well con‐ trolled and their concentrations remained below the regulation limits considered for both bio‐ masses, except CO in the SD combustion test in relation to the German guidelines, which refer

to waste incineration and are stricter than the other regulations.

12000 kg h-1, as reported by Virmond (2007).

7% and are given in Table 7.

### **4.2. Biomass combustion**

Co-combustion of agro-industrial residues in thermal power plants is not necessarily a low cost alternative for the thermal treatment of wastes. There is the possibility of interaction be‐ tween the components and the main fuels in such a way that either the operating behavior of the conversion system is improved or the emissions are reduced (Werther, 2007). The emission of pollutants generated during combustion is strongly related to the biomass prop‐ erties. Pollutant formation mechanisms and many other parameters related to the combus‐ tion process must be monitored due to the formation of highly problematic compounds such as NOx, SO2, benzene, toluene, ethyl-benzene, and (o-,m-,p-)xylenes (BTEX), polycyclic aro‐ matic hydrocarbons (PAH), polychlorinated dibenzo-p-dioxins and polychlorinated diben‐ zofurans (PCDD/PCDF) (Chagger et al., 1998; Kumar et al., 2002; Mckay, 2002; Stanmore, 2004; Watanabe et al., 2004), and have to be controlled in order to comply with the stringent limits set by recent environmental legislation. Chlorine-associated, high-temperature corro‐ sion and the potential corrosion problems associated with burning biomass fuels have been previously discussed (Nielsen et al., 2000). Fuel nitrogen can be a problem in terms of NOx emissions. The conversion of nitrogen in systems fired by solid fuels (mainly coal, but also biomass) has been reviewed in detail, as well as the combustion characteristics of different biomass fuels, the potential applications of renewable energy sources as the prime energy sources in various countries, and the problems associated with biomass combustion in boiler systems (Demirbas, 2004; Werther, 2000).

The pollutant emissions due to incomplete biomass combustion can be effectively controlled by an optimized combustion process, *i.e.*, enhanced mixing, sufficient residence time at high temperatures (>850 °C), and low total excess air (Demirbas, 2005), as well as the appropriate choice of the combustion device.

Given the higher energy value of the biosolids (LHV equal to 22.60 MJ kg-1) compared to sawdust (LHV equal to 16.55 MJ kg-1), as shown in Table 2, the substitution of 10 wt% of sawdust with this residue can increase the thermal energy production by approximately 4% compared to the combustion of sawdust alone, leading to a sawdust saving of 1950 ton per year, besides the economic benefits related to reduced landfill disposal. However, the gas‐ eous emissions have to be monitored so as not to infringe current legislations.

The evaluation of the feasibility of the utilization of the biosolids originating from the WWTP studied was performed through combustion testing of the biosolids as the sole fuel in a pilot-scale cyclone combustor (model Drako, Albrecht, Brazil) with a burning capacity of 100 kg h-1, as described by Virmond et al. (2011), and in a furnace equipped with a recip‐ rocating-grate coupled to a boiler at the meat processing plant with the capacity to process 12000 kg h-1, as reported by Virmond (2007).

A study by de Sena et al. (2009) verified low pollution loads for the sludge (BS) originating from the WWTP, with respect to the most relevant inorganic and organic priority pollutants as monitored by the US EPA, at the case study meat processing plant located in the south of Brazil. Although other pollutants such as veterinary drugs, pesticides and surfactants were not investigated in this first analytical approach, they are of high concern. However, this study was a preliminary report for future monitoring of other food processing segments lo‐

Co-combustion of agro-industrial residues in thermal power plants is not necessarily a low cost alternative for the thermal treatment of wastes. There is the possibility of interaction be‐ tween the components and the main fuels in such a way that either the operating behavior of the conversion system is improved or the emissions are reduced (Werther, 2007). The emission of pollutants generated during combustion is strongly related to the biomass prop‐ erties. Pollutant formation mechanisms and many other parameters related to the combus‐ tion process must be monitored due to the formation of highly problematic compounds such as NOx, SO2, benzene, toluene, ethyl-benzene, and (o-,m-,p-)xylenes (BTEX), polycyclic aro‐ matic hydrocarbons (PAH), polychlorinated dibenzo-p-dioxins and polychlorinated diben‐ zofurans (PCDD/PCDF) (Chagger et al., 1998; Kumar et al., 2002; Mckay, 2002; Stanmore, 2004; Watanabe et al., 2004), and have to be controlled in order to comply with the stringent limits set by recent environmental legislation. Chlorine-associated, high-temperature corro‐ sion and the potential corrosion problems associated with burning biomass fuels have been previously discussed (Nielsen et al., 2000). Fuel nitrogen can be a problem in terms of NOx emissions. The conversion of nitrogen in systems fired by solid fuels (mainly coal, but also biomass) has been reviewed in detail, as well as the combustion characteristics of different biomass fuels, the potential applications of renewable energy sources as the prime energy sources in various countries, and the problems associated with biomass combustion in boiler

The pollutant emissions due to incomplete biomass combustion can be effectively controlled by an optimized combustion process, *i.e.*, enhanced mixing, sufficient residence time at high temperatures (>850 °C), and low total excess air (Demirbas, 2005), as well as the appropriate

Given the higher energy value of the biosolids (LHV equal to 22.60 MJ kg-1) compared to sawdust (LHV equal to 16.55 MJ kg-1), as shown in Table 2, the substitution of 10 wt% of sawdust with this residue can increase the thermal energy production by approximately 4% compared to the combustion of sawdust alone, leading to a sawdust saving of 1950 ton per year, besides the economic benefits related to reduced landfill disposal. However, the gas‐

The evaluation of the feasibility of the utilization of the biosolids originating from the WWTP studied was performed through combustion testing of the biosolids as the sole fuel in a pilot-scale cyclone combustor (model Drako, Albrecht, Brazil) with a burning capacity of 100 kg h-1, as described by Virmond et al. (2011), and in a furnace equipped with a recip‐

eous emissions have to be monitored so as not to infringe current legislations.

cated in different regions of Brazil.

systems (Demirbas, 2004; Werther, 2000).

choice of the combustion device.

**4.2. Biomass combustion**

720 Food Industry

Grate firing is one of the main technologies that are currently used for biomass combustion aiming at heat and power production. Grate-fired boilers can fire a wide range of fuels with varying moisture content and show great potential in biomass combustion (Goërner, 2003). The plant-scale furnace was operated at a fuel feed rate of 2604 kg h-1 (moisture content of approximately 50 wt%) at 900 °C, with 59% excess air and without gas recirculation. The combustion test lasted for approximately 2 h after the system had reached steady state.

In the pilot-scale plant the combustion of SD was carried out at a fuel feed rate of 32 kg h-1 (moisture content of 9.16 wt%), with gas recirculation of 20% at an average temperature of 642 °C in a cyclone combustor (Drako, Albrecht, Brazil), which has been described by Vir‐ mond et al. (2011). The average temperature at the front stage of the combustor was 1052 °C and at the outlet it was 1024 °C, and an air-to-fuel (A/F) ratio of 9.08 (theoretical A/F ratio of 7.23 based on the fuel composition) was used. For the LFP combustion test, the conditions applied to the cyclone combustor were: fuel feed rate of 43 kg h-1 (moisture content of 11.44 wt%), with gas recirculation of 20% at an average temperature of 800 °C. The average tem‐ perature at the front stage of the combustor was 868 °C, at the outlet of the combustor it was 1080 °C, and the A/F ratio was 11.82 (theoretical A/F ratio of 7.76 based on the fuel composi‐ tion). CO, O2, SO2, CxHy (measured as CH4), NO, and NO2 emissions were measured using a Greenline MK2 (Eurotron) analyzer and BTEX emission measurements were based on the adsorption and desorption of gases which were analyzed by gas chromatography. Emis‐ sions of BTEX were expressed as Total Organic Carbon (TOC). The detailed methodology for emissions sampling and analysis during the combustion tests, as well as the complete set of results, have been previously reported by Floriani et al. (2010) and Virmond et al. (2007, 2008) for LFPSD1:9 combustion, and by Virmond et al. (2011) for SD and LFP. Thus, only the main points are highlighted herein. The gaseous emissions observed in the combustion tests and the respective regulation limits were corrected to the reference oxygen content (O2ref) of 7% and are given in Table 7.

Since no data on the combustion of meat processing or slaughterhouse wastes had been previ‐ ously published, no comparison was possible. However, the results for the contaminants re‐ ported were compared with the emission limits established by national and international environmental agencies, such as the Brazilian guidelines issued by The National Council of the Environment (CONAMA, 2002) for gaseous emissions in the thermal treatment of wastes; the American guidelines issued by the US Environmental Protection Agency (US EPA, 2002) for emissions from commercial and industrial solid waste incineration units; and the German Guidelines 17.BlmSchV (17.BlmSchV, 2003) for emissions from biomass combustion and from biomass co-combustion. Concerning the combustion tests performed in the pilot-scale cyclone combustor with SD and LFP as fuels, the emissions of CO, CO2, CxHy and TOC were well con‐ trolled and their concentrations remained below the regulation limits considered for both bio‐ masses, except CO in the SD combustion test in relation to the German guidelines, which refer to waste incineration and are stricter than the other regulations.


to the fact that wood and wood-based materials are extensively used as fuel for thermal en‐ ergy generation in the Brazilian food industry. Chlorine, PAHs and PCBs are among the ele‐ ments or compounds that must be studied in greater depth as they are precursors to the

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

Industrial solid wastes must be disposed of safely, and co-firing them with SD has been shown in other studies by the authors, which are currently underway, to be profitable using the same pilot-scale cyclone combustor and different biomasses. The advantages are both a reduction in the consumption of primary fuels and the recovering of energy from wastes in‐ side the plant, which would normally be disposed of in landfills, potentially causing envi‐

During this study, only preliminary tests were performed, such as the determination of the chemical composition of the biogas and the exhaust gases when the biogas was burned. Measurements were performed at several partner pig farms close to the case study plant that rear pigs from 45 to 110 days of life. At these farms there were relatively small horizon‐

without previous treatment. The hydraulic retention time was approximately 30 days and

Table 8 shows the average chemical composition and calorific values of the biogas. To ana‐ lyze the composition of biogas, a biogas analysis kit was used (Alfakit, Brazil) which is

CH4 (v/v%) 45-65 57 CO2 (v/v%) 35-55 34 H2S (v/v%) >1020 - CH4/CO2 0.82-1.86 1.7 HHV (kJ Nm-3) 17996-25995 *-* LHV(kJ Nm-3) 16200-23400 *-*

At the time this study was completed the farms were burning only biogas to avoid harmful emissions and to provide a better disposal/reuse options for the waste. At all farms there were simple flares to burn the gas, and thus the gaseous emissions were evaluated. CO, SO2, NO, NO2, O2, and CxHy were measured using a Greenline MK2 (Eurotron) analyzer and the sampling point was located at the top of the chimney. Results are not presented in this docu‐

1Data reproduced from Silva et al. (2005); HHV is Higher Heating Value; LHV is Lower Heating Value

) in which the input consisted only in pig wastes

http://dx.doi.org/10.5772/53163

723

**Average chemical composition Reference values1**

formation of dioxins and partly of furans.

**4.3. Biogas production and combustion**

tal-type biodigestors (approximately 450 m3

d-1.

ronmental problems.

the entrance flow 8 m3

based on colorimetric methods.

**Table 8.** Average chemical composition of biogas

1NOx expressed in terms of NO2; TOC is Total Organic Carbon; 2Data from Virmond et al. (2011); 3Data from Floriani et al. (2010) and Virmond et al. (2007, 2008); 4CONAMA 316/02, thermal treatment of wastes (CONAMA, 2002); n.a. is Not Applicable; 5US EPA, solid waste incineration (US EPA, 2000); 617.BlmSchV 24 h, <50 MW, co-combustion of wastes (17.BlmSchV, 2003); 717.BlmSchV 24 h, direct combustion of wastes (17.BlmSchV, 2003)

**Table 7.** Gaseous emissions from the combustion tests at O2ref=7%

The effect of the biomass composition on gaseous emissions was clearly observed, especially considering the N and S fuel contents in LFP, which led to concentrations of these pollutants being higher than the established limits.

The use of the biosolids originating from the meat processing plant investigated in this study as a fuel in the pilot cyclone combustor was shown to be feasible; however, further research is required concerning the control of SO2 and NOx emissions to avoid exceeding the very strict emission limits as well as the occurrence of fouling and slagging.

In relation to the combustion test performed with the mixture of SD and LFP (LFPSD1:9), the high levels of CxHy and CO emitted indicate incomplete combustion. This can be attrib‐ uted to the high moisture content of the biomass (50.23 wt%, as shown in Table 2), the lower combustion temperature (approximately 900 °C) compared to the other two tests performed in the pilot-scale combustor (approximately 1000 °C) and the absence of gas recirculation. Additionally, the control of the operating conditions of the large-scale plant is more difficult to achieve, due to the restricted testing time or minimal variation from the normal operation with the SD. Firing a biomass with low moisture content and flue gas recirculation could provide better oxidation conditions. Due to the lower nitrogen concentration found in LFPS1:9 compared to LFP, as well as to the low operating combustion temperature, NOx emissions remained below the limits established by CONAMA and US EPA.

The co-combustion of LFP and SD with lower-N fuel content reduced the NOx in the gas‐ eous emissions compared to the burning of LFP alone. In fact, this option is the most feasible in Brazil considering the relatively high NOx emissions related to both the fuel nitrogen and to the fact that wood and wood-based materials are extensively used as fuel for thermal en‐ ergy generation in the Brazilian food industry. Chlorine, PAHs and PCBs are among the ele‐ ments or compounds that must be studied in greater depth as they are precursors to the formation of dioxins and partly of furans.

Industrial solid wastes must be disposed of safely, and co-firing them with SD has been shown in other studies by the authors, which are currently underway, to be profitable using the same pilot-scale cyclone combustor and different biomasses. The advantages are both a reduction in the consumption of primary fuels and the recovering of energy from wastes in‐ side the plant, which would normally be disposed of in landfills, potentially causing envi‐ ronmental problems.

## **4.3. Biogas production and combustion**

**CO**

±21.97

±10.30

±12.39

wastes (17.BlmSchV, 2003); 717.BlmSchV 24 h, direct combustion of wastes (17.BlmSchV, 2003)

very strict emission limits as well as the occurrence of fouling and slagging.

emissions remained below the limits established by CONAMA and US EPA.

**Table 7.** Gaseous emissions from the combustion tests at O2ref=7%

being higher than the established limits.

**CO2 (%)**

10.32 ±0.03

10.33 ±0.05

10.39 ±0.02

*CONAMA* <sup>4</sup> *124.88 n.a. n.a. 560.00 280.00 n.a. US EPA* <sup>5</sup> *196.16 n.a. n.a. 796.02 57.09 n.a. 17.BlmSchV (24 h; <50 MW)* <sup>6</sup> *140.00 n.a. n.a. 373.33 186.67 9.33 17.BlmSchV (24 h)7 70.00 n.a. n.a. 280.00 70.00 14.00*

1NOx expressed in terms of NO2; TOC is Total Organic Carbon; 2Data from Virmond et al. (2011); 3Data from Floriani et al. (2010) and Virmond et al. (2007, 2008); 4CONAMA 316/02, thermal treatment of wastes (CONAMA, 2002); n.a. is Not Applicable; 5US EPA, solid waste incineration (US EPA, 2000); 617.BlmSchV 24 h, <50 MW, co-combustion of

The effect of the biomass composition on gaseous emissions was clearly observed, especially considering the N and S fuel contents in LFP, which led to concentrations of these pollutants

The use of the biosolids originating from the meat processing plant investigated in this study as a fuel in the pilot cyclone combustor was shown to be feasible; however, further research is required concerning the control of SO2 and NOx emissions to avoid exceeding the

In relation to the combustion test performed with the mixture of SD and LFP (LFPSD1:9), the high levels of CxHy and CO emitted indicate incomplete combustion. This can be attrib‐ uted to the high moisture content of the biomass (50.23 wt%, as shown in Table 2), the lower combustion temperature (approximately 900 °C) compared to the other two tests performed in the pilot-scale combustor (approximately 1000 °C) and the absence of gas recirculation. Additionally, the control of the operating conditions of the large-scale plant is more difficult to achieve, due to the restricted testing time or minimal variation from the normal operation with the SD. Firing a biomass with low moisture content and flue gas recirculation could provide better oxidation conditions. Due to the lower nitrogen concentration found in LFPS1:9 compared to LFP, as well as to the low operating combustion temperature, NOx

The co-combustion of LFP and SD with lower-N fuel content reduced the NOx in the gas‐ eous emissions compared to the burning of LFP alone. In fact, this option is the most feasible in Brazil considering the relatively high NOx emissions related to both the fuel nitrogen and

**CxHy (mg Nm- ³)**

> 0.00 ±0.00

> 0.00 ±0.00

554.44 ±7.91 **NOx 1**

241.58 ±26.31

1727.43 ±229.93

> 497.94 ±19.04

**SO2 (mg Nm- ³)**

> 0.00 ±0.00

363.54 ±90.80

128.69 ±4.31

**TOC (mg Nm- ³)**

> 1.27 ±0.57

> 1.23 ±0.12

> 1.72 ±0.83

**(mg Nm- ³)**

**(mg Nm- ³)**

SD biomass2 93.58

722 Food Industry

LFP biomass2 63.33

LFPSD1:9 biomass3 734.83

During this study, only preliminary tests were performed, such as the determination of the chemical composition of the biogas and the exhaust gases when the biogas was burned. Measurements were performed at several partner pig farms close to the case study plant that rear pigs from 45 to 110 days of life. At these farms there were relatively small horizon‐ tal-type biodigestors (approximately 450 m3 ) in which the input consisted only in pig wastes without previous treatment. The hydraulic retention time was approximately 30 days and the entrance flow 8 m3 d-1.

Table 8 shows the average chemical composition and calorific values of the biogas. To ana‐ lyze the composition of biogas, a biogas analysis kit was used (Alfakit, Brazil) which is based on colorimetric methods.


1Data reproduced from Silva et al. (2005); HHV is Higher Heating Value; LHV is Lower Heating Value

#### **Table 8.** Average chemical composition of biogas

At the time this study was completed the farms were burning only biogas to avoid harmful emissions and to provide a better disposal/reuse options for the waste. At all farms there were simple flares to burn the gas, and thus the gaseous emissions were evaluated. CO, SO2, NO, NO2, O2, and CxHy were measured using a Greenline MK2 (Eurotron) analyzer and the sampling point was located at the top of the chimney. Results are not presented in this docu‐ ment because each burner presented different burning efficiencies and they were still in the adjustment phase. However, by the end of the project, all gaseous emissions were below the limits imposed by Brazilian Legislation. The SO2 requires greater caution due to the pres‐ ence of H2S and therefore a pre-treatment has to be considered before the process can be considered adequate. H2S can easily react with iron oxides and hydroxides, requiring the presence of water, and this can thus be considered a good method to remove the H2S from biogas (Zichari, 2003).

TiO2/H2O2 could be carried out in terms of their effectiveness in the treatment of slaughter‐ house secondary effluent. Hence, the most important consideration to be evaluated is which treatment can ensure that the standards and limits set by legislation are achieved, thus avoiding undesirable impact on the environment (such as the discharge of persistent organic

Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

http://dx.doi.org/10.5772/53163

725

Regarding the solid wastes, the substitution of 10 wt% of the sawdust with the biosolids originating from the physicochemical wastewater treatment can increase the thermal energy production by approximately 4% compared to the combustion of sawdust alone, leading to an economy of 1950 tons per year of sawdust besides providing savings in relation to land‐ fill disposal. Additionally, co-combustion is the most feasible option for energy recovery from this waste in Brazil, making it possible to control the burning process, to avoid the oc‐ currence the fouling and slagging and to meet the emission limits established in the relevant legislation. Considering that wood and wood-based materials are extensively used as fuels for thermal energy generation in the Brazilian food industry, the mixture of such a small mass fraction of this solid waste with sawdust should not require significant changes to the

Industrial solid wastes must be disposed of safely, and co-firing them with sawdust was shown to be profitable using a pilot-scale cyclone combustor in studies currently underway in our research group. The biogas produced from pig wastes has great potential to become another important bioenergy option for the Brazilian agroindustrial sector. Additionally, anaerobic digestion has other environmental benefits besides the production of a renewable energy carrier, which include the possibility of nutrient recycling and reduction of waste volumes. Nevertheless, studies are needed to investigate the effects of variations in the input to a biodigestor, how the waste composition influences the overall stability of the process

The comprehensive technical-scientific analyses of the actions concerning water, wastewater and solid waste management carried out in the case study meat processing plant indicated that environmentally, financially and socially sustainable practices can be successfully im‐

compounds into rivers) and providing economic benefits.

and the product quality, and options for the biogas application.

BTEX – Benzene, Toluene, Ethyl-benzene and (o-,m-,p-)xylenes

plemented in any type and size of food processing plant.

current operating conditions.

**Nomenclature**

AOPs – Advanced Oxidation Processes

COD – Chemical oxygen demand

BSE – Bovine Spongiform Encephalopathy

BOD5 – Biochemical oxygen demand (5 days)

DWTP – Drinking Water Treatment Plant

## **5. Conclusions**

The water balance analysis carried out considering all processing steps at the case study plant indicated that the minimization of the fresh water consumption at the four major con‐ sumption points could account for some 806 m3 d-1. Concerning wastewater reuse, the four streams identified as having a real possibility for reuse totaled approximately 1383 m3 d-1. These need simple reconditioning treatment before application to processes without direct contact with food products, that is, in non-potable uses (*e.g.* cooling water, toilet flushing water or irrigation around the plant), thus saving fresh potable water. The theoretical fresh water reduction after water minimization and wastewater reuse was 25.4% with a financial saving of around \$434,622.00 per year.

Additionally, to reduce even further the percentage of fresh water consumption, indirect wastewater reuse could be carried out after reconditioning by applying tertiary treatments, such as advanced oxidation processes (AOPs), to treat the secondary effluent (after secon‐ dary activated sludge treatment). The tertiary-treated water effluent could then be used in other processes without contact with food products. The tertiary treatment model proposed was a heterogeneous AOP system (UV/TiO2/H2O2) which can be applied to urban, rural or industrial effluents where the factors inhibiting their reuse as water of potable quality are the presence of suspended solids (even at low concentration), dissolved organic matter, re‐ calcitrant micro-pollutants (trace compounds) and high concentrations of nitrate and nitrite. However, laboratory tests should be carried out with real wastewater to evaluate the effi‐ ciency of each process step.

For the treatment of the effluent from the case study poultry hatchery, a chemical or physi‐ cochemical process would be the best option due to the low biodegradability of the effluent (COD/BOD5 = 4.6) and the presence of persistent compounds, which are not removed by bi‐ ological processes. All treatments evaluated, particularly the photo-Fenton reaction, resulted in an increased biodegradability of the effluent, in other words, an increase in the portion of the material susceptible to degradation by biological processes. Thus, a biological process should be added as a final step in the effluent treatment, as a post-treatment mainly to re‐ move the previously-formed more biodegradable compounds (with lower molar mass) and the nutrients that are not eliminated by the physicochemical process, *e.g.*, nitrate. Also, a comparison of the pros and cons (especially costs and efficiency) of the two treatments (a) photo-Fenton + simple biological treatment (such as stabilization ponds) and (b) UV/ TiO2/H2O2 could be carried out in terms of their effectiveness in the treatment of slaughter‐ house secondary effluent. Hence, the most important consideration to be evaluated is which treatment can ensure that the standards and limits set by legislation are achieved, thus avoiding undesirable impact on the environment (such as the discharge of persistent organic compounds into rivers) and providing economic benefits.

Regarding the solid wastes, the substitution of 10 wt% of the sawdust with the biosolids originating from the physicochemical wastewater treatment can increase the thermal energy production by approximately 4% compared to the combustion of sawdust alone, leading to an economy of 1950 tons per year of sawdust besides providing savings in relation to land‐ fill disposal. Additionally, co-combustion is the most feasible option for energy recovery from this waste in Brazil, making it possible to control the burning process, to avoid the oc‐ currence the fouling and slagging and to meet the emission limits established in the relevant legislation. Considering that wood and wood-based materials are extensively used as fuels for thermal energy generation in the Brazilian food industry, the mixture of such a small mass fraction of this solid waste with sawdust should not require significant changes to the current operating conditions.

Industrial solid wastes must be disposed of safely, and co-firing them with sawdust was shown to be profitable using a pilot-scale cyclone combustor in studies currently underway in our research group. The biogas produced from pig wastes has great potential to become another important bioenergy option for the Brazilian agroindustrial sector. Additionally, anaerobic digestion has other environmental benefits besides the production of a renewable energy carrier, which include the possibility of nutrient recycling and reduction of waste volumes. Nevertheless, studies are needed to investigate the effects of variations in the input to a biodigestor, how the waste composition influences the overall stability of the process and the product quality, and options for the biogas application.

The comprehensive technical-scientific analyses of the actions concerning water, wastewater and solid waste management carried out in the case study meat processing plant indicated that environmentally, financially and socially sustainable practices can be successfully im‐ plemented in any type and size of food processing plant.

## **Nomenclature**

ment because each burner presented different burning efficiencies and they were still in the adjustment phase. However, by the end of the project, all gaseous emissions were below the limits imposed by Brazilian Legislation. The SO2 requires greater caution due to the pres‐ ence of H2S and therefore a pre-treatment has to be considered before the process can be considered adequate. H2S can easily react with iron oxides and hydroxides, requiring the presence of water, and this can thus be considered a good method to remove the H2S from

The water balance analysis carried out considering all processing steps at the case study plant indicated that the minimization of the fresh water consumption at the four major con‐ sumption points could account for some 806 m3 d-1. Concerning wastewater reuse, the four streams identified as having a real possibility for reuse totaled approximately 1383 m3 d-1. These need simple reconditioning treatment before application to processes without direct contact with food products, that is, in non-potable uses (*e.g.* cooling water, toilet flushing water or irrigation around the plant), thus saving fresh potable water. The theoretical fresh water reduction after water minimization and wastewater reuse was 25.4% with a financial

Additionally, to reduce even further the percentage of fresh water consumption, indirect wastewater reuse could be carried out after reconditioning by applying tertiary treatments, such as advanced oxidation processes (AOPs), to treat the secondary effluent (after secon‐ dary activated sludge treatment). The tertiary-treated water effluent could then be used in other processes without contact with food products. The tertiary treatment model proposed was a heterogeneous AOP system (UV/TiO2/H2O2) which can be applied to urban, rural or industrial effluents where the factors inhibiting their reuse as water of potable quality are the presence of suspended solids (even at low concentration), dissolved organic matter, re‐ calcitrant micro-pollutants (trace compounds) and high concentrations of nitrate and nitrite. However, laboratory tests should be carried out with real wastewater to evaluate the effi‐

For the treatment of the effluent from the case study poultry hatchery, a chemical or physi‐ cochemical process would be the best option due to the low biodegradability of the effluent (COD/BOD5 = 4.6) and the presence of persistent compounds, which are not removed by bi‐ ological processes. All treatments evaluated, particularly the photo-Fenton reaction, resulted in an increased biodegradability of the effluent, in other words, an increase in the portion of the material susceptible to degradation by biological processes. Thus, a biological process should be added as a final step in the effluent treatment, as a post-treatment mainly to re‐ move the previously-formed more biodegradable compounds (with lower molar mass) and the nutrients that are not eliminated by the physicochemical process, *e.g.*, nitrate. Also, a comparison of the pros and cons (especially costs and efficiency) of the two treatments (a) photo-Fenton + simple biological treatment (such as stabilization ponds) and (b) UV/

biogas (Zichari, 2003).

724 Food Industry

**5. Conclusions**

saving of around \$434,622.00 per year.

ciency of each process step.


BOD5 – Biochemical oxygen demand (5 days)


HHV – Higher Heating Value LFP – Biosolids originating from the physicochemical treatment of the meat processing in‐ dustry wastewater LFPSD 1:9 – Mixture of LFP and SD in a mass ratio of 1:9 LHV – Lower Heating Value PAH – Polycyclic Aromatic Hydrocarbons PCB – Polychlorinated Biphenyls PCDD/PCDF – Polychlorinated dibenzo-p-dioxins and Polychlorinated dibenzofurans SD – Wood Sawdust TEF – Toxicity Equivalent Factor TOC – Total Organic Carbon W2M – Water and Wastewater Management WWTP – Wastewater Treatment Plant

**References**

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codlegi=338>.

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## **Acknowledgments**

The authors would like to acknowledge BRF - Brasil Foods for providing the infrastructure and financial support, as well as the National Council for Scientific and Technological De‐ velopment (CNPq) and the Brazilian Federal Agency for Support and Evaluation of Gradu‐ ate Education (CAPES) for the grants supporting this study.

## **Author details**

Humberto J. José1 , Regina F. P. M. Moreira1 , Danielle B. Luiz1,3, Elaine Virmond1,4, Aziza K. Genena1,5, Silvia L. F. Andersen1 , Rennio F. de Sena1,6 and Horst Fr. Schröder2


## **References**

HHV – Higher Heating Value

LHV – Lower Heating Value

PCB – Polychlorinated Biphenyls

TEF – Toxicity Equivalent Factor

TOC – Total Organic Carbon

**Acknowledgments**

**Author details**

Humberto J. José1

PAH – Polycyclic Aromatic Hydrocarbons

W2M – Water and Wastewater Management

ate Education (CAPES) for the grants supporting this study.

, Regina F. P. M. Moreira1

Aziza K. Genena1,5, Silvia L. F. Andersen1

2 RWTH Aachen University, Germany

6 Federal University of Paraíba, Brazil

4 EMBRAPA Agroenergy, Brazil

1 Federal University of Santa Catarina, Brazil

3 EMBRAPA Fishery and Aquaculture, Brazil

5 Federal Technological University of Paraná, Brazil

WWTP – Wastewater Treatment Plant

LFPSD 1:9 – Mixture of LFP and SD in a mass ratio of 1:9

dustry wastewater

726 Food Industry

SD – Wood Sawdust

LFP – Biosolids originating from the physicochemical treatment of the meat processing in‐

PCDD/PCDF – Polychlorinated dibenzo-p-dioxins and Polychlorinated dibenzofurans

The authors would like to acknowledge BRF - Brasil Foods for providing the infrastructure and financial support, as well as the National Council for Scientific and Technological De‐ velopment (CNPq) and the Brazilian Federal Agency for Support and Evaluation of Gradu‐

, Danielle B. Luiz1,3, Elaine Virmond1,4,

, Rennio F. de Sena1,6 and Horst Fr. Schröder2


[11] de Sena, R.F., Tambosi, J.L., Genena, A.K., Moreira, R.F.P.M., Schröder, H.Fr., & José, H.J. (2009). Treatment of meat industry wastewater using dissolved air flotation and advanced oxidation processes monitored by GC–MS and LC–MS. *Chemical Engineer‐ ing Journal*, Vol. 152, No. 1 (Oct 2009), pp. 151–157, ISSN 1385-8947.

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Water and Wastewater Management and Biomass to Energy Conversion in a Meat Processing Plant in Brazil...

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**Chapter 31**

**Seaweeds for Food and Industrial Applications**

Marine macroalgae, or the term seaweeds, are plant-like organisms that generally live attached to rock or other hard substrata in coastal areas. The classification into divisions is based on various properties such as pigmentation, chemical nature of photosynthetic storage product, the organization of photosynthetic membranes, and other morphological fea‐ tures. Traditionally, they belong to four different groups, empirically distinguished since the mid-nineteenth century on the basis of color: **blue-green algae** (phylum: Cyanophyta, up to 1500 species), **red algae** (phylum: Rhodophyta, about 6000 species), **brown algae** (phylum: Ochrophyta, classes: Phaeophyceae, about 1750 species), and **green algae** (phylum: Chlorophyta, classes: Bryopsidophyceae, Chlorophyceae, Dasycladophyceae, Prasinophy‐ ceae, and Ulvophyceae, about 1200 species). However, each of these groups has microscop‐ ics, if not unicellular, represantatives. All seaweeds at some stage in their life cycles are unicellular, as spores or zygotes, and may be temporarily planktonic. The blue-green algae are widesperead on temperate rocky and sandy shores and have occasionally been acknowledged in seaweed floras. Seaweeds are found growing throughouth the world oceans and seas none is found to be poisonous (Bold and Wyne, 1985; Guiry, 2009; Lobban and Harrison, 2000). Why seaweed is important? Most people don't realize how impor‐ tant marine macroalgae are, both ecologically and commercially. In fact, seaweeds are crucial primary producer in oceanic aquatic food webs. They are rich both in minerals and essential trace elements, and raw materials for the pharmaceutical and cosmetics industry (Chap‐ man, 1970). Seaweed is a very versatile product widely used for food in direct human consumption. Its classified taxonomically as algae and they represent a food group that is not normally ingested in unprocessed form to any great extent in Western societies. Humankind is no strangers to the use of algae as a food source. Even if seaweeds have been used as a human food since ancient times, particularly in the region bounded by China, the

> © 2013 Kılınç et al.; licensee InTech. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

© 2013 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

distribution, and reproduction in any medium, provided the original work is properly cited.

and reproduction in any medium, provided the original work is properly cited.

Berna Kılınç, Semra Cirik, Gamze Turan,

Additional information is available at the end of the chapter

Hatice Tekogul and Edis Koru

http://dx.doi.org/10.5772/53172

**1. Introduction**

## **Seaweeds for Food and Industrial Applications**

Berna Kılınç, Semra Cirik, Gamze Turan, Hatice Tekogul and Edis Koru

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/53172

## **1. Introduction**

Marine macroalgae, or the term seaweeds, are plant-like organisms that generally live attached to rock or other hard substrata in coastal areas. The classification into divisions is based on various properties such as pigmentation, chemical nature of photosynthetic storage product, the organization of photosynthetic membranes, and other morphological fea‐ tures. Traditionally, they belong to four different groups, empirically distinguished since the mid-nineteenth century on the basis of color: **blue-green algae** (phylum: Cyanophyta, up to 1500 species), **red algae** (phylum: Rhodophyta, about 6000 species), **brown algae** (phylum: Ochrophyta, classes: Phaeophyceae, about 1750 species), and **green algae** (phylum: Chlorophyta, classes: Bryopsidophyceae, Chlorophyceae, Dasycladophyceae, Prasinophy‐ ceae, and Ulvophyceae, about 1200 species). However, each of these groups has microscop‐ ics, if not unicellular, represantatives. All seaweeds at some stage in their life cycles are unicellular, as spores or zygotes, and may be temporarily planktonic. The blue-green algae are widesperead on temperate rocky and sandy shores and have occasionally been acknowledged in seaweed floras. Seaweeds are found growing throughouth the world oceans and seas none is found to be poisonous (Bold and Wyne, 1985; Guiry, 2009; Lobban and Harrison, 2000). Why seaweed is important? Most people don't realize how impor‐ tant marine macroalgae are, both ecologically and commercially. In fact, seaweeds are crucial primary producer in oceanic aquatic food webs. They are rich both in minerals and essential trace elements, and raw materials for the pharmaceutical and cosmetics industry (Chap‐ man, 1970). Seaweed is a very versatile product widely used for food in direct human consumption. Its classified taxonomically as algae and they represent a food group that is not normally ingested in unprocessed form to any great extent in Western societies. Humankind is no strangers to the use of algae as a food source. Even if seaweeds have been used as a human food since ancient times, particularly in the region bounded by China, the

© 2013 Kılınç et al.; licensee InTech. This is an open access article 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. © 2013 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Korean Peninsula and Japan. But the commercial exploitation of this resource is only a few decades old, after World War II, when the focus was set on a possible insufficient protein supply due to the rapid increase of the world population. Today those countries are the largest consumers of marine algae as food. However, as nationals from these countries have migrated to other parts of the Earth, the demand for seaweedfor food has followed them, for example, in some parts of the North and South America. Nowadays, seaweeds are major coastal resources which are valuable to human consumption and environment in many countries. Edible seaweeds were widely consumed, especially in Asian countries (e.g., Japan, China, Korea, Taiwan, Singapore, Thailand, Brunei, Cambodia, and Vietnam, but also in South Africa, Indonesia, Malaysia, Belize, Peru, Chile, the Canadian Maritimes, Scandina‐ via, South West England, Ireland, Wales, California, Philippines, and Scotland) as fresh, dried, or ingredients in prepared foods. Their photosynthetic mechanism is similar to that of land-based plants. They are generally more efficient in converting solar energy into biomass, mainly because of their simple cellular structure and being submerged in an aqueous environment with access to water, CO2, and other nutrients. Same time, macroal‐ gae are considered as the food supplement for 21st century, because they contain proteins, lipids, polysaccharides, minerals, vitamins, and enzymes. In common, seaweeds are rich in vitamins A, E, C, and Niacin with similar content in red algae (Rhodophyta), brown algae (Ochrophyta) and green algae (Chlorophyta). The concentration of vitamins B12, B1, panthothetic acid, folic, and folinic acids are generally higher in greens and reds than in browns. The brown algae possess organic iodine in greater amounts. Marine algae are similar to oats in protein and carbohydrate values. The green and red algae appear higher in crude protein far tested about 2 to 4 %. All algae contain high content of cabohydrates (sugar and starches) in polysaccharide biochemical structure which is a natural nontoxic colloidal substance that has been used as mucilaginous material referred to as gel. The nutrients composition of seaweed vary and is affected by species, geographic area, season and temperature of water. These sea-vegetables are of nutritional interest as they are low calorie food, but rich in vitamins, minerals and dietary fibres. Seaweeds, which have traditionally been used by the Western food industry for their polysaccharide extractives 'alginate, carrageenan and agar' also contain compounds with potential nutritional benefits. Sea‐ weeds have recently been approved in France for human consumption (as vegetables and condiments), thus opening new opportunities for the food industry. These seaweed ingredients must meet industrial and technical specifications and consumer safety regula‐ tions. It is also an ingredient for the global food and cosmetics industries and is used as fertilizer and as an animal feed additive. Total annual value of production is estimated at almost US\$ 6 billion of which food products for human consumption represent US \$ 5 billion. Total annual use by the global seaweed industry is about 8 million tonnes of wet seaweed. Seaweed can be collected from the wild but is now increasingly cultivated. It falls into three broad groups based on pigmentation; brown, red and green seaweed. Use of seaweed as food has strong roots in Asian countries such as China, Japan and the Repub‐ lic of Korea, but demand for seaweed as food has now also spread to North America, South America and Europe. China is by far the largest seaweed producer followed by the Republic of Korea and Japan but seaweeds are today produced in all continents. Red and brown

seaweeds are also used to produce hydrocolloids; alginate, agar and carrageenan, which are used as thickening and gelling agents. Today, approximately 1 million tonnes of wet seaweed are harvested and extracted to produce about 55 000 tonnes of hydrocolloids, valued at

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The use of seaweed as food has been traced back to the fourth century in Japan and the sixth century in China. In 1750's, an English physician successfully used ash from kelp (Phaeophyceae) which is rich in iodine to treat goiter. Kelp was also used to treath obesity in 19 th. century, and agar was used as a laxative. Seaweeds were used as a source of iodine. And their crude extracts were used for clarification in brewing. Another hydrocolloid, carrageen, found initially in the red seaweed *Chondrus crispus* was known in Ireland since 1810. Alginic acid, a hydrocolloid found in all brown seaweeds, was discovery first by Charles Stanford in the 1880s. Development of a large scale alginate industry began California and in Scotland in the late 1920s and early 1930s, respectively. *Laminaria japonica* was cultivated in China from the 1950s. The hydrocolloids have found increasing industri‐ al and food applications in those years. Today China, Japan and the Republic of Korea are the largest consumers of seaweed as food. However, as nationals from these countries have migrated to other parts of the world, the demand for seaweed for food has followed them, as, for example, in some parts of the United States of America and South America. Increasing demand over the last fifty years outstripped the ability to supply requirements from natural (wild) stocks. Research into the life cycles of these seaweeds has led to the development of cultivation industries that now produce more than 90 percent of the market's demand. In Ireland, Iceland and Nova Scotia (Canada), a different type of seaweed has traditionally been eaten, and this market is being developed. Some government and commercial organizations in France have been promoting seaweeds for restaurant and domestic use, with some success. An informal market exists among coastal dwellers in some developing countries where there has been a tradition of using fresh seaweeds as vegetables and in salads. Various red and brown seaweeds are used to produce three hydrocolloids: agar, alginate and carrageenan. A hydrocolloid is a non-crystalline substance with very large molecules and which dissolves in water to give a thickened (viscous) solution. Alginate, agar and carrageenan are water-soluble carbohydrates that are used to thicken (increase the viscosity of) aqueous solutions, to form gels (jellies) of varying degrees of firmness, to form water-soluble films, and to stabilize some products, such as ice cream (they inhibit the formation of large ice crystals so that the ice cream can retain a smooth texture). Sea‐ weeds as a source of these hydrocolloids dates back to 1658, when the gelling properties of agar, extracted with hot water from a red seaweed, were first discovered in Japan. Ex‐ tracts of Irish Moss, another red seaweed, contain carrageenan and were popular as thickening agents in the nineteenth century. It was not until the 1930s that extracts of brown seaweeds, containing alginate, were produced commercially and sold as thickening and gelling agents. Industrial uses of seaweed extracts expanded rapidly after the Second World

almost US \$ 600 million (McHug, 2003).

**2. Historical background on the use of seaweeds**

seaweeds are also used to produce hydrocolloids; alginate, agar and carrageenan, which are used as thickening and gelling agents. Today, approximately 1 million tonnes of wet seaweed are harvested and extracted to produce about 55 000 tonnes of hydrocolloids, valued at almost US \$ 600 million (McHug, 2003).

## **2. Historical background on the use of seaweeds**

Korean Peninsula and Japan. But the commercial exploitation of this resource is only a few decades old, after World War II, when the focus was set on a possible insufficient protein supply due to the rapid increase of the world population. Today those countries are the largest consumers of marine algae as food. However, as nationals from these countries have migrated to other parts of the Earth, the demand for seaweedfor food has followed them, for example, in some parts of the North and South America. Nowadays, seaweeds are major coastal resources which are valuable to human consumption and environment in many countries. Edible seaweeds were widely consumed, especially in Asian countries (e.g., Japan, China, Korea, Taiwan, Singapore, Thailand, Brunei, Cambodia, and Vietnam, but also in South Africa, Indonesia, Malaysia, Belize, Peru, Chile, the Canadian Maritimes, Scandina‐ via, South West England, Ireland, Wales, California, Philippines, and Scotland) as fresh, dried, or ingredients in prepared foods. Their photosynthetic mechanism is similar to that of land-based plants. They are generally more efficient in converting solar energy into biomass, mainly because of their simple cellular structure and being submerged in an aqueous environment with access to water, CO2, and other nutrients. Same time, macroal‐ gae are considered as the food supplement for 21st century, because they contain proteins, lipids, polysaccharides, minerals, vitamins, and enzymes. In common, seaweeds are rich in vitamins A, E, C, and Niacin with similar content in red algae (Rhodophyta), brown algae (Ochrophyta) and green algae (Chlorophyta). The concentration of vitamins B12, B1, panthothetic acid, folic, and folinic acids are generally higher in greens and reds than in browns. The brown algae possess organic iodine in greater amounts. Marine algae are similar to oats in protein and carbohydrate values. The green and red algae appear higher in crude protein far tested about 2 to 4 %. All algae contain high content of cabohydrates (sugar and starches) in polysaccharide biochemical structure which is a natural nontoxic colloidal substance that has been used as mucilaginous material referred to as gel. The nutrients composition of seaweed vary and is affected by species, geographic area, season and temperature of water. These sea-vegetables are of nutritional interest as they are low calorie food, but rich in vitamins, minerals and dietary fibres. Seaweeds, which have traditionally been used by the Western food industry for their polysaccharide extractives 'alginate, carrageenan and agar' also contain compounds with potential nutritional benefits. Sea‐ weeds have recently been approved in France for human consumption (as vegetables and condiments), thus opening new opportunities for the food industry. These seaweed ingredients must meet industrial and technical specifications and consumer safety regula‐ tions. It is also an ingredient for the global food and cosmetics industries and is used as fertilizer and as an animal feed additive. Total annual value of production is estimated at almost US\$ 6 billion of which food products for human consumption represent US \$ 5 billion. Total annual use by the global seaweed industry is about 8 million tonnes of wet seaweed. Seaweed can be collected from the wild but is now increasingly cultivated. It falls into three broad groups based on pigmentation; brown, red and green seaweed. Use of seaweed as food has strong roots in Asian countries such as China, Japan and the Repub‐ lic of Korea, but demand for seaweed as food has now also spread to North America, South America and Europe. China is by far the largest seaweed producer followed by the Republic of Korea and Japan but seaweeds are today produced in all continents. Red and brown

736 Food Industry

The use of seaweed as food has been traced back to the fourth century in Japan and the sixth century in China. In 1750's, an English physician successfully used ash from kelp (Phaeophyceae) which is rich in iodine to treat goiter. Kelp was also used to treath obesity in 19 th. century, and agar was used as a laxative. Seaweeds were used as a source of iodine. And their crude extracts were used for clarification in brewing. Another hydrocolloid, carrageen, found initially in the red seaweed *Chondrus crispus* was known in Ireland since 1810. Alginic acid, a hydrocolloid found in all brown seaweeds, was discovery first by Charles Stanford in the 1880s. Development of a large scale alginate industry began California and in Scotland in the late 1920s and early 1930s, respectively. *Laminaria japonica* was cultivated in China from the 1950s. The hydrocolloids have found increasing industri‐ al and food applications in those years. Today China, Japan and the Republic of Korea are the largest consumers of seaweed as food. However, as nationals from these countries have migrated to other parts of the world, the demand for seaweed for food has followed them, as, for example, in some parts of the United States of America and South America. Increasing demand over the last fifty years outstripped the ability to supply requirements from natural (wild) stocks. Research into the life cycles of these seaweeds has led to the development of cultivation industries that now produce more than 90 percent of the market's demand. In Ireland, Iceland and Nova Scotia (Canada), a different type of seaweed has traditionally been eaten, and this market is being developed. Some government and commercial organizations in France have been promoting seaweeds for restaurant and domestic use, with some success. An informal market exists among coastal dwellers in some developing countries where there has been a tradition of using fresh seaweeds as vegetables and in salads. Various red and brown seaweeds are used to produce three hydrocolloids: agar, alginate and carrageenan. A hydrocolloid is a non-crystalline substance with very large molecules and which dissolves in water to give a thickened (viscous) solution. Alginate, agar and carrageenan are water-soluble carbohydrates that are used to thicken (increase the viscosity of) aqueous solutions, to form gels (jellies) of varying degrees of firmness, to form water-soluble films, and to stabilize some products, such as ice cream (they inhibit the formation of large ice crystals so that the ice cream can retain a smooth texture). Sea‐ weeds as a source of these hydrocolloids dates back to 1658, when the gelling properties of agar, extracted with hot water from a red seaweed, were first discovered in Japan. Ex‐ tracts of Irish Moss, another red seaweed, contain carrageenan and were popular as thickening agents in the nineteenth century. It was not until the 1930s that extracts of brown seaweeds, containing alginate, were produced commercially and sold as thickening and gelling agents. Industrial uses of seaweed extracts expanded rapidly after the Second World War, but were sometimes limited by the availability of raw materials. In the 1950's, it was found that *Gracilaria* spp. treated with alkali produced higher strengthgels. After several years, *Gracilaria* can be cultivated successfully on a commercial scale, it is now used more widely. Once again, research into life cycles has led to the development of cultivation industries that now supply a high proportion of the raw material for some hydrocolloids. Today, approximately 1 million tonnes of wet seaweed are harvested and extracted to produce the above three hydrocolloids. Total hydrocolloid production is about 55 000 tonnes, with a value of US \$ 585 million. Alginate production (US \$ 213 million) is by extraction from brown seaweeds, all of which are harvested from the wild; cultivation of brown seaweeds is too expensive to provide raw material for industrial uses. Agar production (US \$ 132 million) is principally from two types of red seaweed, one of which has been cultivated since the 1960-70s, but on a much larger scale since 1990, and this has allowed the expan‐ sion of the agar industry. Carrageenan production (US \$ 240 million) was originally dependent on wild seaweeds, especially Irish Moss, a small seaweed growing in cold waters, with a limited resource base. However, since the early 1970s the industry has expanded rapidly because of the availability of other carrageenan-containing seaweeds that have been successfully cultivated in warm-water countries with low labour costs. Today, most of the seaweed used for carrageenan production comes from cultivation, although there is still some demand for Irish Moss and some other wild species from South America. Seaweed meal, used an additive to animal feed, has been produced in Norway, where its produc‐ tion was pioneered in the 1960s. It is made from brown seaweeds that are collected, dried and milled. Drying is usually by oil-fired furnaces, so costs are affected by crude oil prices. Approximately 50 000 tonnes of wet seaweed are harvested annually to yield 10 000 tonnes of seaweed meal, which is sold for US \$ 5 million. Fertilizer uses of seaweed date back at least to the nineteenth century. Early usage was by coastal dwellers, who collected stormcast seaweed, usually large brown seaweeds, and dug it into local soils. The growth area in seaweed fertilizers is in the production of liquid seaweed extracts. These can be pro‐ duced in concentrated form for dilution by the user. Several can be applied directly onto plants or they can watered in, around the root areas. There have been several scientific studies that prove these products can be effective. In 1991, it was estimated that about 10 000 tonnes of wet seaweed were used to make 1 000 tonnes of seaweed extracts with a value of US \$ 5 million. However, the market has probably doubled in the last decade because of the wider recognition of the usefulness of the products and the increasing popularity of organic farming, where they are especially effective in the growing of vegetables and some fruits. Cosmetic products, such as creams and lotions, sometimes show on their labels that the contents include "marine extract", "extract of alga", "seaweed extract" or similar. Usually this means that one of the hydrocolloids extracted from seaweed has been added. Algi‐ nate or carrageenan could improve the skin moisture retention properties of the product. Pastes of seaweed, made by cold grinding or freeze crushing, are used in thalassotherapy, where they are applied to the person's body and then warmed under infrared radiation. This treatment, in conjunction with seawater hydrotherapy, is said to provide relief for rheumatism and osteoporosis (De Roeck-Holtzhauer, 1991).

**3. Sources of seaweed**

**3.1. Red seaweeds**

**3.2. Brown seaweeds**

A seaweed may belong to one of several groups of multicellular algae: the red algae, brown algae and green algae,. As these three groups are not thought to have a common multicellular ancestor, the seaweeds are a polyphyletic group. In addition, some tuft-forming blue green algae (Cyanobacteria) are sometimes considered as seaweeds — "seaweed" is a colloquial term and lacks a formal definition. Two specific environmental requirements dominate seaweed ecology. These are the presence of seawater (or at least brackish water) and the presence of light sufficient to drive photosynthesis. Another common requirement is a firm attachment point. As a result, seaweeds most commonly inhabit the littoral zone and within that zone more frequently on rocky shores than on sand or shingle. Seaweeds occupy a wide range of ecological niches. The highest elevation is only wetted by the tops of sea spray, the lowest is several meters deep. In some areas, littoral seaweeds can extend several miles out to sea. The limiting factor in such cases is sunlight availability. The deepest living seaweeds are some species of red algae. A number of species such as *Sargassum* have adapted to a fully planktonic niche and are free-floating, depending on gas-filled sacs to maintain an acceptable depth. Others have adapted to live in tidal rock pools. In this habitat seaweeds must withstand rapidly

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Red seaweeds have had a more diverse evolution than the green and the brown. Many species cannot stand desiccation and dominate the inter-tidal rock pools. Others tolerate desiccation, such as the purple laver which can often be seen stretched out like a dry black film over mussle beds on rocky beaches. Red seaweeds such as *Polysiphonia lanosa* are epiphytes, these are plants that grow on other plants for physical support. In this case the epiphyte benefits from the host's buoyancy lifting it closer to the sunlight. The red colour of the seaweeds is due to the larger amount of red phycoblin pigments overriding the green pigment chlorophyll. The main biomass of red algae worldwide is provided by the Corallinaceae and Gigartinaceae. The red algae *Gelidium*, *Gracilaria*, *Pterocladis* and other many red algae are used in the manufacture of the important agar, used widely as a growth medium for microorganism and other biotech‐ nological and food applications. Another important red seaweed alga is *Eucheuma* used in the production of Carrageenan, an important product used in cosmetics, food processing and industrial uses, as well as a food source. Some of the most significant caargeenan species include *Betaphycus gelatinae*, *Eucheuma denticulatum*, and several species of the genus *Kappa‐*

Laminaria sp. ′kombu′, Undaria sp. ′wakame′, Hizikia fusiforme ′hiziki′ is edible and an important resource Asia countries especiaqlly China and Japan. They are consumed raw, boiled or dried material with sweetened green beans, jelly, crushed ice, and coconut milk in Southern Vietnam (Tsutsui et. al., 2005). Laminaria sp. was in plentiful supply in Japan, mainly from the northern island of Hokkaido, where several naturally growing species were available.

changing temperature and salinity and even occasional drying

*phycus* including *K. alvarezii* (Lobban and Harrison, 1994).

## **3. Sources of seaweed**

War, but were sometimes limited by the availability of raw materials. In the 1950's, it was found that *Gracilaria* spp. treated with alkali produced higher strengthgels. After several years, *Gracilaria* can be cultivated successfully on a commercial scale, it is now used more widely. Once again, research into life cycles has led to the development of cultivation industries that now supply a high proportion of the raw material for some hydrocolloids. Today, approximately 1 million tonnes of wet seaweed are harvested and extracted to produce the above three hydrocolloids. Total hydrocolloid production is about 55 000 tonnes, with a value of US \$ 585 million. Alginate production (US \$ 213 million) is by extraction from brown seaweeds, all of which are harvested from the wild; cultivation of brown seaweeds is too expensive to provide raw material for industrial uses. Agar production (US \$ 132 million) is principally from two types of red seaweed, one of which has been cultivated since the 1960-70s, but on a much larger scale since 1990, and this has allowed the expan‐ sion of the agar industry. Carrageenan production (US \$ 240 million) was originally dependent on wild seaweeds, especially Irish Moss, a small seaweed growing in cold waters, with a limited resource base. However, since the early 1970s the industry has expanded rapidly because of the availability of other carrageenan-containing seaweeds that have been successfully cultivated in warm-water countries with low labour costs. Today, most of the seaweed used for carrageenan production comes from cultivation, although there is still some demand for Irish Moss and some other wild species from South America. Seaweed meal, used an additive to animal feed, has been produced in Norway, where its produc‐ tion was pioneered in the 1960s. It is made from brown seaweeds that are collected, dried and milled. Drying is usually by oil-fired furnaces, so costs are affected by crude oil prices. Approximately 50 000 tonnes of wet seaweed are harvested annually to yield 10 000 tonnes of seaweed meal, which is sold for US \$ 5 million. Fertilizer uses of seaweed date back at least to the nineteenth century. Early usage was by coastal dwellers, who collected stormcast seaweed, usually large brown seaweeds, and dug it into local soils. The growth area in seaweed fertilizers is in the production of liquid seaweed extracts. These can be pro‐ duced in concentrated form for dilution by the user. Several can be applied directly onto plants or they can watered in, around the root areas. There have been several scientific studies that prove these products can be effective. In 1991, it was estimated that about 10 000 tonnes of wet seaweed were used to make 1 000 tonnes of seaweed extracts with a value of US \$ 5 million. However, the market has probably doubled in the last decade because of the wider recognition of the usefulness of the products and the increasing popularity of organic farming, where they are especially effective in the growing of vegetables and some fruits. Cosmetic products, such as creams and lotions, sometimes show on their labels that the contents include "marine extract", "extract of alga", "seaweed extract" or similar. Usually this means that one of the hydrocolloids extracted from seaweed has been added. Algi‐ nate or carrageenan could improve the skin moisture retention properties of the product. Pastes of seaweed, made by cold grinding or freeze crushing, are used in thalassotherapy, where they are applied to the person's body and then warmed under infrared radiation. This treatment, in conjunction with seawater hydrotherapy, is said to provide relief for

738 Food Industry

rheumatism and osteoporosis (De Roeck-Holtzhauer, 1991).

A seaweed may belong to one of several groups of multicellular algae: the red algae, brown algae and green algae,. As these three groups are not thought to have a common multicellular ancestor, the seaweeds are a polyphyletic group. In addition, some tuft-forming blue green algae (Cyanobacteria) are sometimes considered as seaweeds — "seaweed" is a colloquial term and lacks a formal definition. Two specific environmental requirements dominate seaweed ecology. These are the presence of seawater (or at least brackish water) and the presence of light sufficient to drive photosynthesis. Another common requirement is a firm attachment point. As a result, seaweeds most commonly inhabit the littoral zone and within that zone more frequently on rocky shores than on sand or shingle. Seaweeds occupy a wide range of ecological niches. The highest elevation is only wetted by the tops of sea spray, the lowest is several meters deep. In some areas, littoral seaweeds can extend several miles out to sea. The limiting factor in such cases is sunlight availability. The deepest living seaweeds are some species of red algae. A number of species such as *Sargassum* have adapted to a fully planktonic niche and are free-floating, depending on gas-filled sacs to maintain an acceptable depth. Others have adapted to live in tidal rock pools. In this habitat seaweeds must withstand rapidly changing temperature and salinity and even occasional drying

#### **3.1. Red seaweeds**

Red seaweeds have had a more diverse evolution than the green and the brown. Many species cannot stand desiccation and dominate the inter-tidal rock pools. Others tolerate desiccation, such as the purple laver which can often be seen stretched out like a dry black film over mussle beds on rocky beaches. Red seaweeds such as *Polysiphonia lanosa* are epiphytes, these are plants that grow on other plants for physical support. In this case the epiphyte benefits from the host's buoyancy lifting it closer to the sunlight. The red colour of the seaweeds is due to the larger amount of red phycoblin pigments overriding the green pigment chlorophyll. The main biomass of red algae worldwide is provided by the Corallinaceae and Gigartinaceae. The red algae *Gelidium*, *Gracilaria*, *Pterocladis* and other many red algae are used in the manufacture of the important agar, used widely as a growth medium for microorganism and other biotech‐ nological and food applications. Another important red seaweed alga is *Eucheuma* used in the production of Carrageenan, an important product used in cosmetics, food processing and industrial uses, as well as a food source. Some of the most significant caargeenan species include *Betaphycus gelatinae*, *Eucheuma denticulatum*, and several species of the genus *Kappa‐ phycus* including *K. alvarezii* (Lobban and Harrison, 1994).

#### **3.2. Brown seaweeds**

Laminaria sp. ′kombu′, Undaria sp. ′wakame′, Hizikia fusiforme ′hiziki′ is edible and an important resource Asia countries especiaqlly China and Japan. They are consumed raw, boiled or dried material with sweetened green beans, jelly, crushed ice, and coconut milk in Southern Vietnam (Tsutsui et. al., 2005). Laminaria sp. was in plentiful supply in Japan, mainly from the northern island of Hokkaido, where several naturally growing species were available. Undaria sp. has been harvested from natural resources for many years in the China, Japan and Korean region. Another algae Cladosiphon okamuranus ′mozuku′ as salad in Okinawa-Japan (Thoma, 1997; Zhang et.al., 2007; Zhu et.al., 2009 ). Sargassum sp. is known as horsetail and it is eaten as soup or dressed with soybean sauce, or after being processed in Korea (Madlener, 1997) and in Hawaii (Novaczek, 2001). In the Pasific region, Rosenvingea sp. or slippery cushion, Turbinaria or spiny leaf are eaten as soup or omelet Colpomenia sp. or paperly sea bubble as chop soup, stew or salad. Hydroclatharus sp. or sea colonder, Dictyota sp. or brown, Padina or sea fan ribbon weeds as a food dressing, soup or stew (Novaczek, 2001).

of seaweeds to products increased the concentrations of K, Ca, Mg and Mn. The presence of Nori caused an increase in levels of serine, glycine, alanine, valine, tyrosine, phenylalanine and arginine, whereas Wakame and Sea Spaghetti produced no significant changes in amino acid profiles in the model systems. López-López *et.al*., 2009). The nutritional compositions of 34 edible seaweed products of the *Laminaria* sp.,*Undaria pinnatifida*, *Hizikia fusiforme* and *Porphyra* sp. varieties were analyzed.The marine macroalgae varieties tested demonstrated low lipid contents with 2.3 ± 1.6 g/100 g semi-dry sample weight(s.w.) and proved to be a rich source of dietary fibre (46.2 ± 8.0 g/100 g s.w). The pure protein content of seaweed products varied widely (26.6 ± 6.3 g/100 g s.w. in red algae varieties and 12.9 ± 6.2 g/100 g s.w. in brown algae varieties). All essential amino acids were detected in the seaweed species tested and red algae species featured uniquely high concentrations of taurine when compared to brown algae varieties (Dawczynski *et al*., 2007). The total lipid, protein, ash and individual fatty acid contents of edible seaweeds that had been canned (*Saccorhiza polyschides* and *Himanthalia elongata*) or dried (*H. elongata*, *Laminaria ochroleuca*, *Undaria pinnatifida*, *Palmaria* sp. and *Porphyra* sp.) Total lipid content ranged from 0.70±0.09 to 1.80±0.14 g/(100 g dry weight). The four most abundant fatty acids were C16:0, C18:1ω9, C20:46 and C20:5ω3. Unsaturated fatty acids predominated in all the Brown seaweeds studied, and saturated fatty acids in the red seaweeds, but both groups are balanced sources of ω3 and ω6 acids. Ash content ranged from 19.07±0.61 to 34.00±0.11 g/(100 g dry weight), and protein content from 5.46±0.16 to 24.11±1.03

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Red macro-algae (*Gracilaria* spp.) are used as a fresh food in Hawaii. Species commonly marketed include *G. coronopifolia*, *G. parvispora*, *G. salicornia* and *G. tikvahiae*, however, these seaweeds have a short postharvest life of about 4 days (Paul and Chen, 2008). Seaweeds are a rich source of phytochemicals having anti-oxidant and antimicrobial properties. Presence of fibres and minerals helps in improving the mineral content reduce the salt content. The adding of seaweeds or their extracts to food products will help in reducing the utilization of chemical preservatives (Gupta and Abu-Ghannam, 2011). Edible sea‐ weeds contain various bioactive compounds with potential health benefits and their use as functional ingredients opens up new prospects for food processing, meat product formula‐ tions included. Seaweeds basically contain high proportions of polysaccharides along with various other potentially beneficial compounds such as good-quality protein and essen‐ tial fatty acids, particularly long-chain n-3 polyunsaturated fatty acids (PUFAs). Alginates are the most abundant ionicpolysaccharides present in brown seaweeds (Fernández-Martín *et al.,* 2009). Some seaweed polysaccharides are used by food industry as texture modifiers because of their high viscosity and gelling properties. In Asia seaweeds have been used for centuries in salads, soups and as low calorie dietetic foods. The diatery fibre which constitutes 25-75 % of the dry weight of marine algae and represents their major component, is primarily souble fibre.(Jiménez-Escrig and Sánchez-Muniz, 2000). In particular, miyeok (*Undaria pinnatifida*) is often served in soup,salad, and sidedishes.

g/(100 g dry weight) (Sanchez-Machado, *et. al*.,2004).

**5. Edible seaweed in foods**

#### **3.3. Green seaweeds**

Green seaweeds are found on both sandy and rocky beaches. Many can tolerate low salinity and will colonise areas where rivers meet the sea. The green colour of the seaweed is due to the green pigment chlorophyll required for the photosynthesis of light. Using only chlorophyll means that green seaweeds require good levels of light and therefore will not thrive in shadowed areas or too any depth. It does give them an advantage, the ability to live higher up shore without competition from the red or brown seaweeds. The green saeaweeds *Ulva* sp., *Enteromorpha* sp., *Monostroma* sp., *Caulerpa* sp., *Codium* sp., are commonly known as source of food. In Asia countries especially Japan, dried fronds of edible *Monostroma* sp. and *Enteromor‐ pha* sp are being known as ′aonori-green laver-ele ele-lulua-lumi boso′.These algae are eaten by humans as edible raw, dried, or cooked. They used in preperation of ′nori-jam′ soup (Lobban and Harrison, 1994; Novaczek, 2001).

## **4. Nutritonal composition of edible seaweeds**

Proximate composition (moisture, ash, protein and oil content), total dietary fibre content and physicochemical properties of three brown and two red edible Spanish seaweeds, namely: *Himanthalia elongata* (sea spaghetti), *Bifurcaria bifurcata, Laminaria saccharina* (sweet kombu), *Mastocarpus stellatus* and *Gigartina pistillata* were studied. Ashes (24.9–36.4%) were high in all samples. Protein content ranged from 10.9 to 25.7%, being much higher for *Laminaria* (25.7%) followed by the red seaweeds (15.5–21.3%). Minor components were lipids (0.3–0.9%) in all samples except for *Bifurcaria* (5.6%).In conclusion, these seaweeds can be estimated as a good source of food fibre, protein and minerals for human consumption (Gómez-Ordóñez et al., 2010). Mineral content was determined in several brown (*Fucus vesiculosus, Laminaria digitata*, *Undaria pinnatifida*) and red (*Chondrus crispus, Porphyra tenera*)edible marine sea vegetables. Seaweeds contained high proportions of ash (21.1–39.3%) and sulphate (1.3–5.9%). In brown algae, ash content (30.1–39.3%) was higher than in red algae (20.6–21.1%). Edible brown and redseaweeds could be used as a food supplement to help meet the recommended daily intake of some essential minerals and trace elements (Rupérez, 2002). Sea spaghetti (*Himanthalia elongata*), Wakame (*Undaria pinnatifida*), and Nori (*Porphyra umbilicalis*), on fatty acid compo‐ sition, amino acid profile, protein score, mineral content and antioxidant capacity in low-salt meat emulsion model systems. The addition of seaweeds caused an increase in ω-3 polyun‐ saturated fatty acids (PUFA) and a decrease in the ω-6/ ω-3 PUFA ratio. In general, addition of seaweeds to products increased the concentrations of K, Ca, Mg and Mn. The presence of Nori caused an increase in levels of serine, glycine, alanine, valine, tyrosine, phenylalanine and arginine, whereas Wakame and Sea Spaghetti produced no significant changes in amino acid profiles in the model systems. López-López *et.al*., 2009). The nutritional compositions of 34 edible seaweed products of the *Laminaria* sp.,*Undaria pinnatifida*, *Hizikia fusiforme* and *Porphyra* sp. varieties were analyzed.The marine macroalgae varieties tested demonstrated low lipid contents with 2.3 ± 1.6 g/100 g semi-dry sample weight(s.w.) and proved to be a rich source of dietary fibre (46.2 ± 8.0 g/100 g s.w). The pure protein content of seaweed products varied widely (26.6 ± 6.3 g/100 g s.w. in red algae varieties and 12.9 ± 6.2 g/100 g s.w. in brown algae varieties). All essential amino acids were detected in the seaweed species tested and red algae species featured uniquely high concentrations of taurine when compared to brown algae varieties (Dawczynski *et al*., 2007). The total lipid, protein, ash and individual fatty acid contents of edible seaweeds that had been canned (*Saccorhiza polyschides* and *Himanthalia elongata*) or dried (*H. elongata*, *Laminaria ochroleuca*, *Undaria pinnatifida*, *Palmaria* sp. and *Porphyra* sp.) Total lipid content ranged from 0.70±0.09 to 1.80±0.14 g/(100 g dry weight). The four most abundant fatty acids were C16:0, C18:1ω9, C20:46 and C20:5ω3. Unsaturated fatty acids predominated in all the Brown seaweeds studied, and saturated fatty acids in the red seaweeds, but both groups are balanced sources of ω3 and ω6 acids. Ash content ranged from 19.07±0.61 to 34.00±0.11 g/(100 g dry weight), and protein content from 5.46±0.16 to 24.11±1.03 g/(100 g dry weight) (Sanchez-Machado, *et. al*.,2004).

## **5. Edible seaweed in foods**

Undaria sp. has been harvested from natural resources for many years in the China, Japan and Korean region. Another algae Cladosiphon okamuranus ′mozuku′ as salad in Okinawa-Japan (Thoma, 1997; Zhang et.al., 2007; Zhu et.al., 2009 ). Sargassum sp. is known as horsetail and it is eaten as soup or dressed with soybean sauce, or after being processed in Korea (Madlener, 1997) and in Hawaii (Novaczek, 2001). In the Pasific region, Rosenvingea sp. or slippery cushion, Turbinaria or spiny leaf are eaten as soup or omelet Colpomenia sp. or paperly sea bubble as chop soup, stew or salad. Hydroclatharus sp. or sea colonder, Dictyota sp. or brown,

Green seaweeds are found on both sandy and rocky beaches. Many can tolerate low salinity and will colonise areas where rivers meet the sea. The green colour of the seaweed is due to the green pigment chlorophyll required for the photosynthesis of light. Using only chlorophyll means that green seaweeds require good levels of light and therefore will not thrive in shadowed areas or too any depth. It does give them an advantage, the ability to live higher up shore without competition from the red or brown seaweeds. The green saeaweeds *Ulva* sp., *Enteromorpha* sp., *Monostroma* sp., *Caulerpa* sp., *Codium* sp., are commonly known as source of food. In Asia countries especially Japan, dried fronds of edible *Monostroma* sp. and *Enteromor‐ pha* sp are being known as ′aonori-green laver-ele ele-lulua-lumi boso′.These algae are eaten by humans as edible raw, dried, or cooked. They used in preperation of ′nori-jam′ soup

Proximate composition (moisture, ash, protein and oil content), total dietary fibre content and physicochemical properties of three brown and two red edible Spanish seaweeds, namely: *Himanthalia elongata* (sea spaghetti), *Bifurcaria bifurcata, Laminaria saccharina* (sweet kombu), *Mastocarpus stellatus* and *Gigartina pistillata* were studied. Ashes (24.9–36.4%) were high in all samples. Protein content ranged from 10.9 to 25.7%, being much higher for *Laminaria* (25.7%) followed by the red seaweeds (15.5–21.3%). Minor components were lipids (0.3–0.9%) in all samples except for *Bifurcaria* (5.6%).In conclusion, these seaweeds can be estimated as a good source of food fibre, protein and minerals for human consumption (Gómez-Ordóñez et al., 2010). Mineral content was determined in several brown (*Fucus vesiculosus, Laminaria digitata*, *Undaria pinnatifida*) and red (*Chondrus crispus, Porphyra tenera*)edible marine sea vegetables. Seaweeds contained high proportions of ash (21.1–39.3%) and sulphate (1.3–5.9%). In brown algae, ash content (30.1–39.3%) was higher than in red algae (20.6–21.1%). Edible brown and redseaweeds could be used as a food supplement to help meet the recommended daily intake of some essential minerals and trace elements (Rupérez, 2002). Sea spaghetti (*Himanthalia elongata*), Wakame (*Undaria pinnatifida*), and Nori (*Porphyra umbilicalis*), on fatty acid compo‐ sition, amino acid profile, protein score, mineral content and antioxidant capacity in low-salt meat emulsion model systems. The addition of seaweeds caused an increase in ω-3 polyun‐ saturated fatty acids (PUFA) and a decrease in the ω-6/ ω-3 PUFA ratio. In general, addition

Padina or sea fan ribbon weeds as a food dressing, soup or stew (Novaczek, 2001).

**3.3. Green seaweeds**

740 Food Industry

(Lobban and Harrison, 1994; Novaczek, 2001).

**4. Nutritonal composition of edible seaweeds**

Red macro-algae (*Gracilaria* spp.) are used as a fresh food in Hawaii. Species commonly marketed include *G. coronopifolia*, *G. parvispora*, *G. salicornia* and *G. tikvahiae*, however, these seaweeds have a short postharvest life of about 4 days (Paul and Chen, 2008). Seaweeds are a rich source of phytochemicals having anti-oxidant and antimicrobial properties. Presence of fibres and minerals helps in improving the mineral content reduce the salt content. The adding of seaweeds or their extracts to food products will help in reducing the utilization of chemical preservatives (Gupta and Abu-Ghannam, 2011). Edible sea‐ weeds contain various bioactive compounds with potential health benefits and their use as functional ingredients opens up new prospects for food processing, meat product formula‐ tions included. Seaweeds basically contain high proportions of polysaccharides along with various other potentially beneficial compounds such as good-quality protein and essen‐ tial fatty acids, particularly long-chain n-3 polyunsaturated fatty acids (PUFAs). Alginates are the most abundant ionicpolysaccharides present in brown seaweeds (Fernández-Martín *et al.,* 2009). Some seaweed polysaccharides are used by food industry as texture modifiers because of their high viscosity and gelling properties. In Asia seaweeds have been used for centuries in salads, soups and as low calorie dietetic foods. The diatery fibre which constitutes 25-75 % of the dry weight of marine algae and represents their major component, is primarily souble fibre.(Jiménez-Escrig and Sánchez-Muniz, 2000). In particular, miyeok (*Undaria pinnatifida*) is often served in soup,salad, and sidedishes. Gamma irradiation at 10 kGy is sufficient to sterilizefreeze-dried miyeokguk without significant deterioration in the sensory quality,and thus,the freeze-dried and irradiated miyeokguk at 10 kGy fulfills themicrobiological requirements as spacefood (Song *et al*., 2012). The sausages were produced with two types of carrageenan (i- and j-) in four levels (0%, 1%, 2% and 3%). Carrageenan had a better effect on such characteristics as pH, weight loss and lipid oxidation of the sausages, as well as, on sensory attributes. The carrageen‐ an level of 3% negatively affected the firmness of the sausages.Carrageenan added at levels up to 2% had a positive effect on the physicochemical and microbiological characteristics of the lowfat fermented sausages. (Koutsopoulos *et al*., 2008). Cultivated *Ulva rigida* was utilized by using marination technology. Fresh and boiled (at 100˚C for 2 min.) *Ulva rigida* were marinated with two different formulations by using 2 % lemon salt and 2 % vinegar. The marination of *Ulva rigida* were made at room temperature for 20 days. Marinated fresh and boiled ulva rigida by using lemon salt and vinegar can be an alternative for human foods (Kılınç *et al*., 2011). Breads were made by using *Lemna minor* (Tekogul *et al*., 2011) and *Ulva rigida* (Turan *et al*., 2011). The shelf-life of breads by using *Ulva rigida* were determined as unacceptable on day 5 at room temperature whereas on day 10 at 4˚C. When compared with control groups, the shelf-life of breads containing *Ulva rigida* were deter‐ mined longer shelf-life. Breads prepared with *Ulva rigida* extended the shelf-life of breads for 2 days in two different storage period. *Lemna minor* extended the shelf-life of breads. The shelf-life of breads with *Lemna minor* were extended the acceptable limit on day 8 at room temperature whereas on day 12 at 4 ˚C. But control group extended this acceptable limit on day 3 at room temperature, on day 8 at 4 ˚C (Tekogul *et al.,* 2011).

production, and the partial heavy metals mobilisation to enable the metal removal for improved fertiliser quality (Nkemka and Murto, 2012). The red alga *Chondracanthus squarrulosus* was cultured under semi-controlled conditions to valuate growth (biomass production) with agricultural fertilizers (ammonium nitrate, ammonium sulphate and urea) vs. analytical grade inorganic salts; sodium nitrate (analytical grade) and seawater were

Seaweeds for Food and Industrial Applications

http://dx.doi.org/10.5772/53172

743

Seaweeds are being studied on the use of many industrial applications such as food, cosmetics, chemistry, paint, medicine, etc., at nowadays. In Western countries has traditionally concen‐ trated on the extraction of compounds used by pharmaceutical, cosmetics, and food industries (Wijesinghe and Jeon, 2012a). Biologically active compounds of seaweeds (phlorotannins, carotenoids, alginic acid, fucoidan, peptides) have been demonstrated to play a significant role in prevention of certain degenerative diseases such as cancer, inflammation, arthritis, diabetes and hypertension. Therefore, seaweed derived active components, whose immense biochem‐ ical diversity looks like to become a rich source of novel chemical entities for the use as functional ingredients in many industrial applications such as functional foods, pharmaceut‐ icals and cosmeceuticals (Wijesinghe and Jeon, 2012b). Commercially available varieties of marine macroalgae are commonly used to as ′seaweeds′ Conventional, macroalgae can be classified as brown algae (Phaeophyta), red algae (Rhodophyta), and green algae (Chlorophy‐ ta), depending on their nutrient and chemical composition. Red and brown algae are mainly used as human food sources. The protein content of seaweed species varies greatly and demonstrates a dependence on such factors as season and environmental growth conditions. For example, the protein content of brown algae species, e.g., *Laminaria japonica*, *Hizikia fusiforme* or *Undaria pinnatifida*, is relatively low with 7–16 g/100 g dry weight (d.w.) (Jurković *et al.*, 1995; Kolb *et al.,* 1999; Rupérez and Saura-Calixto, 2001). On the other hand, red algae, e.g., *Palmaria palmata* (Dulse) and *Porphyra tenera* contain 21–47 g protein/100 g d.w. (Fleurence, 1999; Rupérez and Saura-Calixto, 2001).The protein in algae contains all essential amino acids (EAA) and all EAA are available throughout the year although seasonal variations in their concentrations are known to occur (Galland-Irmouli *et al.,* 1999). For example, the proportion of EAA is 45–49% in *Hizikia* sp. and *Eisenia bicyclis* (Arame). In both these brown algae varieties, Ecological factory is the first limiting EAA, followed by Lys (Kolb *et al*., 1999). The EAA contents of some species (e.g., *Porphyra* sp.) can be compared with those of soy and egg protein (Fleurence, 1999; Galland-Irmouli *et al*., 1999). In addition to, high concentrations of Arg, Asp and Glu peptides are found in many macroalgae species (Fleurence, 1999). The fat content of marine macroalgae accounts for 1–6 g/100 g d.w. (Fleurence *et al*., 1994; Jurković *et al*., 1995; Herbreteau *et al*., 1997). In some brown algae varieties, such as *Hizikia* sp. and *Eisenia bicyclis* (Arame), only 0.7–0.9 g/100 g d.w. of fat content were found (Kolb *et al.,* 1999). Brown seaweeds are rich in fucose rich sulfated polysaccharides fucoidans (Wijesinghe and Jeon, 2012a). Polysaccharides produced by marine seaweeds form the basis of an economically important and expanding global industry. Key products are agars, agaroses, algins, and carrageenans.

used as controls (Pacheco-Ruiz *et al*., 2004).

**6. Conclusion and outlook**

#### **5.1. Fermented seaweed**

Brown edible seaweeds as a sole source of nutrition for the growth of lactic acid bacteria. Growth kinetics of lactic acid bacteria (LAB; *Lactobacillus plantarum*) was studied using three species of edible Irish brown seaweeds *Himanthalia elongata*, *Laminaria digitata* and *Laminaria saccharina*. The results of this study present an indication of the potential of fermentation of seaweeds using LAB with a possibility towards the development of a range of functional foods (Gupta *et al*., 2011). Low molecular weight polysaccharides from seaweed as prebiotics. *Gelidium* seaweed showed significant increase in bifidobacterial populations. Agar and alginate bearing seaweeds indicate prebiotic potential (Ramnani *et al*., 2012). Brown macroal‐ gae contain high concentration of mannitol and laminarian. *Clostrium acetobutylicum* ferments these seaweed extract substrates to butanol. Seaweed fermentation exhibited triauxic growth: glucose-mannitol- laminarin.Butanol yields in seaweed and pure glucose fermentations were comparable (Huesemann *et al*., 2012).

#### **5.2. Seaweeds used as fertilizer and biogas production**

Seaweed are used as a fertilizer which is suitable for use in organic agriculture (López-Mosquera *et al.,* 2011). Energy-rich methane can be harnessed from seaweed deposits by anaerobic digestion. However, the high heavy metal content in the seaweed and its digestates limits their use as fertilisers. The efficient utilisation of seaweed for biogas

production, and the partial heavy metals mobilisation to enable the metal removal for improved fertiliser quality (Nkemka and Murto, 2012). The red alga *Chondracanthus squarrulosus* was cultured under semi-controlled conditions to valuate growth (biomass production) with agricultural fertilizers (ammonium nitrate, ammonium sulphate and urea) vs. analytical grade inorganic salts; sodium nitrate (analytical grade) and seawater were used as controls (Pacheco-Ruiz *et al*., 2004).

## **6. Conclusion and outlook**

Gamma irradiation at 10 kGy is sufficient to sterilizefreeze-dried miyeokguk without significant deterioration in the sensory quality,and thus,the freeze-dried and irradiated miyeokguk at 10 kGy fulfills themicrobiological requirements as spacefood (Song *et al*., 2012). The sausages were produced with two types of carrageenan (i- and j-) in four levels (0%, 1%, 2% and 3%). Carrageenan had a better effect on such characteristics as pH, weight loss and lipid oxidation of the sausages, as well as, on sensory attributes. The carrageen‐ an level of 3% negatively affected the firmness of the sausages.Carrageenan added at levels up to 2% had a positive effect on the physicochemical and microbiological characteristics of the lowfat fermented sausages. (Koutsopoulos *et al*., 2008). Cultivated *Ulva rigida* was utilized by using marination technology. Fresh and boiled (at 100˚C for 2 min.) *Ulva rigida* were marinated with two different formulations by using 2 % lemon salt and 2 % vinegar. The marination of *Ulva rigida* were made at room temperature for 20 days. Marinated fresh and boiled ulva rigida by using lemon salt and vinegar can be an alternative for human foods (Kılınç *et al*., 2011). Breads were made by using *Lemna minor* (Tekogul *et al*., 2011) and *Ulva rigida* (Turan *et al*., 2011). The shelf-life of breads by using *Ulva rigida* were determined as unacceptable on day 5 at room temperature whereas on day 10 at 4˚C. When compared with control groups, the shelf-life of breads containing *Ulva rigida* were deter‐ mined longer shelf-life. Breads prepared with *Ulva rigida* extended the shelf-life of breads for 2 days in two different storage period. *Lemna minor* extended the shelf-life of breads. The shelf-life of breads with *Lemna minor* were extended the acceptable limit on day 8 at room temperature whereas on day 12 at 4 ˚C. But control group extended this acceptable

limit on day 3 at room temperature, on day 8 at 4 ˚C (Tekogul *et al.,* 2011).

Brown edible seaweeds as a sole source of nutrition for the growth of lactic acid bacteria. Growth kinetics of lactic acid bacteria (LAB; *Lactobacillus plantarum*) was studied using three species of edible Irish brown seaweeds *Himanthalia elongata*, *Laminaria digitata* and *Laminaria saccharina*. The results of this study present an indication of the potential of fermentation of seaweeds using LAB with a possibility towards the development of a range of functional foods (Gupta *et al*., 2011). Low molecular weight polysaccharides from seaweed as prebiotics. *Gelidium* seaweed showed significant increase in bifidobacterial populations. Agar and alginate bearing seaweeds indicate prebiotic potential (Ramnani *et al*., 2012). Brown macroal‐ gae contain high concentration of mannitol and laminarian. *Clostrium acetobutylicum* ferments these seaweed extract substrates to butanol. Seaweed fermentation exhibited triauxic growth: glucose-mannitol- laminarin.Butanol yields in seaweed and pure glucose fermentations were

Seaweed are used as a fertilizer which is suitable for use in organic agriculture (López-Mosquera *et al.,* 2011). Energy-rich methane can be harnessed from seaweed deposits by anaerobic digestion. However, the high heavy metal content in the seaweed and its digestates limits their use as fertilisers. The efficient utilisation of seaweed for biogas

**5.1. Fermented seaweed**

742 Food Industry

comparable (Huesemann *et al*., 2012).

**5.2. Seaweeds used as fertilizer and biogas production**

Seaweeds are being studied on the use of many industrial applications such as food, cosmetics, chemistry, paint, medicine, etc., at nowadays. In Western countries has traditionally concen‐ trated on the extraction of compounds used by pharmaceutical, cosmetics, and food industries (Wijesinghe and Jeon, 2012a). Biologically active compounds of seaweeds (phlorotannins, carotenoids, alginic acid, fucoidan, peptides) have been demonstrated to play a significant role in prevention of certain degenerative diseases such as cancer, inflammation, arthritis, diabetes and hypertension. Therefore, seaweed derived active components, whose immense biochem‐ ical diversity looks like to become a rich source of novel chemical entities for the use as functional ingredients in many industrial applications such as functional foods, pharmaceut‐ icals and cosmeceuticals (Wijesinghe and Jeon, 2012b). Commercially available varieties of marine macroalgae are commonly used to as ′seaweeds′ Conventional, macroalgae can be classified as brown algae (Phaeophyta), red algae (Rhodophyta), and green algae (Chlorophy‐ ta), depending on their nutrient and chemical composition. Red and brown algae are mainly used as human food sources. The protein content of seaweed species varies greatly and demonstrates a dependence on such factors as season and environmental growth conditions. For example, the protein content of brown algae species, e.g., *Laminaria japonica*, *Hizikia fusiforme* or *Undaria pinnatifida*, is relatively low with 7–16 g/100 g dry weight (d.w.) (Jurković *et al.*, 1995; Kolb *et al.,* 1999; Rupérez and Saura-Calixto, 2001). On the other hand, red algae, e.g., *Palmaria palmata* (Dulse) and *Porphyra tenera* contain 21–47 g protein/100 g d.w. (Fleurence, 1999; Rupérez and Saura-Calixto, 2001).The protein in algae contains all essential amino acids (EAA) and all EAA are available throughout the year although seasonal variations in their concentrations are known to occur (Galland-Irmouli *et al.,* 1999). For example, the proportion of EAA is 45–49% in *Hizikia* sp. and *Eisenia bicyclis* (Arame). In both these brown algae varieties, Ecological factory is the first limiting EAA, followed by Lys (Kolb *et al*., 1999). The EAA contents of some species (e.g., *Porphyra* sp.) can be compared with those of soy and egg protein (Fleurence, 1999; Galland-Irmouli *et al*., 1999). In addition to, high concentrations of Arg, Asp and Glu peptides are found in many macroalgae species (Fleurence, 1999). The fat content of marine macroalgae accounts for 1–6 g/100 g d.w. (Fleurence *et al*., 1994; Jurković *et al*., 1995; Herbreteau *et al*., 1997). In some brown algae varieties, such as *Hizikia* sp. and *Eisenia bicyclis* (Arame), only 0.7–0.9 g/100 g d.w. of fat content were found (Kolb *et al.,* 1999). Brown seaweeds are rich in fucose rich sulfated polysaccharides fucoidans (Wijesinghe and Jeon, 2012a). Polysaccharides produced by marine seaweeds form the basis of an economically important and expanding global industry. Key products are agars, agaroses, algins, and carrageenans.

These are used on ingredients in food, pharmaceuticals and diverse consumer products and industrial processes (Renn, 1997). Red algae (e.g., *Porphyra* sp.) have high concentrations of eicosapentaenoic acid (C20:5, ω -3, EPA),with 48.0–51.0% of total fatty acid methyl esters (FAME), and marginal concentrations of arachidonic acid (C20:4, ω-6, ARA), with 2.1–10.9% of total FAME and, linoleic acid (C18:2, ω -6, LA), with 1.3–2.5% of total FAME (Fleurence *et al*., 1994; Takagi *et al*., 1985). In contrast, brown algae (e.g., *Laminaria* sp., *Undaria* sp., *Hizikia* sp.) have high concentrations of oleic acid (C18:1, ω -9, OA) with 4.1–20.9% of total FAME, LA with 4.0–7.3% of total FAME as well as α-linolenic acid (C18:3, ω -3, ALA) with 3.6–13.8% of total FAME but low concentrations of EPA with 5.9–13.6% of total FAME (Fleurence *et al.,* 1994; Takagi *et al.,* 1985). Interestingly, in *Porphyra* sp., *Laminaria* sp., and *Undaria* sp., the concen‐ trations of docosahexaenoic acid (C22:6, ω -3, DHA) and docosapentaenoic acid (C22:5, ω -3, DPA) were below the detection limit (less than 0.1% of total FAME (Fleurence *et al*., 1994; Takagi *et al.,* 1985).The types and abundance of carbohydrates vary strongly between algae species. Typical carbohydrates in red algae varieties consist of floridean starch (*α*-1.4-binding glucan), cellulose, xylan, and mannan. The water-soluble fibre fraction is formed by sulfurcontaining galactans, e.g., agar and carrageen (Jiménez-Escrig and Sánchez-Muniz, 2000; Van den Hoek *et al*., 1993). The typical carbohydrates in brown algae varieties consist of fucoidan, laminaran (*β*-1.3-glucan), cellulose, alginates, and mannitol. Brown algae fibres are mainly cellulose and insoluble alginates. Alginates are Ca, Mg, or Na salts of alginic acid (1.4-linked polymer of *β*-*d*-mannuronic acid and *α-l*-guluronic acid). The amorphous, slimy fraction of brown algae fibres consists mainly of water-soluble alginates and/or fucoidan. Main reserve polysaccharides of Phaeophyta are laminaran (*β*-1.3-glucan) and mannitol (Kolb *et al.,* 1999; Dawczynski *et al*., 2007). The typical algae carbohydrates are not digestible by the human gastrointestinal tract and, therefore, they are dietary fibres. The content of total dietary fibre ranges from 33–50 g/100 g d.w. (Jiménez-Escrig and Cambrodon, 1999, Lahaye, 1991). Ac‐ cordingly, the fibre content of seaweed varieties is higher than those found in most fruits and vegetables. The human consumption of algal fibre has been proven to be health-promoting and it benefits are well documented in the scientific literature. The consumption of this dietary fibre has been related to the following health promoting effects: **1)** its consumption promotes the growth and protection of the beneficial intestinal flora (Fujii *et al*., 1992, Goni *et al*., 2001), **2)** its consumption, in combination with high glycemic load foods, reduces the overall glycemic response, macroalgae fibre acts as a hypoglycaemic (Goni, Valdivieso, & Garcia-Alonso, 2000), **3)** its consumption greatly increases stool volume (Jiménez-Escrig & Sánchez-Muniz, 2000) and **4)** its consumption reduces the risk of colon cancer (Guidel-Urbano & Goni, 2002). In addition, seaweeds varieties are rich sources of vitamin C, vitamin B-complex, e.g., folic acid and B12, and vitamin A precursors, such as *β*-carotene (McDermid and Stuercke, 2003, Takenaka *et al.,* 2001; Watanabe *et al*., 2002). Because the seaweed species are rich in beneficial nutrients, in countries such as China, Japan, and Korea, they have been commonly utilised in human alimentation (since ancient times) (Lahaye, 1991). For example, Japanese people consume more than 1.6 kg algae (d.w.) per year *per capita* (Fleurence, 1999). In addition to their importance as traditional the Asian foods, macroalgae species are utilised industrially as a source of hydrocolloids, such as agar, carrageen, and alginate (Jiménez-Escrig & Sánchez-Muniz, 2000). Over the past few decades, the consumption of seaweed products has increased

in European countries. Currently, approximately 15–20 edible algae strains are being com‐ monly marketed for consumption in Europe. These seaweed varieties differ greatly in their quality, colour, consistency, and nutrient content. Nowadays, for this reason the studies of algology evaluate and compares the nutrient and chemical contents of many commercially available seaweed products which were locally purchased in European food stores and

, Hatice Tekogul2

1 Ege University Fisheries Faculty, Dept. Of Fisheries and Seafood Processing Technology,

2 Ege University Fisheries Faculty, Dept. of Aquaculture Algae Culture Laboratory, Borno‐

[1] Bold, H. C, & Wyne, M. J. (1985). *Introduction to the algae: Structure and Reproduction*,

[3] Dawczynski, C, Schubert, R, & Jahreis, G. (2007). Amino acids, fatty acids, and dietary

[4] De Roeck-holtzhauer, J. (1991). Uses of Seaweeds in Cosmetics. *In:* Seaweed Resources in Europe: Uses and Potential. M. G. Guiry andn G. Blunden (editors). John Wiley and

[5] Fujii, T, Kuda, T, Saheki, K, & Okuzumi, M. (1992). Fermentation of water-soluble polysaccharides of brown algae by human intestinal bacteria *in vitro*, *Nippon Suisan*

[6] Fleurence, J, Gutbier, G, Mabeau, S, & Leray, C. (1994). Fatty acids from 11 marine macroalgae of the French Brittany coast, *Journal of Applied Phycology*, , 6, 527-532. [7] Fleurence, J. (1999). Seaweed proteins: Biochemical, nutritional aspects and potential

[8] Fernández-martín, F, López-lópez, I, & Cofrades, S. Jiménez Colmenero F. ((2009). Influence of adding Sea Spaghetti seaweed and replacing the animal fat with olive oil or a konjac gel on pork meat batter gelation. Potential protein/alginate association. *Meat*

[2] Chapman, V. J. (1970). *Seaweeds and Their Uses*, Chapman & Hall. London, , 334.

and Edis Koru2

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speciality shops (Herbreteau *et al.,* 1997; Dawczynski *et al*., 2007).

, Gamze Turan2

Second Edition, New Jersey, Prentice-Hall, Inc., USA, , 720.

fibre in edible seaweed products, *J. of Food Chemistry*, , 103

uses, *Trends in Food Science and Technology*, , 10, 25-28.

**Author details**

Bornova, Izmir, Turkey

va, Izmir, Turkey

**References**

, Semra Cirik2

Sons, Ltd. England, , 83-93.

*Gakk*, , 58, 149-152.

*Science,* , 83, 209-217.

Berna Kılınç<sup>1</sup>

in European countries. Currently, approximately 15–20 edible algae strains are being com‐ monly marketed for consumption in Europe. These seaweed varieties differ greatly in their quality, colour, consistency, and nutrient content. Nowadays, for this reason the studies of algology evaluate and compares the nutrient and chemical contents of many commercially available seaweed products which were locally purchased in European food stores and speciality shops (Herbreteau *et al.,* 1997; Dawczynski *et al*., 2007).

## **Author details**

These are used on ingredients in food, pharmaceuticals and diverse consumer products and industrial processes (Renn, 1997). Red algae (e.g., *Porphyra* sp.) have high concentrations of eicosapentaenoic acid (C20:5, ω -3, EPA),with 48.0–51.0% of total fatty acid methyl esters (FAME), and marginal concentrations of arachidonic acid (C20:4, ω-6, ARA), with 2.1–10.9% of total FAME and, linoleic acid (C18:2, ω -6, LA), with 1.3–2.5% of total FAME (Fleurence *et al*., 1994; Takagi *et al*., 1985). In contrast, brown algae (e.g., *Laminaria* sp., *Undaria* sp., *Hizikia* sp.) have high concentrations of oleic acid (C18:1, ω -9, OA) with 4.1–20.9% of total FAME, LA with 4.0–7.3% of total FAME as well as α-linolenic acid (C18:3, ω -3, ALA) with 3.6–13.8% of total FAME but low concentrations of EPA with 5.9–13.6% of total FAME (Fleurence *et al.,* 1994; Takagi *et al.,* 1985). Interestingly, in *Porphyra* sp., *Laminaria* sp., and *Undaria* sp., the concen‐ trations of docosahexaenoic acid (C22:6, ω -3, DHA) and docosapentaenoic acid (C22:5, ω -3, DPA) were below the detection limit (less than 0.1% of total FAME (Fleurence *et al*., 1994; Takagi *et al.,* 1985).The types and abundance of carbohydrates vary strongly between algae species. Typical carbohydrates in red algae varieties consist of floridean starch (*α*-1.4-binding glucan), cellulose, xylan, and mannan. The water-soluble fibre fraction is formed by sulfurcontaining galactans, e.g., agar and carrageen (Jiménez-Escrig and Sánchez-Muniz, 2000; Van den Hoek *et al*., 1993). The typical carbohydrates in brown algae varieties consist of fucoidan, laminaran (*β*-1.3-glucan), cellulose, alginates, and mannitol. Brown algae fibres are mainly cellulose and insoluble alginates. Alginates are Ca, Mg, or Na salts of alginic acid (1.4-linked polymer of *β*-*d*-mannuronic acid and *α-l*-guluronic acid). The amorphous, slimy fraction of brown algae fibres consists mainly of water-soluble alginates and/or fucoidan. Main reserve polysaccharides of Phaeophyta are laminaran (*β*-1.3-glucan) and mannitol (Kolb *et al.,* 1999; Dawczynski *et al*., 2007). The typical algae carbohydrates are not digestible by the human gastrointestinal tract and, therefore, they are dietary fibres. The content of total dietary fibre ranges from 33–50 g/100 g d.w. (Jiménez-Escrig and Cambrodon, 1999, Lahaye, 1991). Ac‐ cordingly, the fibre content of seaweed varieties is higher than those found in most fruits and vegetables. The human consumption of algal fibre has been proven to be health-promoting and it benefits are well documented in the scientific literature. The consumption of this dietary fibre has been related to the following health promoting effects: **1)** its consumption promotes the growth and protection of the beneficial intestinal flora (Fujii *et al*., 1992, Goni *et al*., 2001), **2)** its consumption, in combination with high glycemic load foods, reduces the overall glycemic response, macroalgae fibre acts as a hypoglycaemic (Goni, Valdivieso, & Garcia-Alonso, 2000), **3)** its consumption greatly increases stool volume (Jiménez-Escrig & Sánchez-Muniz, 2000) and **4)** its consumption reduces the risk of colon cancer (Guidel-Urbano & Goni, 2002). In addition, seaweeds varieties are rich sources of vitamin C, vitamin B-complex, e.g., folic acid and B12, and vitamin A precursors, such as *β*-carotene (McDermid and Stuercke, 2003, Takenaka *et al.,* 2001; Watanabe *et al*., 2002). Because the seaweed species are rich in beneficial nutrients, in countries such as China, Japan, and Korea, they have been commonly utilised in human alimentation (since ancient times) (Lahaye, 1991). For example, Japanese people consume more than 1.6 kg algae (d.w.) per year *per capita* (Fleurence, 1999). In addition to their importance as traditional the Asian foods, macroalgae species are utilised industrially as a source of hydrocolloids, such as agar, carrageen, and alginate (Jiménez-Escrig & Sánchez-Muniz, 2000). Over the past few decades, the consumption of seaweed products has increased

744 Food Industry

Berna Kılınç<sup>1</sup> , Semra Cirik2 , Gamze Turan2 , Hatice Tekogul2 and Edis Koru2

1 Ege University Fisheries Faculty, Dept. Of Fisheries and Seafood Processing Technology, Bornova, Izmir, Turkey

2 Ege University Fisheries Faculty, Dept. of Aquaculture Algae Culture Laboratory, Borno‐ va, Izmir, Turkey

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## *Edited by Innocenzo Muzzalupo*

Due to the increase in world population (more than seven billion inhabitants) the global food industry has the largest number of demanding and knowledgeable consumers. This population requires food products that fulfill the high quality standards established by the food industry organizations. Food shortages threaten human health, and also the disastrous extreme climatic events make food shortages even worse. This collection of articles is a timely contribution to issues relating to the food industry. The objective of this book is to provide knowledge appropriate for students, university researchers, and in general, for anyone wishing to obtain knowledge of food processing and to improve the food product quality.

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Food Industry

Food Industry