Food Chemistry 225 (2017) 10–22
Contents lists available at ScienceDirect
Food Chemistry journal homepage: www.elsevier.com/locate/foodchem
Review
Bioactives from fruit processing wastes: Green approaches to valuable chemicals Jhumur Banerjee a, Ramkrishna Singh a, R. Vijayaraghavan b, Douglas MacFarlane b, Antonio F. Patti b, Amit Arora a,⇑ a b
CTARA, IITB-Monash Research Academy, IIT Bombay, Mumbai, Maharashtra 400076, India School of Chemistry, Faculty of Science, Monash University, Clayton Campus, VIC 3800, Australia
a r t i c l e
i n f o
Article history: Received 2 August 2016 Received in revised form 6 December 2016 Accepted 27 December 2016 Available online 28 December 2016 Keywords: Fruit processing waste Bioactives Biorefinery Nutraceuticals
a b s t r a c t Fruit processing industries contribute more than 0.5 billion tonnes of waste worldwide. The global availability of this feedstock and its untapped potential has encouraged researchers to perform detailed studies on value-addition potential of fruit processing waste (FPW). Compared to general food or other biomass derived waste, FPW are found to be selective and concentrated in nature. The peels, pomace and seed fractions of FPW could potentially be a good feedstock for recovery of bioactive compounds such as pectin, lipids, flavonoids, dietary fibres etc. A novel bio-refinery approach would aim to produce a wider range of valuable chemicals from FPW. The wastes from majority of the extraction processes may further be used as renewable sources for production of biofuels. The literature on value addition to fruit derived waste is diverse. This paper presents a review of fruit waste derived bioactives. The financial challenges encountered in existing methods are also discussed. Ó 2017 Elsevier Ltd. All rights reserved.
Contents 1. 2. 3.
4. 5. 6. 7.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Current use and disposal Patterns for FPW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Composition and application of FPW based bioactives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Bioactive carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Proteins and peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Lipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4. Polyphenols and other secondary metabolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5. Pharmaceutical excipients from FPW. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Extraction of bioactive compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Conventional vs modern extraction methods for FPW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Identification of challenges in valorisation of FPW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Role of fractionation in extraction of bioactives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Economic considerations and industrial examples of FPW utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concluding remarks and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
⇑ Corresponding author at: Indian Institute of Technology, Powai, Maharashtra, India. E-mail address:
[email protected] (A. Arora). http://dx.doi.org/10.1016/j.foodchem.2016.12.093 0308-8146/Ó 2017 Elsevier Ltd. All rights reserved.
11 11 11 13 14 14 14 14 15 15 15 17 18 19 20 20
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
1. Introduction The vast imbalance between food production and consumption may be estimated from the fact that on average 30–40% of food is wasted in many parts of the world (Laufenberg, Kunz, & Nystroem, 2003; Parfitt, Barthel, & Macnaughton, 2010; Wadhwa & Bakshi, 2013). Out of many factors contributing to the global environmental burden in recent years, the effect of fruit waste has been identified as a major concern. For instance, the fraction of discarded materials in the majority of fruit processing industries is typically very high (Laufenberg et al., 2003; Parfitt et al., 2010) depending on the location and method of harvest (e.g. mango 30–50%, banana 20%, pomegranate 40–50% and citrus 30–50%). This fruit waste, being rich in moisture and microbial loads, lead directly to environmental pollution. Processing industries, especially in developing countries, face the constraints of finance, space and in some cases stringent government regulations with respect to waste disposal. The majority of these industries are micro and small-scale which mainly fall under informal sector and, thus, processing waste is considered to be of negligible value compared to the processed fruit. The current classification of FPW (fruit processing waste) as ‘‘general waste” makes it an ignored feedstock globally. Compared to developed countries such as Europe, where the fruit and vegetable processing waste was found to be fifth highest contributor (8% of total food waste) to overall food waste (Fava, Totaro, Diels, Reis, Duarte, Carioca, H, M., Ferreira, & B. S., 2015), majority of the fruit and vegetable processing sector data for developing countries was found to be fragmented and insufficient (Wadhwa & Bakshi, 2013). Primary data from developing countries indicate that large scale industries process FPW into biogas or compost it to obtain biofertilizer. Waste from organized and unorganized processing industries, with the exception of very few major composting and biogas generation facilities, is for the most part disposed of through municipal waste disposal systems. Many recent reports have focussed on food waste recovery (Pfaltzgraff, De bruyn, Cooper, Budarin, & Clark, 2013) and general approaches to lignocellulosic biomass value addition from this waste (Credou & Berthelot, 2014; Van Dyk & Pletschke, 2012). The segregation and study of FPW as a particular type of food waste helps in the development of additional biorefinery processes and ultimately improve the economics of food waste based bio-refinery concept. With respect to waste reduction and recovery, a biorefinery operation would have a substantial incentive to develop products and processes for byproduct and waste utilization. This paper will review current status of FPW utilization and valorisation and discuss its potential as a bio-refinery feedstock of the future.
2. Current use and disposal Patterns for FPW Millions of dollars are spent globally to dispose of FPW (OkinoDelgado & Fleuri, 2015). For instance, in Europe, the disposal of 1 tonne of solid waste or 1 m3 of effluent costs $28–60 which includes a landfill tax of $10 (Gendebien et al., 2001). In developing countries such as India, the average transportation cost was found to be $11–15 per tonne per trip (FICCI, 2010) which may indicate > $300 million for total landfilling cost. Land filling term in Indian context is implicitly filling of dumping grounds with solid waste. Due to high moisture content of fruit waste, incineration may not be efficient and viable option compared to general solid waste. Though landfilling is a standard disposal method, it is the least economical way to deal with this global issue. Landfilling is also associated with risks of greenhouse gas emissions (Roggeveen, 2010). For example, global food processing waste related greenhouse gas emission was found to be the third highest contributor after total emissions for China and USA (Eckard & Victoria, 2008; FAO,
11
2013). FPW accounted for 16% of this total food waste with a contribution of 6% (>20 million tonnes of carbon dioxide equivalent) of global greenhouse gas emissions (FAO, 2013), (mainly methane and nitrous oxide due to decomposition inside landfills). Asia, Europe and North America were found to be the highest contributors (FAO, 2013; NGWA, 2016). The valorisation of FPW as a soil improvement additive is a common approach which is followed extensively in many countries. Composting and the use of charcoal has a long history in agriculture (Sener et al., 2015) and has been used to promote agronomic productivity for centuries. This tradition can be modernized by way of pyrolysis equipment especially engineered to heat the biomass at designated temperatures in the absence of oxygen. The resulting product is termed as biochar. Biochar can potentially provide a number of benefits to the soil including carbon sequestration, improve quality of acidic soil by increasing the pH of the soil, habitat for microorganisms and exchange sites for plant nutrient support. Contrary to composting, it provides a significant reduction of greenhouse gas emissions (Sener et al., 2015), thus, biochar materials are receiving significant attention from scientists, engineers and farmers. To date several exploratory studies have assessed the response of bacteria, fungi, and enzymes to biochar (Lehmann, Rillig, Thies, Masiello, Hockaday, & Crowley, 2011) incorporation into soil. Various critical examinations of the effects of biochar on crop yields and soil properties have indicated that different outcomes are obtained, both beneficial and negative, depending on a number of variables. These include, the type of biomass used to produce the biochar, conditions used to make the biochar, soil type, addition of other components (e.g. minerals and other plant nutrients) climate and the interaction between microbiota and the active substances (e.g. polyphenols) and the effect of sorption of minerals due to the differential porosity. Significant further research, especially in the understanding of plant nutrients from FPW, is needed to understand the effects of these different variables on the efficacy of biochar (Lehmann et al., 2011; Mlambo & Mapiye, 2015). Looking at the availability of biomass other than FPW, it seems that FPW may not provide greater advantages when compared with other agricultural residues, in soil improvement alone. However, the key issues to be addressed are nutrient recovery from the feedstock into soil.
3. Composition and application of FPW based bioactives Various compositional studies of the FPW suggests presence of a wide range of bioactive compounds in different residual fractions. These bioactive compounds are essentially primary and secondary metabolites of plants. Phenolics, alkaloids, glycosides (the active metabolite bound to a sugar moiety), volatile oils, mucilage, gums and oleoresins are some of the examples of secondary metabolites (Biesalski, Dragsted, Elmadfa, Grossklaus, Muller, Schrenk, Walter, & Weber, 2009). Bioactive-rich extracts may be used in a diverse range of novel applications due to the proven health effects on long term consumption. Apart from being a rich source of bioactive carbohydrates such as pectin, FPW may be an important source for recovery of cellulose from peels (Pfaltzgraff, De bruyn, M., Cooper, E. C., Budarin, V., & Clark, & J. H., 2013), hemicellulose from pomace (Chantaro, Devahastin, & Chiewchan, 2008; Scheller & Ulvskov, 2010; Singh, Banerjee, & Arora, 2015), lignin (Van Dyk & Pletschke, 2012) from peels and seed coats (Van Dyk & Pletschke, 2012; Scheller & Ulvskov, 2010). Cellulose can be converted into sugars and further to biofuels and biochemicals. Mesoporous cellulose can also be obtained as a by-product of pectin extraction. It was found to be effective in variety of applications such as catalysis, chemical sensors and molecular separation as a
12
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
Fig. 1. Bioactives present in a model fruit processing waste and recent trend in applications.
Table 1 Proximate composition analysis of various fruit processing waste (values denoted in%). Waste
Moisture Fat
Carbohydrate Pectin
Cellulose Lignin HemiCrude cellulose protein
Starch Ash
Crude fibre
Reference (Nawirska & Kwas´niewska, 2005) (Al-Sayed & Ahmed, 2013)
Apple pomace 3.9–5.4 (dry) Watermelon rinds 10.6 (wet) Potato peels 60–70
3.4–3.9
48–62
3.5–14.2
8.5
20.4
24.4
4.4–5.6
–
1.6
4.7–48.7
2.4
56
19–21
20
10
23
11.2
–
13
17.28
0.6–1
60.2–63
3–4
55.2
14.2
11.7
16.7–17
66–70 7–8
7–9
Watermelon seeds Tomato pomace
6–7
21.9
26.3
–
31
–
17
16.3–17
–
2.4
22.2
84.7
0.3
4.5
2
9.1
5.3
11
7.3
0.5–1
0.7
7–10
Carrot waste
5–6
1.0–1.2
32
3.8
30
32.2
12.3
8.6
–
9.07 8.6
Pomegranate peel
13.7
1.7
80.5
27.9
26.2
5.6
10.8
3.1
–
3.3
membrane (Pfaltzgraff et al., 2013). Fig. 1 shows a model fruit waste as a source of bioactive compounds. In general, seeds contain bioactive lipids and polyphenols while peels are a rich source of dietary fibres. The recent trend in various bioactive based appli-
11.2
(Mukherjee, Adhikari, & Rai, 2008) (Wani et al., 2008) (Del Valle, Cámara, & Torija, 2006) (Nawirska & Kwas´niewska, 2005) (Ullah, Ali, Khan, Khurram, Hussain, & Rahman, 2012)
cation area is also shown which predicts that value added chemicals surround the largest part of recent studies. The food and health applications from these extracted bioactive compounds is an important ongoing field of research.
13
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22 Table 2 Bioactives present in fruit processing waste. Bioactives
Sources
Average Concentration range
Bioactivity
Antioxidant assay values
Possible Usage
Reference
Flavonols
Tomato pomace, pomegranate peels, orange peels, tamarind seeds, mango peels
0.02–0.14% w/w on wet basis
Antioxidant
124–453 mmol/g (FRAP assay)
(Cam, Icyer, & Erdogan, 2014)
Phenolic acids (Ferulic acid, Vanillic acid, Caffeic acid) Flavonones
Mango peels & kernel, guava seeds, orange peel, wheat germ waste, apple pomace
0.02–0.2% w/w
Antioxidants
200–1200 ppm (FRAP assay)
Citrus peels, Cucumber peels, tomato peel, citrus seeds
2–14% w/w
Antioxidant
100 lg/ml 1000 lg/ml (FRAP assay)
Anthocyanidines
Grape waste, berry pomaces, sapota pomaces, corn cob waste, Litchi pericarp and seeds
0.8%w/w
90 mM (antiinflammatory assay)
Carotenoids
Tomato peel, mango peel, Papaya peels, pumpkin seeds
0.07–0.1%w/w
Food colour additive, Antioxidant, anticancer Radical scavenger
Natural preservatives Anticancer agents Natural preservatives Anticancer agents Cardioprotective agents Pain relievers in arthritis Pain relievers Anticancer agents
Anthocyanins
Watermelon peels, Pomegranate pith and carp
1–1.5%w/w
Chemopreventive, antioxidant
Anticancer antiageing formulations Anticancer
(Huchin, Estrada, Estrada, Cuevas, & Sauri, 2013) (Al-Sayed & Ahmed, 2013)
Saponins
Sapota seeds
Antibacterial
Amino acids and proteins Pectins
Kinnow-mandarin waste, pineapple peels, papaya peels, Mango peel, apple pomace, citrus peels, banana peels
0.09–0.13% w/w 7–13%w/w
(Kothari & Seshadri, 2010) (El-Safy, Salem, & Abd El-Ghany, 2012) (Emaga et al., 2008)
Lignans & xyloglucans
Watermelon rinds, tamarind seed
17–30%w/w
Dietary fibres
Watermelon rind, Flax seed cake, tamarind seeds, carrot peel and pomace Apple peels, banana stem
30–60%w/w
Antibacterial formulations Protein rich food substitute Gelling agents in food Fat free food additive Fat substitutents anti-obesity Swellable polymer in food Low calorie food Pharmaceuticals
Pomegranate seed, mango kernel, tomato seed
10–30%w/w
Glycosides
Bioactive lipids
12–30%w/w
0.02–1%w/w
Protein source for malnutrition Food additive, thickening agent
Dietary fibre, food additives Intestinal health promoter, skin regeneration, Anticancer, antioxidant, Source of essential and non essential fatty acids
0.2–3.3 mol trolox equivalent/mol (FRAP assay) 4-6 mmol/L of extract (FRAP assay) 13–25 lM for DPPH assay NA NA
NA NA
0.5–2 mM trolox equivalent (FRAP assay) NA
Nutraceuticals Antiobesity formulations
(Kothari & Seshadri, 2010)
(Attard et al., 2014)
(Yu, Dandekar, Toledo, Singh, & Patil, 2007)
(Al-Sayed & Ahmed, 2013) (Roeck, Sila, Duvetter, Van Loey, & Hendrickx, 2008) (Milner & Romagnolo, 2010) (Mandawgade & Patravale, 2008)
[%w/w: % of total mass taken, FRAP: Ferric reducing antioxidant power, DPPH: 2,2-diphenyl-1 picrylhydrazyl]; NA is not available.
The proximate composition of various FPW are presented in Table 1. The various bioactive fractions that are available in FPW generally include carbohydrates, proteins, lipids and secondary metabolites as summarised in Table 2 and discussed further in detail below. 3.1. Bioactive carbohydrates Polysaccharides constitute a diverse family of natural polymers comprised of aldoses and/or ketoses linked via glycosidic linkages (Miller, 2004). They can be classified as homoglycans and heteroglycans (Miller, 2004) depending upon the kind of monosaccharide as constituent unit. These polysaccharides show a range of bioactivity such as anticancer and anti-inflammatory actions (Morris, Belshaw, Waldron, & Maxwell, 2013). Recently, there has been increased research interest in lignocellulosic biomass obtained from FPW as a renewable source of bioactive polysaccharides. FPW is composed of cellulose (40–50%), hemicellulose (20–30%) and lignin (10–25%) along with other polysaccharides (MinjaresFuentes et al., 2014). There has been a shift in focus from cellulose as just a fibrous solid, to a material platform for use in diagnostics, pharmaceuticals and nutraceuticals (Credou & Berthelot, 2014). Cellulose and its derivative forms were used in diagnostic and biomedical applications due to their sugar lowering effect, anti-
body immobilization, hydrogel forming ability, water retention and biodegradability (Liu, Willför, & Xu, 2015). Hemicellulose, the second most abundant biopolymer, comprises the xyloglucans, xylans, mannans and glucomannans (Scheller & Ulvskov, 2010). Xylan upon controlled hydrolysis produces xylooligosaccharides (XOS), which are oligomers of b-1,4linked xylose residues with various substituents including acetyl, phenolic, and uronic acid (Aachary & Prapulla, 2011). Oligosaccharides such as XOS belong to a class of dietary fibres. These are resistant to action by human gut enzymes and pass undigested into the colon, wherein they are fermented by colonic microbiota (Singh et al., 2015). Fermentation of such oligosaccharides produces short chain fatty acids (Singh et al., 2015), which provide a range of health benefits including maintenance of gut health and microbiota, antioxidant and antitumor activity, metabolic control of glucose and lipid profile and immunomodulation. Along with XOS, inulin, fructooligosaccharides, galactooligosaccharides, and maltooligosaccharides represent a class of non-starch polysaccharide based dietary fibres (Liu, Fishman, Kost, & Hicks, 2003; Singh et al., 2015). Resistant starch constitutes yet another class of dietary fibre; this refers to the portion of starch that resists digestion in the gastrointestinal tract and is partially or completely fermented in the colon producing various health benefits (Fuentes-Zaragoza,
14
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
Riquelme-Navarrete, Sánchez-Zapata, & Pérez-Álvarez, 2010). Resistant starch can be obtained from FPW (mango kernels, banana peels, etc.) and also can be obtained synthetically by chemical modification of starch. Recently, dietary fibre has been promoted as a nutritional supplements for hypertension, obesity and antidiabetic formulations (Nawirska & Kwas´niewska, 2005). Reports on bioactive carbohydrate extraction from FPW are limited and further investigation of this area would be valuable. 3.2. Proteins and peptides FPW, particularly seeds, are rich in protein content. Bioactive peptides, obtained by hydrolysis of the proteins, were found to exhibit various pharmacological properties ranging from antihypertensive to anti-inflammatory (Pelegrini, Noronha, Muniz, Vasconcelos, Chiarello, Oliveira, & Franco, 2006; Udenigwe & Aluko, 2012). The presence of some amino acids like histidine and aromatic amino acids like phenylalanine was also found to be effective in quenching metal ions, reactive oxygen species and, thus, act as antioxidants (Deng, Shen, Xu, Kuang, Guo, Zeng, S., Gao, Li, Li., Lin, Xi., Xie, Jie-Feng., Xia, En-Qin., Li, Sha., Wu, Shan., Chen, Feng., Ling, Wen-Hua., Li, Hua, & Bin., 2012). Isolation of vicilin-like protein from watermelon seeds (Wani, Kaur, Ahmed, & Sogi, 2008), leptin from jackfruit seeds (Devalaraja, Jain, & Yadav, 2011) or proteolytic enzyme actinidin from kiwi fruit seeds (Boland, 2013), reveals a range of the active compounds which may be favourable for absorption from the small intestine and thus, can be correlated with bioavailability. Actinidin was found to degrade proteins in the small intestine. It has also been evaluated as a protein additive in dairy products (Puglisi, Petrone, Piero, & Lo, 2012) where it was found to break the milk proteins into smaller fragments. Under gastric conditions, it was found to increase absorption of beef proteins and soy protein isolates (Puglisi et al., 2012). Passion fruit seeds were also reported to contain an antifungal protein similar to albumin proteins (Pelegrini et al., 2006). 3.3. Lipids Lipids present in FPW include fatty acids, waxes, isoprenoid hydrocarbons, acylglycerols along with carotenoids, sterols and vitamins (Chow & Lobb, 2007). The residues of processed citrus fruits, kernels from mango processing, apricot seeds, pomegranate seeds and tomato seeds contain a significant amount of oil (10–50% by weight of total waste). Iranian tomato seed oil was reported to contain saturated and unsaturated fatty acid compositions of 18.3% and 81.7%, respectively (Lisichkov, Kuvendziev, & Lisichkov, 2011). Among FPW based commercial products, pomegranate seed oil was found to be a rich source of punicic acid, which belongs to a class of conjugated omega-5-fatty acids (Goula & Adamopoulos, 2012). The oil was found to be effective in inhibiting breast cancer proliferation and showed anti-asthmatic, anti-oxidant and antiobesity properties (Goula, 2013; Patterson, Wall, Fitzgerald, Ross, & Stanton, 2012). Mango kernel fat triglyceride composition and thermal behaviour were shown to have similar properties to that of cocoa butter due to its unique fatty acid profile. The ratio of saturated to unsaturated fatty acids was found to be 40:60 (Sonwai, Kaphueakngam, & Flood, 2012). The blending of mango oils with other oils such as palm oil has widely been studied as an alternative to cocoa butter (Akanda, Sarker, Norulaini, Ferdosh, Rahman, & Omar, 2013; Sonwai et al., 2012). The oils and fats from some FPW have also been used for skin healing creams due to their emollient and anti-ageing properties (Mandawgade & Patravale, 2008). Oils rich in conjugated fatty acids have been found to prevent cancer growth (Grossmann, Mizuno, Schuster, & Cleary, 2010).
3.4. Polyphenols and other secondary metabolites Work presented by several authors (Da Silva, De Figueiredo, Ricardo, Vieira, De Figueiredo, Brasil, & Gomes, 2014; Guo, Yang, Wei, Li, Xu, & Jiang, 2003) has shown that the concentration of secondary metabolites is often greater in the FPW compared to the fruit pulp. Polyphenols have received considerable attention as bioactive compounds because of their capacity to replace synthetic preservatives due to their ability to scavenge free radicals and prevent oxidation reactions in food. Also, phenolic antioxidants regulate the generation of free radicals in vivo, thus, preventing cell damage and oxidative stress (Deng et al., 2012). Non-specific polyphenolics which are generally found in FPW are catechins from mango peels and kernels (Abdalla, Darwish, Ayad, & ElHamahmy, 2007), ellagitannins from raspberry pomace (Da Silva et al., 2014), chlorogenic acid from apple pomace (Da Silva et al., 2014), polymethoxylated flavones such as tangeretin in citrus peels (Deng et al., 2012) and flavonoids such as punicalin and punicalagin in pomegranate peels (Aviram, Volkova, Coleman, Dreher, Reddy, Ferreira, & Rosenblat, 2008). Only a few polyphenolic extracts from FPW have reached commercialization. The two well-known examples are resveratrol from grape pomace and olive waste (Abdalla et al., 2007; Akhtar, Ismail, Fraternale, & Sestili, 2015). In recent research work, incorporation of 400 ppm of methanolic extract of mango kernels and 5% mango kernel oil into sunflower oil was shown to retain oil stability against rancidity for up to 12 months while 5000 ppm of mango kernel extract prevented growth of bacteria in milk when stored at room temperature for 15 days (Abdalla et al., 2007). Many recent reports (Akhtar et al., 2015) describe the efficacy of pomegranate peel extracts in preventing instability in food products such as bread, probiotic ice creams, juices, wines and jams. The food products were found to contain 0.2–0.4% of total extract when the minimum inhibitory concentration for preventing bacterial growth was found to be in the range of 4-25 mg/ml. Similarly Ferric reducing antioxidant power (FRAP) analysis revealed that a concentration of 50 ppm of prickly pear seed extract prevented oxidation of margarine as compared to a control sample (Chougui, Djerroud, Naraoui, Hadjal, Aliane, Zeroual, & Larbat, 2015) containing vitamin E (100 ppm). The extract was found to contain a mixture of sixteen polyphenols including hydroxycinnamic acid and exhibited a potent antioxidant activity equivalent to marketed antioxidants. It is apparent that a cocktail of phenols act in a better way than the isolated compound (Chougui et al., 2015). The efficacy of crude mixtures may be cost effective as downstream processing cost can be minimized if ‘‘cocktail” extracts are useful. For example, pomegranate peel extract was found to exhibit antiatherogenic activity (Aviram et al., 2008) in mice through a decrease of the macrophage content by 53% as compared to placebo (no extract) and thus could be potentially developed as a treatment for atherosclerosis for humans. On the other hand, extraction and concentration of a specific compound from crude can help target a specific disease in the body. 3.5. Pharmaceutical excipients from FPW Polysaccharides, gum exudates, and proteins derived from FPW processing waste find application in pharmaceutical use as polymers. This is exemplified by the application of chitosan, carrageenan, ispaghula and similar natural products that are utilized as thickening agents, emulsifying agents and cosmetic additives (Kumar & Negi, 2012; Kuzmenko, Hägg, Toriz, & Gatenholm, 2014; Rabbani, Teka, Zaman, Majid, Khatun, & Fuchs, 2001). Cellulose, the most abundant polymer is used as diluent or filler in solid oral dosage formulations and can be obtained from various fruit peels (Credou & Berthelot, 2014). Furthermore, chemical
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
derivatization of cellulose via etherification, esterification, and cross-linking or graft copolymerization yield derivatives which find widespread application (Credou & Berthelot, 2014; FuentesZaragoza et al., 2010). These derivatives can be used as disintegrating agents, enteric coating polymers and monolithic membrane systems. A linear polysaccharide, pectin (Emaga, Ronkart, Robert, Wathelet, & Paquot, 2008) is composed of alpha (1–4)-linked dgalacturonic acid residues, is widely extracted from fruits and used as gelling agent or thickener (Liu et al., 2003). It has also been used as prophylactic agent in diarrhoea (Liu et al., 2003; Rabbani et al., 2001) mucoadhesive polymer and for colon targeted drug delivery systems (Kumar & Negi, 2012). Xylan, an important constituent of hemicellulose has been used in wound dressing, in drug delivery for inflammatory bowel disease as thermoresponsive hydrogels and tissue engineering (Kumar & Negi, 2012). 4. Extraction of bioactive compounds There are numerous methods used for the extraction of bioactives from solid and liquid biomass waste streams. Traditional methods include: solid-liquid extraction, soxhlet extraction and liquid-liquid extraction. The disadvantages associated with these methods are high solvent consumption, high energy consumption, risk of thermal degradation of heat-labile components, and longer extraction times. As discussed further below, more recently, novel processes of extraction have emerged including supercritical fluid extraction (Lisichkov et al., 2011; Pereira & Meireles, 2010), microwave assisted extraction (Fishman, Chau, Cooke, & Hotchkiss, 2008), ultrasonication in the presence of various solvents (Dorta, Lobo, & González, 2013; Minjares-Fuentes et al., 2014), pressurized liquid extraction (Galanakis, 2012), pulse electric field extraction (Galanakis, 2012) and ionic liquid extraction (Chowdhury, Vijayaraghavan, & MacFarlane, 2010). The shift from conventional organic solvent based processes to novel, zero waste processes (Budarin, Shuttleworth, Dodson, Hunt, J., Lanigan, B., Marriott, R., Milkowski, Kris, J., Wilson, Ashley, J., Breeden, Simon., Fan, Jiajun., Clark, & J. H., 2011) necessitates the development of greener methods. Since the yield of bioactive compounds from FPW is influenced mainly by the conditions under which the process is carried out, one must optimize the sequence of extraction process e.g. removal of external waxes and lipids prior to aqueous processing may increase the selectivity and thus, economic value of the process (Budarin et al., 2011).
15
and safety. For example, the most preferred solvent among alcohols is ethanol due to its lower boiling point, quick recovery and the ‘‘generally regarded as safe” status as defined by the US FDA (FDA., 2004). However, alcohol as a solvent may not always be useful since many of compounds such as carotenoids are more soluble in aprotic solvents. The yield of hydroxylated components which are commonly present in mango kernel waste was found to be optimum with ethanol, while methoxylated components which are present in peel required less polar solvents such as acetone (Dorta et al., 2013). An acetone-water (1:1) mixture was found to be the best solvent for FPW where polyphenols were protein bound. It may be seen from the Table 3 that green extraction methods such as enzyme based extraction and microwave assisted extraction assists in the recovery of significant quantity of bioactives such as pectin (e.g., 8.3% of pectin yield from Yuza peels) (Lim, Yoo, Ko, & Lee, 2012). Further recent examples of other feedstocks are discussed with an aim to show that alternative/novel green extraction methods are more sustainable compared to conventional methods and may be an environment friendly replacement for organic solvent based methods. Ionic liquids are a novel medium for extraction of bioactives. Often termed as designer solvents, these are organic salts in a liquid state (Forsyth, Pringle, & MacFarlane, 2004). These liquids are viscous, good ion conductors, non-ionizing, high boiling point systems and favour solubility over a large range (Forsyth et al., 2004). The advantage of using ionic liquids is that the properties can be selected or tuned to dissolve hydrophilic or hydrophobic molecules at room temperature (Idris, Vijayaraghavan, Patti, & MacFarlane, 2014). Several examples of ionic liquids in bioactive extraction include 1-alkyl-3methylimidazolium-based ILs for grape seed polyphenols, (Yanes, Gratz, Baldwin, Robison, & Stalcup, 2001) N, N-dimethylammonium N,N-dimethylcarbamate (DIMCARB) for catechu tannins (Vijayaraghavan & MacFarlane, 2014), 1-butyl-3methylimidazolium tetrafluoroborate for extraction of amines from citrus (Arce, Pobudkowska, Rodríguez, & Soto, 2007). Application of distillable ionic liquids in extraction of circumin through alkyl carbamate analogues (Vijayaraghavan & MacFarlane, 2014), recovery of keratin from feathers (Idris et al., 2014) and tannins from plant extracts (Chowdhury et al., 2010) demonstrates the potential for relatively facile and complete recovery of the ionic liquids used in the extraction.
5. Identification of challenges in valorisation of FPW 4.1. Conventional vs modern extraction methods for FPW The route from FPW to bioactive recovery is challenging, mainly because of the selective nature of the extraction methods. Among the several factors which may affect selection of methods, the quantum of material is a major concern. Due to the perishable nature and large quantity at one time, most of the conventional processes such as organic solvent based lipid extraction or extraction of individual compounds are difficult to scale up. The majority of recent studies have evolved around greener methods, such as supercritical carbon dioxide based extraction, microwave assisted extraction and ultrasonication. Microwave and ultrasonication are widely accepted as compared to the former owing to their ease of applicability for high moisture substrates. Internal moisture of the FPW helps in disruption of the structure when the molecules are subjected to excitation using external energy sources such as microwaves (Attard, Watterson, Budarin, Clark, & Hunt, 2014). Where water may not be used as extraction medium the solvent choice becomes an important concern, as it impacts on the final product, disposal and removal methods, cost of manufacturing
The industrial scale valorisation of any alternative feedstock depends on its availability. Thus, selection of a fruit which is processed in larger quantities along with its annual presence is important. For this reason, majority of research in this field has happened (as shown in Tables 2 and 3) around citrus and grape waste. Mango, pomegranate, banana are other processed fruits which have been explored as potential feedstocks for an integrated biorefinery, especially in developing countries such as China, India, Malaysia and Indonesia. Due to seasonal availability for some of these fruits, a sequential process in a multi-feedstock system would be useful. For instance, mango is largely processed in summers while pomegranate, banana, kiwi, orange are processed regularly. Thus, at one time, a single type of feedstock can be utilized and the process can be continued along with regular fruit processing. Transportation of industrial FPW, which is often received as a mixture of various parts of processed fruit or vegetable by-products is a challenge. A decentralized system which is closer to the processing industries may be more efficient. The developing country model indicates presence of processing industries in a scattered form, but often located in close proximity to one
16
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
Table 3 Laboratory scale extraction methods for fruit processing waste. Fraction
Pomace
Sample
Grape
Apple Apple pomace dry Tomato Tomato
Carrot Carrot Yuza (Citrus)
Peels
Yuza (Citrus) Banana Carrot
Citrus Mango Mango Mango
Watermelon
Seeds
Kernel
Extraction method
Extraction parameters pH
T (°C)
t (h)
Solvent
Solute/solvent
Ultrasound assisted extraction Solvent extraction Microwave extraction (P = 499.4 W) Sonicated assisted(40KHz) Microwave assisted sonicated (98 W, 40 kHz) Saponification method Solvent extraction Chemical
2
75
1
Citric acid solution
–
100
0.6
1
–
–
Enzymatic (Viscozyme) Acid-water extraction Dietary fibre by blanching and drying, pectin by solvent extraction Microwave (large scale) Homogenisation Solvent extraction Solvent extraction and centrifugation Sonication
Yield
Bioactive
Reference
01:10
32.3%
Pectin
(Minjares-Fuentes et al., 2014)
Water
01:10
0.01%
(Cam et al., 2014)
2.1
HCl-ethanol
0.07
15%
Total phenolics Pectin
86.4
0.5
Ethyl acetate
01:08
89.4%
Lycopene
(Lianfu & Zelong, 2008)
–
–
0.1
Ethyl acetate
01:10
97.5%
Lycopene
(Lianfu & Zelong, 2008)
–
70
0.5
01:08
8.8%
b-carotene
(Chantaro et al., 2008)
–
25
15
EtOH+(2N KOH + diisopropyl ether) Acetone water (1:1)
01:10
1%
(Chantaro et al., 2008)
–
85
1
01:40
7.3%
–
40
1
1:20 w/v
8%
Pectin
(Lim et al., 2012)
2
90
1
0.25% ammonium oxalate- ethanol (precipitation) 0.0001 fungal-b glucanase unit HCl- alcohol
Total polyphenolics Pectin
01:29
22%
Pectin
(Emaga et al., 2008)
1.3– 3.0
90
1
0.05 M HCl + 2propyl alcohol
01:06
45.4% 8.4%
Dietary fibre and pectin
(Chantaro et al., 2008)
–
120
0.1
Acidified water
01:10
10.8%
Pectin
(Pfaltzgraff et al., 2013)
2
1
Acetone (80%)
01:20
40.6%
Dietary fibre
–
50– 100 22
1
Methanol
01:20
2%
2
25
0.25
Acetone (80%)
01:20
9%
Total phenolics Total phenolics
(Ajila & Prasada Rao, 2013) (Sogi, Siddiq, Greiby, & Dolan, 2013) (Ajila & Prasada Rao, 2013)
4
>4
0.25
Methanol
01:50
0.2%
(Wang, Chen, Wu, Wang, Liao, & Hu, 2007)
(Lim et al., 2012)
Sharlyn melon Orange Orange
Sonication
4
>4
0.25
Methanol
01:50
0.06%
Microwave Ionic liquid extraction
– –
110 80
0.5 3
01:20 01:02.5
11.5% 5%
Watermelon
Microwave
1.5
–
0.03
Hexane 1-ethyl-3methylimidazolium acetate Water
Total phenolics Total phenolics d-limonene Peel oil
01:20
26%
Pectin
Citrus sinensis Citrus paradise Citrus paradise Watermelon
Microwave extraction Supercritical fluid Supercritical fluid Alkaline hydrolysis Soxhlet extraction Hydrotropic extraction Microwave assistedhomogenisationcentrifugation Microwave assisted enzyme extraction
–
110
0.5
Hexane
01:20
14.1%
Peel oil
(Maran, Sivakumar, Thirugnanasambandham, & Sridhar, 2014) (Attard et al., 2014)
–
50
1
Carbon dioxide
–
Limonene
(Yu et al., 2007)
–
50
0.7
–
Naringin
(Yu et al., 2007)
–
50
0.2
Seed protein
(Wani et al., 2008)
–
70
6
Carbon dioxide(20% EtOH) Sodium hydroxide solution Hexane
01:07
0.6% (at P = 48.3 MPa) 0.02% (at 41.4 MPa 80% of seed meal 40%
Seed oil
–
45
6
1:9
0.06%
Seed oil
8
–
0
Sodium cumenesulphonate Acetone-water (50:50)
01:30
8.7% TAE
Total phenolics
(Huchin, V., I., R., L. F., & E., 2013) (Dandekar, Jayaprakasha, & Patil, 2008) (Dorta et al., 2013)
5
44
1.1
(Cellulase, hemicellulase, pectinase, bglucosidase, proteinase) + water
01:06
64.1%
Oil
Pouteria sapota Citrus aurantium Mango
Pumpkin
01:10
(Al-Sayed & Ahmed, 2013) (Al-Sayed & Ahmed, 2013) (Rabbani et al., 2001) (Bica, Gaertner, & Rogers, 2011)
(Jiao, Li, Gai, Li, Wei, Fu, & Ma, 2014)
[T: temperature, t: time, EtOH: ethanol, BHT: Butylated hydroxytoluene, % on w/w basis, db: dry basis, MPa: Mega pascal, GAE: Gallic acid equivalent, RE: Rutin equivalent, TAE: Tannic acid equivalent].
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
another due to availability of raw material in specific geographical regions. For example, mango processing units in India are concentrated in two regions, viz. Ratnagiri in Maharashtra and Chittoor district in Andhra Pradesh. In India, average pulping waste collected from a medium scale mango processing industry is about 50–100 tonnes/day. Some areas have more than 10 units within 50 km radius. Therefore, collection of 500–1000 tonnes waste/day is feasible in Indian context. Since mango pulping is a seasonal business and pulping continues only for 4 months, we assumed that plant operate 24 h per day and 180 days per year with collection of 240 tonnes/day waste per day which could be procured within 20 km radius of the facility. Maharashtra state alone contributes to 70% of total pomegranate production in India (NHB, 2015). With Govt. of India’s support, pomegranate production and productivity has increased significantly in last few years. Recovery of ready substrates for biofuels, biobased chemicals production and extraction of valuable components from the available quantum of waste would be an ideal setting to generate significant revenue from waste. Utilization of pomegranate waste is an interesting area for investigation from the view point of biorefinery because the large volumes grown and concentration of significant wastes are available particularly at pomegranate juicing plants. Also, with a strong initiative of Ministry of Food Processing Industries towards Food parks in India will further help develop potential of such biorefineries. Converting a renewable non-fossil carbon, such as pomegranate processing waste to multiple value added products would assure a continual energy and material supply. Limited reports are available on the storage methods of FPW where blanching, pressing and hot air drying have been shown to be appropriate methods for long term storage (Nagel, Neidhart, Anders, Elstner, Korhummel, Sulzer, & Rentschler, 2014). Alternatively, wet feedstock can be processed in an integrated biorefinery. Recent developments in olive mill waste processing (ElMekawy, Diels, Bertin, De Wever, & Pant, 2014), citrus waste processing (Pfaltzgraff et al., 2013), mango waste processing (Banerjee, Vijayaraghavan, Arora, MacFarlane, & Patti, 2016) etc. suggest a possibility of processing the wet feedstock directly via methods such as microwave digestion in which the structure is disrupted
17
first, followed by recovery of pectins and polyphenols and then the residual mass may be treated through an anaerobic fermentation process to recover platform chemicals such as volatile fatty acids (Scoma, Bertin, Zanaroli, Fraraccio, & Fava, 2011). 5.1. Role of fractionation in extraction of bioactives The economic feasibility of the extraction method depends on the maximum recovery of bioactives from the FPW. Unlike simpler lignocellulosic biomass, where cellulose and lignin form most of the structure, FPW show structural diversity. In general, any seed contain a woody shell and a softer core in which mainly oleoprotein, glycoprotein and glycolipid may construct most of the biomass (El-Safy, Salem, & Abd El-Ghany, 2012). Peels are fibrous in nature in which cellulose is found abundantly along with lignin, hemicellulose, pectins etc (Matharu, Houghton, Lucas-Torres, & Moreno, 2016; Pfaltzgraff, 2014). The structural study though important, is not well studied with respect to fruit waste seeds. Certain green methods such as enzymatic and ionic liquid based extraction may be designed for known structural properties which ultimately leads to sequential separation. For example, enzymatic extraction is a recent lipid recovery approach in which disruption of the sample matrix is used with the help of specific enzymes such as proteases, pectinase, viscozyme (Novozymes) etc. (Gaur, Sharma, Khare, & Gupta, 2007; Puri, Kaur, Singh, & Kanwar, 2008). Alkaline protease was used in extraction of lipid from mango kernels (Gaur et al., 2007) in a three phase partition method. The method is environmentally safer compared to hexane based extraction, but the residue generated from the lipid removal may contain high amounts of precipitated salt, recovery of which may pose an additional challenge and restricts its scale up. The disadvantage of enzymatic method is its cost, which can be decreased using enzyme immobilization. It is a technique to recycle the enzymes and increase the productivity by fixation of enzymes in a polymer matrix (Puri et al., 2008). Certain food grade polysaccharides may be helpful in entrapment of these enzymes owing to their biocompatibility. The immobilization technique was successfully used to separate naringin and hesperidine from orange to prevent bitterness in the juice (Ribeiro, Rocha, Sepodes, Mota-Filipe, &
Fig. 2. An integrated Biorefinery model for FPW.
18
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
Ribeiro, 2008). Another study reported carrier free immobilization of glucoamylase and pullulanase with glutaraldehyde reported an enhanced starch to sugar conversion, thermal stability and recycling of the enzymes (Talekar, Desai, Pillai, Nagavekar, Ambarkar, Surnis, & Mulla, 2013). To further modify such existing green methods, a fractionation strategy (Fig. 2) would improvise the cost and efficiency of these processes, e.g. recovery of lipids from kernels may be helpful followed by protein and phenolics recovery from the residue. There are two major products obtained from mango peels viz. pectin and total polyphenols. The ultimate residue rich in cellulose and lignin can be then combined with a biofuel production technique (Do, Lim, Jang, & Chung, 2015; Li, Zhang, & Hu, 2015). The byproducts such as sugars can further be used for biofuels or converted to platform chemicals. The yield and concentration of sugars can be increased by recycling the aqueous stream in the process or using membranes (Galanakis, 2012). The primary advantage of this strategy is that maintaining high sugar concentrations would reduce downstream processing costs significantly, especially distillation and evaporation processes, thus, lower energy input and improved economic viability of biofuels/biobased chemicals production would become possible. Isolating a compound from an extract is a costly process. Emerging techniques such as membrane filtration, adsorption chromatography and enzyme immobilization techniques may be used as cost effective solutions for separation of bioactive molecules (Galanakis, 2012). Ultrafiltration and nanofiltration may help in the separation of bioactives on the basis of molecular weights and particle size. Nanofiltration has been used for separation of phenols from the olive mill waste (Galanakis, 2012). Macromolecules such as proteins and bioactive peptides may be recovered from a pool of bioactives using membranes or gelpermeation chromatography (Udenigwe & Aluko, 2012). The techno-economic feasibility of any extraction and purification process should be assessed for the selection of manufacturing processes, marketing strategies and profitability. Recent years have seen the emergence of process simulation studies in the field of various agricultural and food residues (Do et al., 2015; Li, Ou, et al., 2015; Li, Zhang, et al., 2015; Zhao, Brown, & Tyner, 2015) such as lignocellulosic biomass and dairy waste biorefinery. The product value of bioethanol using empty palm fruit bunches (capacity- 30.2 tonnes/day) were found be to $1.0–1.1/kg compared to existing market price ($0.96/kg) in 2014 (Do et al., 2015). Using empty palm fruit bunches as feedstock in a study on bio-oil production, it was found that a 20,000 tonnes/yr capacity plant may produce bio-oil at a product value of $0.27/kg, payback period of 3.2 yr and return on investment worth 21.9%. The important critical points identified in these techno-economic studies were limited integrated processes, plant size, production yields and limited studies on other FPW feedstocks. The profit margins were found to be high when multiple products were considered from the feedstock (Li, Ou, et al., 2015; Li, Zhang, et al., 2015). Thus, FPW as a feedstock may be an ideal choice. An end to end linkage can be established between the bioproduct and biofuel processes, valorising the feedstock completely. The process models to convert processing waste (as a feedstock) into fuel and value added coproducts are being developed using flowsheet simulators such as Aspen Plus Ò and SuperPro DesignerÒ (Tyler, Jing, Wafa, Duncan, Tschirner, Schilling, & Kazlauskas, 2011). Recent years have seen a significant rise in process and product development aimed at biorefinery models. Palm fruit and Citrus processing waste are the two industrial feedstocks in which highest contribution in terms of literature reports were found during 2013–2016. A gradual progression was observed for the above two feedstocks where lab scale studies were converted to pilot scale study and techno economic feasibility was analyzed.
Other product development challenges are related to the stability of recovered bioactives and the stability of the final products. Thus, stability studies on final products are necessary to determine their shelf life and this is a necessary evaluation parameter prior to pre-market approval.
6. Economic considerations and industrial examples of FPW utilization A very few reports mention the techno-economic feasibility of fruit waste utilization processes (Attard et al., 2014; Pfaltzgraff et al., 2013). Considering the consistent growth of bio based product’s market value which is predicted to increase from €228 billion in 2015 to €515 in 2020 (EFIB, 2016), the scope of co-products recovery from FPW is expected to gain significant importance. The extraction of pectin and d-limonene from orange peels using a microwave refinery process shows a process cost of $7.2 million on processing of 50,000 MT of wet orange peels (Pfaltzgraff et al., 2013) (yield of d-limonene and pectin was 1.5% and 10.8% on a wet basis respectively); the profit generated was $11.3 million when the raw material cost was considered to be zero. The cost of microwave energy consumption was discussed with respect to Europe in that year and may vary as per the production plant location. Considering raw material cost of $0.02/kg of wet orange peel, the net profit can be $10.5 million (Pfaltzgraff et al., 2013). In addition, as the commercial recovery of valuable compounds and materials from FPW increases, the market value of these recovered materials may decrease, unless novel applications can be found which will maintain world demand. The novel application of one of the FPW based products limonene is recently illustrated where limonene can be utilized as a greener alternative replacement to toluene (Paggiola, Stempvoort, Bustamante, Barbero, Hunt, & Clark, 2016). Constraints in supply chain of substrates required to produce limonene was identified as a critical issue which may be resolved if the capital investment cost is minimized by developing the biorefinery in citrus producing regions (for example, Florida in the US; Nagpur in India). Table 4 illustrates a case study for mango waste, which was chosen on the basis of its availability in developing countries. Several studies discussing mango processing waste (Abdalla et al., 2007; Dorta et al., 2013; Nagel et al., 2014) to date have focussed on single product recovery. However, it is clear that a more economical processes could be designed that achieve major product recovery from different parts of the waste such as peels and seeds. Such information would provide the basis of a biorefinery model in FPW utilization. Though operational and set up costs are not shown in Table 4, in the absence of any techno economic feasibility analysis, the revenue generation from a waste of negligible input cost still seems to be encouraging. The recovered starch for an average processing rate of 6% of total Indian produce of mango, may be worth $7 million. The net profit may be calculated on the basis of the cost of the set up and recovery processes. Pectin is in high demand as a food additive in the food and pharmaceutical industries. The recovery of 12 thousand metric tonnes of pectin may fetch a minimum product value of $118 million. Also the quality of starch and pectin from mango kernels and peels were found to be similar to the commercial grades (Nagel et al., 2014; Sandhu & Lim, 2008). Some of the commercial sources of starch and pectin are corn, potato, sunflower and apple pomace. Bioactive lipids like conjugated linoleic acid (CLA) have limited sources in nature e.g. marine sources, flax seeds (Candela, Rabaneda, Dassen, Borje, & Lobo, 2007). The demand for these lipid based products is very high in both developing and developed countries due to their proven health effects (Khoddami, Bin, Man, & Roberts, 2014). Similar classes of lipids
19
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22 Table 4 Value addition from mango processing waste (MT = metric tonnes). Processing rate (%)
2 4 6 8 10
Processed quantity (MT)
360000 720000 1080000 1440000 1800000
Total dry waste (MT)#
25812 51624 77436 103248 129060
Price*
Total Worth of Waste (Million $)
Lipid $7.5/kg
Phenolics $8/kg
Pectin $10/kg
Starch $0.4/kg
Lipids (MT)
Worth in (Million $) (A)
Phenolics (MT)
Worth in (Million $) (B)
Pectin (MT)
Worth in (Million $) (C)
Starch (MT)
Worth in (Million $) (D)
A+B+C+D
1283 2566.1 3849.1 5132.2 6415.2
9.6 19.2 28.9 38.5 48.1
129.1 258.1 387.2 516.2 645.3
1 2.1 3.1 4.1 5.2
3931.2 7862.4 11793.6 15724.8 19656.0
39.3 78.6 117.9 157.2 196.6
5880.6 11761.2 17641.8 23522.4 29403.0
2.4 4.7 7.1 9.4 11.8
52.3 104.6 157.0 209.3 261.6
*
Source: Indiamart.com. Moisture content of mango peel and seed are 80 and 50%, respectively. Values for extraction yield (on dry basis) are based on our lab studies. Total production accounts for production estimate for India (18 million tonnes in 2014). Assumptions have been made for waste generation (30% of processed fruit), recovery of phenolics (0.4–0.5% from peels and seed; d.b), oil (11–13% from mango kernels, d.b), pectin (26–28% from peels, d.b) and starch (50–60% of mango kernel, d.b) respectively. #
Table 5 Recent patents on fruit processing waste. HPW
Patent
Applicant
Title
Products
Use/application
Reference
Mango peels
WO2013141723 A1
Taboada, Evelyn., Francis Dave Siacor., 2013
Pectin, polyphenols
WO2008055894 A1
Lavecchia, R., Zuorro, A., 2008
Gelling agent, stabilizing agent in fruit juices, preservatives Antioxidant, therapeutics
(Taboada & Siacor, 2013)
Tomato processing by products Citrus peels
Preparation of pectin and polyphenolic compositions from mango peels Process for the extraction of lycopene
US20130064947 A1
Movaghar, K, N., Druz, Loren, N., Victoria., P, C., 2013
Conversion Of Citrus Peels Into Fibre, Juice, Naringin, And Oil
Dietary fibre, flavourant, Oil
Nutritional supplement, Food additive
Tamarind seed
EP2575973 A1
Giori, Andrea., Arpini, Sabrina Togni, Stefano., 2013
Tamarind seed polysachharide
Active pharmaceutical ingredient
Pomegranate husk
US20110087043 A1
site-specific inhibitors of histone methyltransferase
lead compounds to develop anti-neoplastic and anti-HIV therapeutics
(Kundu, Vikru, Annavarapu, & Kempegowda, 2011)
Pomegranate peels
US2014/0056930 A1
Kundu, Tapas Kumar, Annavarapu, Vikru, R, S, Bharatha., Hari Kishore, Kempegowda; Mantelingu (Rimonest), 2011 Liker; Harley., 2014
Polyphenols
US2014/0044809 A1
Brainard, Elliott, F., 2014
Treatment of prostrate cancer by increasing doubling time of a prostrate specific antigen Active Pharmaceutical ingredient
(Liker, 2014)
Pomegranate and berry extract Cranberry and pomegranate extract powders
Tamarind seed polysaccharide for use in the treatment of inflammatory diseases Site-specific inhibitors of histone methyltransferase (HMTASE) and process of preparation thereof Method of using pomegranate extracts for increasing prostate specific antigen doubling time Antacid formulations and associated methods
(NafisiMovaghar, Druz, & Victoria, 2013) (Giori, Arpini, & Togni, 2013)
US2014/0010871 A1
Mackler, Ari (POM Wonderful LLC)., 2014
POMcran capsules (25–5000 mg)
(Mackler, 2014)
Methods and compositions of urinary tract infections
are present in pomegranate waste where 80–85% of the seed lipids are CLA (Khoddami et al., 2014). As reported in one of the studies (Fava et al., 2015) the non-specific lipids such as fatty acid mixtures can be used as carbon source to produce polyhydroxyalkanoates where theoretical yield from fatty acid rich carbon source compared to sugars, was found to be approximately two times higher. A few recent examples of FPW based patents have been summarised in Table 5. Pomegranate waste due to its unique polyphenol composition have found application in a wider range of products consisting of antacids, anti-inflammatory and antiseptic formulations. The recovery of pure compounds of high value such as punicagalin in pomegranate (Aviram et al., 2008), mangiferin in mango waste (Ruiz-Montañez, Ragazzo-Sánchez, CalderónSantoyo, Velázquez-de la Cruz, Ramírez de León, & Navarro-
Lycopene
Berry fibre, pomegranate extract, citrates Hydrolyzable tannins as antibacterial agents
(Lavecchia & Zuorro, 2010)
(Brainard, 2014)
Ocaña, 2014) and resveratrol in grape waste (Galanakis, 2012) may also be economical due to their limited sources and high demand.
7. Concluding remarks and future trends FPW consists of 20–50% of total waste produced in fruit processing industries. Currently the use of FPW as a feedstock for recovery of valuable components is limited. The direct collection from processing facilities may help minimize the segregation efforts for processing, thus, significant financial savings can be realized. FPW has been shown to be a viable single starting material for the recovery and production of multiple co-products in an integrated biorefinery model where more than one green process
20
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
can be combined. More efficient and complete utilization of biomass associated with food production will also lead to more sustainable use of all the resources (including water, fertilizers, maintaining soil health and efficient land management). Lipids and waxes can be removed in the first stage followed by aqueous separation of polyphenols, sugars and proteins. The residue rich in structural carbohydrates (and lignin to a lesser extent) may then be utilized for production of biofuels and other chemicals. The residual fibres may also be evaluated for the production of sulfur free lignin which were found to be of more industrial interest in European region due to their environment friendly aspect (Fava et al., 2015). Lipids such as seed oil which are rich in linolenic and linoleic acids may be directly formulated as nutraceuticals for their proven health benefits. Polyphenols may be used in the preservation of food products and pharmaceuticals. The encouraging application of the polyphenols may also be correlated to the interest of large cosmetic manufactures such as L’Oreal. Much emphasis was given on synthesis of C-glycosides for cosmetic applications (Michel Philippe., 2004). The specific class of these glycosides were also abundantly present in some of the fruit wastes and purification may be of great value owing to high value of these products. The successful shift from laboratory to commercial scale for processes such as citrus and mango oil extraction for cosmetic products, natural flavouring agents like limonene, pectin extraction from fruit peels and the growing demand for natural products in the food and beverage industry shows the scope of technological progress in this sector. Overall, the concept of bioactives from FPW and application of green methods for valorization opens new avenues for food, chemical and pharmaceutical industries which have a tremendous potential, especially where availability of FPW is abundant. Limited awareness about FPW in developing countries can be overcome with the help of academia and industry collaboration efforts. The emphasis on green chemistry and greener processes has already attracted interest in working with this type of food waste. These industries must also be intimately linked to the land and agriculture, in considering the most efficient use of the biomass, including closing the loop by returning nutrients and organic matter to the soil, when all other useful products have been recovered. Acknowledgement The authors are grateful to the Ministry of Food Processing Industries (MOFPI) under Department of Science and Technology (DST) – India India for providing funding through the external competitive grants program (Project ID: SERB/MOFPI/0036/2013) and School of Chemistry, Monash University for providing facilities. The authors would like to acknowledge Ms Pushpani Sharma and Mr Nikhil Sirdesai for providing inputs for the figures. References Aachary, A. A., & Prapulla, S. G. (2011). Xylooligosaccharides (XOS) as an emerging prebiotic: microbial synthesis, utilization, structural characterization, bioactive properties, and applications. Comprehensive Reviews in Food Science and Food Safety, 10(1), 2–16. Abdalla, A. E. M. M., Darwish, S. M., Ayad, E. H. E. E., & El-Hamahmy, R. M. (2007). Egyptian mango by-product 1. Compositional quality of mango seed kernel. Food Chemistry, 103(4), 1134–1140. Ajila, C. M., & Prasada Rao, U. J. S. (2013). Mango peel dietary fibre: Composition and associated bound phenolics. Journal of Functional Foods, 5(1), 444–450. Akanda, M. J. H., Sarker, M. Z. I., Norulaini, N., Ferdosh, S., Rahman, M. M., & Omar, A. K. M. (2013). Optimization of supercritical carbon dioxide extraction parameters of cocoa butter analogy fat from mango seed kernel oil using response surface methodology. Journal of Food Science and Technology, 1–8. Akhtar, S., Ismail, T., Fraternale, D., & Sestili, P. (2015). Pomegranate peel and peel extracts: Chemistry and food features. Food Chemistry, 174, 417–425.
Al-Sayed, H. M. A., & Ahmed, A. R. (2013). Utilization of watermelon rinds and sharlyn melon peels as a natural source of dietary fiber and antioxidants in cake. Annals of Agricultural Sciences, 58(1), 83–95. Arce, A., Pobudkowska, A., Rodríguez, O., & Soto, A. (2007). Citrus essential oil terpenless by extraction using 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid: Effect of the temperature. Chemical Engineering Journal, 133(1), 213–218. Attard, T. M., Watterson, B., Budarin, V. L., Clark, J. H., & Hunt, A. J. (2014). Microwave assisted extraction as an important technology for valorising orange waste. New Journal of Chemistry, 38(6), 2278–2283. Aviram, M., Volkova, N., Coleman, R., Dreher, M., Reddy, M. K., Ferreira, D., et al. (2008). Pomegranate phenolics from the peels, arils, and flowers are antiatherogenic: Studies in vivo in atherosclerotic apolipoprotein E-deficient (E0) mice and in vitro in cultured macrophages and lipoproteins. Journal of Agricultural and Food Chemistry, 56(3), 1148–1157. Banerjee, J., Vijayaraghavan, R., Arora, A., MacFarlane, D. R., & Patti, A. F. (2016). Lemon juice based extraction of pectin from mango peels: waste to wealth by sustainable approaches. ACS Sustainable Chemistry & Engineering [In Press]. Miller, Be. J. N. (2004). Carbohydrates. In Kirk-Othmer encyclopedia of chemical technology. , pp. 6-50. Bica, K., Gaertner, P., & Rogers, R. D. (2011). Ionic liquids and fragrances – Direct isolation of orange essential oil. Green Chemistry, 13(8), 1997–1999. Biesalski, H.-K., Dragsted, L. O., Elmadfa, I., Grossklaus, R., Muller, M., Schrenk, D., et al. (2009). Bioactive compounds: definition and assessment of activity. Nutrition (Burbank, Los Angeles County, Calif.), 25(11-12), 1202–1205. Boland, M. (2013). Kiwifruit proteins and enzymes: Actinidin and other significant proteins. Advances in Food and Nutrition Research, 68, 59–80. Brainard, E. F. (2014). Antacid formulations and associated methods. Patent No. US 2014/0044809 A1. U.S. Budarin, V. L., Shuttleworth, P. S., Dodson, J. R., Hunt, A. J., Hunt, A. J., Lanigan, B., et al. (2011). Use of green chemical technologies in an integrated biorefinery. Energy and Environmental Science, 4(2), 471–479. Cam, M., Icyer, N. C., & Erdogan, F. (2014). Pomegranate peel phenolics: microencapsulation, storage stability and potential ingredient for functional food development. LWT-Food Science and Technology, 55(1), 117–123. Candela, C. G., Rabaneda, R. C., Dassen, C., Borje, V. M., & Lobo, R. M. (2007). Omega3 and omega-6 fatty acids. Nutrition and Metabolic Disorders in HIV Infection, 6 (3), 1165–1169. Chantaro, P., Devahastin, S., & Chiewchan, N. (2008). Production of antioxidant high dietary fiber powder from carrot peels. LWT – Food Science and Technology, 41 (10), 1987–1994. Chougui, N., Djerroud, N., Naraoui, F., Hadjal, S., Aliane, K., Zeroual, B., et al. (2015). Physicochemical properties and storage stability of margarine containing Opuntia ficus-indica peel extract as antioxidant. Food Chemistry, 173, 382–390. Chow, C. K., & Lobb, K. (2007). Fatty acid classification and nomenclature. In C. K. Chow (Ed.), Fatty acids in foods and their health implications (third edition, pp. 1–4). . Chowdhury, S. A., Vijayaraghavan, R., & MacFarlane, D. R. (2010). Distillable ionic liquid extraction of tannins from plant materials. Green Chemistry, 12(6), 1023–1028. Credou, J., & Berthelot, T. (2014). Cellulose: from biocompatible to bioactive material. Journal of Materials Chemistry B, 2(30), 4767–4788. Da Silva, L. M. R., De Figueiredo, E. A. T., Ricardo, N. M. P. S., Vieira, I. G. P., De Figueiredo, R. W., Brasil, I. M., et al. (2014). Quantification of bioactive compounds in pulps and by-products of tropical fruits from Brazil. Food Chemistry, 143, 398–404. Dandekar, D. V., Jayaprakasha, G. K., & Patil, B. S. (2008). Hydrotropic extraction of bioactive limonin from sour orange (Citrusaurantium L.) seeds. Food Chemistry, 109(3), 515–520. De Roeck, A., Sila, D. N., Duvetter, T., Van Loey, A., & Hendrickx, M. (2008). Effect of high pressure/high temperature processing on cell wall pectic substances in relation to firmness of carrot tissue. Food Chemistry, 107(3), 1225–1235. Del Valle, M., Cámara, M., & Torija, M. (2006). Chemical characterization of tomato pomace. Journal of the Science of Food and Agriculture, 86(8), 1232–1236. Deng, G. F., Shen, C., Xu, X. R., Kuang, R. D., Guo, Y. J., Zeng, Li S., et al. (2012). Potential of fruit wastes as natural resources of bioactive compounds. International Journal of Molecular Sciences, 13(12), 8308–8323. Devalaraja, S., Jain, S., & Yadav, H. (2011). Exotic fruits as therapeutic complements for diabetes, obesity and metabolic syndrome. Food Research International, 44 (7), 1856–1865. Do, T. X., Lim, Y., Jang, S., & Chung, H. J. (2015). Hierarchical economic potential approach for techno-economic evaluation of bioethanol production from palm empty fruit bunches. Bioresource Technology, 189, 224–235. Dorta, E., Lobo, M. G., & González, M. (2013). Optimization of factors affecting extraction of antioxidants from mango seed. Food and Bioprocess Technology, 6 (4), 1067–1081. Van Dyk, J. S., & Pletschke, B. I. (2012). A review of lignocellulose bioconversion using enzymatic hydrolysis and synergistic cooperation between enzymes— Factors affecting enzymes, conversion and synergy. Biotechnology Advances, 30 (6), 1458–1480. Eckard, R., & Victoria, D. P. I. (2008). Greenhouse gas emissions from agriculture – Reduction options Retrieved from http://www.greenhouse.unimelb.edu.au/ pdf_files/Hamilton_Field_Day2010.pdf. EFIB (2016). EFIB 2016 Retrieved November 25, 2016, from http://www. efibforum.com/news/2015/interview-with-dr-gunter-festel.
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22 ElMekawy, A., Diels, L., Bertin, L., De Wever, H., & Pant, D. (2014). Potential biovalorization techniques for olive mill biorefinery wastewater. Biofuels, Bioproducts and Biorefining, 8(2), 283–293. El-Safy, F. S., Salem, R. H., & Abd El-Ghany, M. E. (2012). Chemical and nutritional evaluation of different seed flours as novel sources of protein. World Journal of Dairy & Food Sciences, 7(1), 59–65. Emaga, T. H., Ronkart, S. N., Robert, C., Wathelet, B., & Paquot, M. (2008). Characterisation of pectins extracted from banana peels (Musa AAA) under different conditions using an experimental design. Food Chemistry, 108(2), 463–471. FAO (2013). Food wastage footprint: Impacts on natural resources - Summary report Retrieved from http://www.fao.org/docrep/018/i3347e/i3347e.pdf. Fava, F., Totaro, G., Diels, L., Reis, M., Duarte, J., Carioca, O. B., et al. (2015). Biowaste biorefinery in Europe: Opportunities and research & development needs. New Biotechnology, 32(1), 100–108. FDA (2004). No Title Retrieved December 12, 2015, from http://www. fda.gov/downloads/Food/IngredientsPackagingLabeling/GRAS/NoticeInventory/ UCM268080. FICCI (2010). Bottlenecks in Indian Food Processing Industry Retrieved from http://ficci.in/sedocument/20073/Food-Processing-bottlenecks-study.pdf. Fishman, M. L., Chau, H. K., Cooke, P. H., & Hotchkiss, A. T. (2008). Global structure of microwave-assisted flash-extracted sugar beet pectin. Journal of Agricultural and Food Chemistry, 56(4), 1471–1478. Forsyth, S. A., Pringle, J. M., & MacFarlane, D. R. (2004). Ionic liquids—an overview. Australian Journal of Chemistry, 57(2), 113–119. Fuentes-Zaragoza, E., Riquelme-Navarrete, M. J. J., Sánchez-Zapata, E., & PérezÁlvarez, J. A. A. (2010). Resistant starch as functional ingredient: A review. Food Research International, 43(4), 931–942. Galanakis, C. M. (2012). Recovery of high added-value components from food wastes: Conventional, emerging technologies and commercialized applications. Trends in Food Science & Technology, 26(2), 68–87. Gaur, R., Sharma, A., Khare, S. K., & Gupta, M. N. (2007). A novel process for extraction of edible oils: Enzyme assisted three phase partitioning (EATPP). Bioresource Technology, 98(3), 696–699. Gendebien, R., Ferguson, J., Brink, H., Horth, M., Davis, R., & Brunet, H. P. J. (2001). Survey of wastes spread on land- Final report study contract Retrieved from http://ec.europa.eu/environment/waste/studies/compost/landspreading.pdf. Giori, A., Arpini, S., & Togni, S. (2013). Tamarind seed polysaccharide for use in the treatment of inflammatory diseases, Patent No. EP2575973 A1, U.S. Goula, A. M. (2013). Ultrasound-assisted extraction of pomegranate seed oil Kinetic modeling. Journal of Food Engineering, 117(4), 492–498. Goula, A. M., & Adamopoulos, K. G. (2012). A method for pomegranate seed application in food industries: Seed oil encapsulation. Food and Bioproducts Processing, 90(4), 639–652. Grossmann, M. E., Mizuno, N. K., Schuster, T., & Cleary, M. P. (2010). Punicic acid is an omega-5 fatty acid capable of inhibiting breast cancer proliferation. International Journal of Oncology, 36(2), 421–426. Guo, C., Yang, J., Wei, J., Li, Y., Xu, J., & Jiang, Y. (2003). Antioxidant activities of peel, pulp and seed fractions of common fruits as determined by FRAP assay. Nutrition Research, 23(12), 1719–1726. Idris, A., Vijayaraghavan, R., Patti, A. F., & MacFarlane, D. R. (2014). Distillable protic ionic liquids for keratin dissolution and recovery. ACS Sustainable Chemistry & Engineering, 2(7), 1888–1894. Jiao, J., Li, Z.-G., Gai, Q.-Y., Li, X.-J., Wei, F.-Y., Fu, Y.-J., & Ma, W. (2014). Microwaveassisted aqueous enzymatic extraction of oil from pumpkin seeds and evaluation of its physicochemical properties, fatty acid compositions and antioxidant activities. Food Chemistry, 147, 17–24. Khoddami, A., Bin, Y., Man, C., & Roberts, T. H. (2014). Physico-chemical properties and fatty acid profile of seed oils from pomegranate (Punica granatum L.) extracted by cold pressing. 553-562. Kothari, V., & Seshadri, S. (2010). In vitro antibacterial activity in seed extracts of Manilkara zapota, Anona squamosa, and Tamarindus indica. Biological Research, 43(2), 165–168. Kumar, S., & Negi, Y. S. (2012). Corn cob xylan-based nanoparticles: ester prodrug of 5-aminosalicylic acid for possible targeted delivery of drug. Journal of Pharmaceutical Sciences and Research, 4, 1995–2003. Kundu, T. K., Vikru, R. S. B., Annavarapu, H. K., & Kempegowda, M. (2011). SiteSpecific Inhibitors of Histone Methyltransferase (HMTASE) and Process of Preparation Thereof. Patent No. 8,003,698, U.S. Kuzmenko, V., Hägg, D., Toriz, G., & Gatenholm, P. (2014). In situ forming spruce xylan-based hydrogel for cell immobilization. Carbohydrate Polymers, 102, 862–868. Laufenberg, G., Kunz, B., & Nystroem, M. (2003). Transformation of vegetable waste into value added products: (A) the upgrading concept; (B) practical implementations. Bioresource Technology, 87(2), 167–198. Lavecchia, R., & Zuorro, A. (2010). Process for the extraction of lycopene misc, Google Patents. Retrieved from http://www.google.com/patents/ US20100055261. Lehmann, J., Rillig, M. C., Thies, J., Masiello, C. A., Hockaday, W. C., & Crowley, D. (2011). Biochar effects on soil biota – A review. Soil Biology and Biochemistry, 43 (9), 1812–1836. Li, B., Ou, L., Dang, Q., Meyer, P., Jones, S., Brown, R., et al. (2015a). Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production. Bioresource Technology, 196, 49–56. Li, Q., Zhang, Y., & Hu, G. (2015b). Techno-economic analysis of advanced biofuel production based on bio-oil gasification. Bioresource Technology, 191, 88–96.
21
Lianfu, Z., & Zelong, L. (2008). Optimization and comparison of ultrasound/ microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomatoes. Ultrasonics Sonochemistry, 15(5), 731–737. Liker, H. (2014). Method of using pomegranate extracts for increasing prostate specific antigen doubling time. Patent No. US 2014/0044809, U.S. Lim, J., Yoo, J., Ko, S., & Lee, S. (2012). Extraction and characterization of pectin from Yuza (Citrus junos) pomace: A comparison of conventional-chemical and combined physical–enzymatic extractions. Food Hydrocolloids, 29(1), 160–165. Lisichkov, K., Kuvendziev, S., & Lisichkov, B. (2011). Isolation of tomato seed oil from tomato waste by application of supercritical fluid CO2 extraction. Quality of Life (Banja Luka)-APEIRON, 3(1-2). Liu, J., Willför, S., & Xu, C. (2015). A review of bioactive plant polysaccharides: Biological activities, functionalization, and biomedical applications. Bioactive Carbohydrates and Dietary Fibre, 5(1), 31–61. Liu, L., Fishman, M. L., Kost, J., & Hicks, K. B. (2003). Pectin-based systems for colonspecific drug delivery via oral route. Biomaterials, 24(19), 3333–3343. Mackler, A. (2014). Methods and compositions for treatment of uriniary tract infections. Patent No. US 2016/9,248,154. U.S. Mandawgade, S. D., & Patravale, V. B. (2008). Formulation and evaluation of exotic fat based cosmeceuticals for skin repair. Indian Journal of Pharmaceutical Sciences, 70(4), 539–542. Maran, J. P., Sivakumar, V., Thirugnanasambandham, K., & Sridhar, R. (2014). Microwave assisted extraction of pectin from waste Citrullus lanatus fruit rinds. Carbohydrate Polymers, 101, 786–791. Matharu, A. S., Houghton, J. A., Lucas-Torres, C., & Moreno, A. (2016). Acid-free microwave-assisted hydrothermal extraction of pectin and porous cellulose from mango peel waste – towards a zero waste mango biorefinery. Green Chemistry [In press]. Michel Philippe. (2004). Green chemistry for sustainable development at L’OREAL : synthesis of new c -glycosides of large interest in cosmetics, 2002051828, 2050. Milner, J. A., & Romagnolo, D. F. (2010). Cancer biology and nutrigenomics. In A. J. Milner & F. D. Romagnolo (Eds.), Bioactive compounds and cancer (pp. 25–43). Totowa, NJ: Humana Press. Minjares-Fuentes, R., Femenia, A., Garau, M. C., Meza-Velázquez, J. A., Simal, S., & Rosselló, C. (2014). Ultrasound-assisted extraction of pectins from grape pomace using citric acid: a response surface methodology approach. Carbohydrate Polymers, 106, 179–189. Mlambo, V., & Mapiye, C. (2015). Towards household food and nutrition security in semi-arid areas: What role for condensed tannin-rich ruminant feedstuffs? Food Research International, 76(Part 4), 953–961. Huchin, M. V., Estrada-Mota, I., Estrada-Leon, R., Cuevas-Glory, L. F., & Sauri-Duch, E. (2013). Chemical composition of crude oil from the seeds of pumpkin (Cucurbita spp.) and mamey sapota (Pouteria sapota Jacq.) grown in Yucatan, Mexico. CyTA – Journal of Food, 11(4), 324–327. Morris, V. J., Belshaw, N. J., Waldron, K. W., & Maxwell, E. G. (2013). The bioactivity of modified pectin fragments. Bioactive Carbohydrates and Dietary Fibre, 1(1), 21–37. Mukherjee, A. K., Adhikari, H., & Rai, S. K. (2008). Production of alkaline protease by a thermophilic Bacillus subtilis under solid-state fermentation (SSF) condition using Imperata cylindrica grass and potato peel as low-cost medium: Characterization and application of enzyme in detergent formulation. Biochemical Engineering Journal, 39(2), 353–361. Nafisi-Movaghar, K., Druz, L. L., & Victoria, C. P. (2013). Conversion of citrus peels into fiber, juice, naringin, and oil. Patent No. US 2013/0064947 A1, U.S. Nagel, A., Neidhart, S., Anders, T., Elstner, P., Korhummel, S., Sulzer, T., et al. (2014). Improved processes for the conversion of mango peel into storable starting material for the recovery of functional co-products. Industrial Crops and Products, 61, 92–105. Nawirska, A., & Kwas´niewska, M. (2005). Dietary fibre fractions from fruit and vegetable processing waste. Food Chemistry, 91(2), 221–225. NGWA (2016). Facts About Global SM Groundwater Usage Retrieved from http:// www.ngwa.org/Fundamentals/use/Documents/global-groundwater-use-fact-sheet. pdf. National Horticultural Board. (2015). Indian Horticulture Database 2013. 1–286. http://nhb.gov.in/area-pro/NHB_Database_2015.pdf; Accessed 03.06.2016. Okino-Delgado, C. H., & Fleuri, L. F. (2015). Orange and mango byproducts: agroindustrial waste as source of bioactive compounds and botanical versus commercial description–A review. Food Reviews International, 32(1), 1–14. Paggiola, G., Stempvoort, S. Van., Bustamante, J., Barbero, J. M. V., Hunt, A. J., & Clark, J. H. (2016). Can bio-based chemicals meet demand? Global and regional casestudy around citrus waste-derived limonene as a solvent for cleaning applications. Biofuels, Bioproducts and Biorefining, 10(6), 686–698. Parfitt, J., Barthel, M., & Macnaughton, S. (2010). Food waste within food supply chains: quantification and potential for change to 2050. Philosophical Transactions of the Royal Society of London B: Biological Sciences, 365(1554), 3065–3081. Patterson, E., Wall, R., Fitzgerald, G. F., Ross, R. P., & Stanton, C. (2012). Health implications of high dietary omega-6 polyunsaturated Fatty acids. Journal of Nutrition and Metabolism, 2012, 539426. Pelegrini, P. B., Noronha, E. F., Muniz, M. A. R., Vasconcelos, I. M., Chiarello, M. D., Oliveira, J. T. A., & Franco, O. L. (2006). An antifungal peptide from passion fruit (Passiflora edulis) seeds with similarities to 2S albumin proteins. Biochimica et Biophysica Acta (BBA)-Proteins and Proteomics, 1764(6), 1141–1146. Pereira, C. G., & Meireles, M. A. A. (2010). Supercritical fluid extraction of bioactive compounds: Fundamentals, applications and economic perspectives. Food and Bioprocess Technology, 3(3), 340–372.
22
J. Banerjee et al. / Food Chemistry 225 (2017) 10–22
Pfaltzgraff, L. A. (2014). The study & development of an integrated & additive-free waste orange peel biorefinery. University of York. Pfaltzgraff, L. A., De bruyn, M., Cooper, E. C., Budarin, V., & Clark, J. H. (2013). Food waste biomass: a resource for high-value chemicals. Green Chemistry, 15(2), 307–314. Puglisi, I., Petrone, G., Piero, A., & Lo, R. (2012). Role of actinidin in the hydrolysis of the cream milk proteins. Food and Bioproducts Processing, 90(3), 449–452. Puri, M., Kaur, A., Singh, R., & Kanwar, J. (2008). Immobilized enzyme technology for debittering citrus fruit juices. In Food enzymes: Application of new technologies. [pp. 91–103]. Rabbani, G. H., Teka, T., Zaman, B., Majid, N., Khatun, M., & Fuchs, G. J. (2001). Clinical studies in persistent diarrhea: dietary management with green banana or pectin in Bangladeshi children. Gastroenterology, 121(3), 554–560. Ribeiro, I. A., Rocha, J., Sepodes, B., Mota-Filipe, H., & Ribeiro, M. H. (2008). Effect of naringin enzymatic hydrolysis towards naringenin on the anti-inflammatory activity of both compounds. Journal of Molecular Catalysis B: Enzymatic, 52–53, 13–18. Roggeveen, K. (2010). Tomato journey from farm to fruit shop: greenhouse gas emissions and cultural analysis. University of Wollongong. Ruiz-Montañez, G., Ragazzo-Sánchez, J. A., Calderón-Santoyo, M., Velázquez-de la Cruz, G., Ramírez de León, J. A., & Navarro-Ocaña, A. (2014). Evaluation of extraction methods for preparative scale obtention of mangiferin and lupeol from mango peels (Mangifera indica L.). Food Chemistry, 159, 267–272. Sandhu, K. S., & Lim, S.-T. (2008). Structural characteristics and in vitro digestibility of Mango kernel starches (Mangifera indica L.). Food Chemistry, 107(1), 92–97. Scheller, H. V., & Ulvskov, P. (2010). Hemicelluloses. Annual Review of Plant Biology, 61(1), 263–289. Scoma, A., Bertin, L., Zanaroli, G., Fraraccio, S., & Fava, F. (2011). A physicochemical– biotechnological approach for an integrated valorization of olive mill wastewater. Bioresource Technology, 102(22), 10273–10279. Sßener, S., Sarıdog˘an, E., Staub, S., binti Ab Aziz, N. S., bin Mohd Nor, M. A., binti Abdul Manaf, S. F., et al. (2015). World conference on technology, innovation and entrepreneurship suitability of biochar produced from biomass waste as soil amendment. In Procedia – social and behavioral sciences (Vol. 195, pp. 2457–2465). . Singh, R. D., Banerjee, J., & Arora, A. (2015). Prebiotic potential of oligosaccharides: A focus on xylan derived oligosaccharides. Bioactive Carbohydrates and Dietary Fibre, 5(1), 19–30. Sogi, D. S., Siddiq, M., Greiby, I., & Dolan, K. D. (2013). Total phenolics, antioxidant activity, and functional properties of ‘‘Tommy Atkins” mango peel and kernel as affected by drying methods. Food Chemistry, 141(3), 2649–2655.
Sonwai, S., Kaphueakngam, P., & Flood, A. (2012). Blending of mango kernel fat and palm oil mid-fraction to obtain cocoa butter equivalent. Journal of Food Science and Technology, 51(10), 2357–2369. Taboada, E., & Siacor, F. D. (2013). Preparation of pectin and polyphenolic compositions from mango peels. misc, Patent No. WO2013/141723 A1, Talamban. Talekar, S., Desai, S., Pillai, M., Nagavekar, N., Ambarkar, S., Surnis, S., et al. (2013). Carrier free co-immobilization of glucoamylase and pullulanase as combi-cross linked enzyme aggregates (combi-CLEAs). RSC Advances, 3(7), 2265–2271. Tyler, D., Jing, Q., Wafa, W., Duncan, S., Tschirner, U., Schilling, J., et al. (2011). Bioresource technology improved pretreatment of lignocellulosic biomass using enzymatically-generated peracetic acid. Bioresource Technology, 102(8), 5183–5192. Udenigwe, C. C., & Aluko, R. E. (2012). Food protein derived bioactive peptides: Production, processing, and potential health benefits. Journal of Food Science, 77 (1), R11–R24. Ullah, N., Ali, J., Khan, F. A., Khurram, M., Hussain, A., & Rahman, I. U. (2012). Proximate composition, minerals content, antibacterial and antifungal activity evaluation of pomegranate (Punica granatum L.) peels powder. Middle-East. Journal of Scientific Research, 11(3), 396–401. Vijayaraghavan, R., & MacFarlane, D. R. (2014). CO2-based alkyl carbamate ionic liquids as distillable extraction solvents. ACS Sustainable Chemistry & Engineering, 2(7), 1724–1728. Wadhwa, M., & Bakshi, S. P. M. (2013). Utilization of fruit and vegetable wastes as livestock feed and as substrates for generation of other value-added products. RAP Publication 2013-04 (FAO). Retrieved from . Wang, S., Chen, F., Wu, J., Wang, Z., Liao, X., & Hu, X. (2007). Optimization of pectin extraction assisted by microwave from apple pomace using response surface methodology. Journal of Food Engineering, 78(2), 693–700. Wani, A. A., Kaur, D., Ahmed, I., & Sogi, D. S. (2008). Extraction optimization of watermelon seed protein using response surface methodology. LWT-Food Science and Technology, 41(8), 1514–1520. Yanes, E. G., Gratz, S. R., Baldwin, M. J., Robison, S. E., & Stalcup, A. M. (2001). Capillary electrophoretic application of 1-alkyl-3-methylimidazolium-based ionic liquids. Analytical Chemistry, 73(16), 3838–3844. Yu, J., Dandekar, D. V., Toledo, R. T., Singh, R. K., & Patil, B. S. (2007). Supercritical fluid extraction of limonoids and naringin from grapefruit (Citrus paradisi Macf.) seeds. Food Chemistry, 105(3), 1026–1031. Zhao, X., Brown, T. R., & Tyner, W. E. (2015). Stochastic techno-economic evaluation of cellulosic biofuel pathways. Bioresource Technology, 198, 755–763.
