Accepted Manuscript

Fractionation of apple by-products as source of new ingredients: Current situation and

perspectives

Holy Nadia Rabetafika, Brahim Bchir, Christophe Blecker, Aurore Richel

PII: S0924-2244(14)00185-X
DOI: 10.1016/j.tifs.2014.08.004
Reference: TIFS 1576

To appear in: Trends in Food Science & Technology

Please cite this article as: Rabetafika, H.N., Bchir, B., Blecker, C., Richel, A., Fractionation of apple by-
products as source of new ingredients: Current situation and perspectives, Trends in Food Science &
Technology (2014), doi: 10.1016/j.tifs.2014.08.004.

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 ACCEPTED MANUSCRIPT
1 Fractionation of apple by-products as source of new ingredients: Current situation and

2 perspectives

3 Holy Nadia Rabetafika1*, Brahim Bchir2, Christophe Blecker2, Aurore Richel1

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4 University of Liège, Gembloux Agro-Bio Tech, Department of Industrial

5 Biological Chemistry, 2, passage des déportés, B-5030 Gembloux, Belgium

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7 University of Liège, Gembloux Agro-Bio Tech, Department of Food Science and

8 Formulation, 2, passage des déportés, B-5030 Gembloux, Belgium

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9 *Corresponding author Tel: +32(0)81/62.26.22

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10 Fax: +32(0)81/62.22.31
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11 *E-mail address: hnrabetafika@ulg.ac.be

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13 Abstract

14 Apple (Malus sp.) is among the most processed fruit that generates high amount of wastes.

15 Depending on processes, various by-products are available offering a great diversity of low-

16 cost raw materials. Biorefinery processes are expected to convert them into new added-value

17 products such as hemicelluloses, oligosaccharides and polyphenols. This paper reviews the

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18 current uses of apple by-products as source of fibre and phytochemicals with special emphasis

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19 on recent fractionation processes. Future trends and challenges of apple by-product reuse are

20 discussed.

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22 Keywords: Apple by-product, dietary fibre, fractionation process, hemicelluloses, pectins,

23 polyphenols
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25 Introduction

26 The waste management is one of the major preoccupations of food industries. The use and the

27 disposal of food wastes are complex due to their high water content and their important

28 organic load susceptible to an enzymatic degradation and a rapid auto-oxidation (Russ &

29 Meyer-Pittrof, 2004). In the case of fruit processing, the production of apple juice generates a

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30 huge volume of waste considering the annual processed tonnage of up to 12 million tons (Mt)

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31 (USAD, 2013). The large amount of by-product prone to microbial decomposition may cause

32 environmental issues if disposed and thus lead to additional waste treatment costs for the food

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33 manufacturers. By contrast, the huge volume of the low-cost by-product possibly will offer

34 economical perspectives of its potentially valuable components. Its use as feed has been

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considered but only a small proportion is retrieved in low-cost livestock diets. Therefore, the
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36 recovery of commodities from the by-products appears advantageous and generates
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37 economical and environmental benefits.

38 The biotechnological processing of apple by-products has been largely prospected. Apple by-
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39 products have been proposed as a substrate for enzymatic catalysed productions of different
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40 chemicals such as citric acid, fuel purposes, flavour components and pigments (Joshi &

41 Devender, 2006). In non-fermentative way, the direct extractions of bioactive molecules such
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42 as dietary fibre, polyphenols and tannins have been reviewed (Bhushan, Kalia, Sharma,

Singh, & Ahuja, 2008; Shalini & Gupta, 2010). In the case of the dietary fibre, many studies
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44 report the feasibility of its extraction at large scale. However, the fractionation of the core

45 components will generate higher added value from apple by-products. In this way, it will

46 contribute to the recent and innovative implementation of the biorefinery concept applied to

47 food wastes for an optimal use and a new value-added creation. Bioactive polyphenols are

48 other valuable compounds in apple by-products that have been considered in the last years.

49 This paper reviews and discusses the current uses of apple by-product as source of dietary

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50 fibre and phytochemicals with special emphasis on their fractionation processes. The

51 heterogeneity of apple by-products and compositions are highlighted. Recent applied

52 technologies are surveyed prior to exploring potential applications. Finally, future trends and

53 challenges of apple by-product re-use are discussed.

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55 Variability of source and composition of apple by-products

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56 Apple (Malus sp.) is among the most traded fruit in the world. The global production has

57 reached 67.9 Mt in 2013 and is expected to have a constant increase within the next years

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58 (USAD, 2013). Eighteen percent of the global production is processed that generates

59 significant volume of by-products. Figure 1 summarises the by-products obtained from the

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apple processing showing that the industrial apple by-product is essentially composed of press
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61 residues from juice and cider manufacturing. The apple semi-industrial processes of freezing,
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62 canning, dehydration also produce by-product containing major residual epidermis and

63 endocarp (Sato et al., 2010).

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64 Pomace is the press residues obtained after processing including those from juice, cider, wine,
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65 distilled spirit and vinegar manufacturing as well as those from the industrial processes of

66 jelly and butter. The solid waste represents 20-35% of the fresh weight of the apple fruit. The
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67 residue is composed of a mixture of peel, core, seed, calyx, stem and pulp. The major fraction

comes from the epi-mesocarp accounting up to 95.5% of the solid waste (Canteri, Nogueira,
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69 Petkowicz, & Wosiacki, 2012).

70 During the juice and cider manufacturing, processes may vary from one company to another.

71 The system of continuous press is the most applied in industrial fruit juice but in small

72 companies discontinuous vertical hydraulic press can be used (Canteri et al., 2012). Before

73 pressing, skins, stalks and pips may be removed during the step of apple crushing thus can

74 influence the composition of the pomace (Riedl, 2013). The addition of pectinolytic enzymes

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75 during the juice manufacturing also affects the final composition of the apple pomace and

76 pectin contents. The cooking step of the syrup, jelly and butter manufacturing implies fibre

77 extraction, specific aromas and sensory characteristics of the pomace (Aguedo et al., 2012).

78 Apple peels accounts for 13% of the weight of the fresh apple fruit (Tarazona-Diàz &

79 Aguayo, 2013). Apple peel by-products are obtained from fresh-cut fruit, apple pie and sauce

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80 manufacturing. Immediately after peeling, the skins are blanched or treated with chemicals to

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81 prevent enzymatic browning (Rupasinghe, Wang, Huber, & Pitts, 2008).

82 Apple seeds are obtained by sieving and separation from apple pomace. The mass fraction of

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83 the seed in apple pomace accounts for 4-7%. Apple seeds contain a cyanogenic glycoside,

84 amygdalin, the degradation of which by β-glucosidase naturally present in human intestine

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can lead to the formation of cyanide causing human severe toxicity (Bolarinwa, Orfila, &
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86 Morgan, 2014; Lu & Foo, 1997). A recent patent proposes a method and an apparatus for the
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87 separation of seeds from fruit pulp (Bhushan, Gupata, Babu, Sharma, & Ahuja, 2013).

88 According to the end-products, various technologies are applied to apple fruits that influence
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89 the composition of the by-products. For example, as seen in table 1, the major component of
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90 apple pomace and peels is constituted by the dietary fibre up to around 65% of dry weight. By

91 contrast, apple seeds contain proteins and oils in huge quantities, respectively up to 49.5%
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92 and 24%. The apple pomace from syrup manufacturing has low pectin and soluble fibre

contents (2.9% and 0.0% respectively) due to the cooking process. The blanching treatment
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94 applied to apple peels concentrates soluble fibre up to 32.1% compared to untreated peels

95 which contain only 5.8% (Henriquez et al., 2010; Rupasinghe et al., 2008). In addition, the

96 diversity of the quantification methods, maturation stage and cultivars may influence the

97 composition. Nevertheless a global trend emerges from data in literature. The insoluble fibre

98 represents the major dietary fibre in all pomace. Cellulose is the most important fraction

99 attaining 43% of the pomace. Hemicelluloses are the second most important fibre in apple

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100 pomace (19.9-32.2%). The phenolic compounds are concentrated in the seed and peel by-

101 products principally as chlorogenic acid and phloridzin. The phenolic compound profile of

102 apple peel contains the following flavanols namely (-) epicatechin and catechin, and the

103 following anthocyanins namely cyanidin-3-galactosides (Table 2).

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105 Extraction and fractionation of apple by-products

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106 Dietary fibre includes soluble and insoluble part constituted mainly by carbohydrate polymers

107 with ten or more monomeric units that are non-hydrolysable by the endogeneous enzyme in

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108 small intestine of human. It includes associated compounds like lignin in the case of plant

109 origins according to the Codex definition (McCleary et al., 2011). As reported, direct drying

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without pretreatment is the most common industrial operation and economical approach for
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111 obtaining valuable fraction from the apple pomace. However, the extraction and the
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112 fractionation of fibre generate high-added value molecules with various application areas.

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114 Fibre concentrate extraction

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115 The extraction of fibre is the easiest way to fractionate apple by-product into fibre concentrate

116 and non-fibre fraction. The isolation of fibre is motivated by its ability to improve physical
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117 and textural properties in many food products as well as its beneficial effects on human

health. Two main processes have been applied to apple by-products in order to isolate the
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119 dietary fibre.

120 The desugaring process is carried out in order to decrease free monosaccharides either by

121 aqueous or by alcoholic extraction generally operated at room temperature. The aqueous

122 method produces pectin-rich fibre with significant amount of bioactive phenolic compounds.

123 The alcoholic process is less efficient to concentrate fibre. The low purity of the obtained

124 fibre is due to protein contaminants (Sun-Waterhouse, Farr, Wibisono, & Saleh, 2008).

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125 Moreover, the ethanolic process extracts bioactive phenolic compounds and decreases the

126 antioxidant activity of the dietary fibre. However, extraction of phenolic compounds better

127 improves the physical properties of fibre like water binding capacity (Kosmala et al., 2010).

128 Another advantage of the alcoholic washing is that the process may prevent the porous

129 collapse and the shrinkage of fibre during the following drying process (Borchani et al.,

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130 2011). From industrial and economical points of view, the aqueous process is the easiest way

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131 to scale-up and is more advantageous in term of cost. The consequences of the desugaring

132 step are the increase of insoluble dietary fibre (IDF) and sometimes slight modification of the

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133 fibre proportion. An improvement of the hydration properties is often observed after the

134 aqueous washing. The aqueous desugaring increased the dietary fibre content by 1.2 fold and

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improved the hydration properties up to 1.4 fold (Rabetafika, Bchir, Aguedo, Paquot, &
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136 Blecker, 2014).
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137 The bleaching process is applied to the brownish apple pomace in order to produce light

138 coloured fibre concentrates. The process with alkaline hydrogen peroxide at pH 12 has been
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139 proven to decolour the apple pomace yielding a cellulose-rich yellow product. The
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140 consequence of the bleaching process is a drastic modification of the fibre proportion due to

141 lignin extraction and the major part of pectins. After bleaching, free sugars are extracted
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142 suggesting that it may also replace the desugaring step (Rabetafika et al., 2014). Such

modification produces improvement of the hydration properties (6.2 g water per g to 10.0 g
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144 per g). A recent patent discloses a decolouring method of apple pomace with alkaline

145 solution/ozone ultrasonic assisted extraction (Chen & Li, 2013). From the economical and

146 environmental points of view, bleaching is not advantageous compared to the desugaring

147 process due to low yields of fibre concentrate (around 50% of initial matter according to

148 Renard et al., (1996)) and the chemical involved. Moreover, the unbleached apple pomace

149 fibre could be integrated into food products i.e. bread, dairy products and beverages.

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150

151 Pectins

152 Pectin is a complex mixture of polysaccharides which major backbone is a polymer of 1,4-α

153 D-galactosyluronic acid residues partially esterified with methyl alcohol at the carboxylic

154 acid. A certain amount of neutral sugars might be present as side chain. The complex

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155 polysaccharides can be composed of up to 17 different monosaccharides and containing more

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156 than 20 different linkages (Voragen, Coenen, Verhoef, & Schols, 2009). Apple pectin is a

157 mixture of complex structure including homogalacturonans, xylogalacturonans and

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158 rhamnogalacturonans with side chains of arabinogalactans and arabinans (de Vries, Voragen,

159 Rombouts, & Pilnik, 1986; Walia, Sharma, Bhushan, Kumar, & Singh, 2013). Depending on

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the cultivars, the pectic fraction of apple pomace has total content of uronic acids up to
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161 53.38%. The number of methoxyl group varies between 48% and 53%. The neutral fraction
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162 represents up to 47.21% whereas the average of degree of esterification, one of the most

163 important parameters that determine its quality, varies up to 72.29% (Sato et al., 2011).
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164 Various processes have been used to extract pectins in apple by-products. The conventional
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165 fractionation method of pectins from apple pomace consists of treating the raw materials with

166 hot mineral acid such as hydrochloric, sulphuric and nitric acids at a pH range of 1.5-3.0.
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167 Compared to mineral acid, organic acid such as citric acid is more efficient to extract pectin

from apple pomace with yield of 13.75% vs. 12.5% for hydrochloric acid extraction (Canteri-
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169 Schemin, Fertonani, Waszczynskyj, & Wosiacki, 2005). The kinetic models of pectin

170 extraction have shown that the yield and the intrinsic viscosity are respectively exponential

171 functions with time and temperature (Cho & Hwang, 2000). Other parameters that influence

172 the yield and quality of pectins are pH and temperature extractions. For example, increase of

173 the temperature results in higher pectin yield (7.9% at 80 °C vs. 8.9% at 90 °C). The pectin

174 yield is higher at pH 1.5 compared to pH 2.0 at 90°C (8.9% vs. 4.2%). By contrast, the purity

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175 of galacturonic acid is higher at pH 1.5 (Garna et al., 2007). At industrial scale, acid or base

176 treated pomace is subjected to subsequent extraction with dilute acid. The viscous extract

177 containing up to 1% soluble pectin is obtained after filtration or centrifugation. The pectin is

178 precipitated, separated and dried to obtain the commercial pectin (Buchholt & Vinter, 1991).

179 This process generally yields high-methoxyl pectin with degree of esterification (DE) of

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180 around 70% (Raj, Rubila, Jayabalan, & Ranganathan, 2012). In order to obtain low-methoxyl

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181 pectin, acidic hydrolysis of high-methoxyl pectin is carried out (Minkov, Minchev, & Paev,

182 1996). The direct production of low methoxyl pectin from apple pomace has shown the effect

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183 of the acid concentration and the duration of extraction period on the DE. Low-methoxyl

184 pectin with DE of 50.79% is obtained by extraction with 0.1 mol L-1 nitric acid during 10 min

185 at 97 °C (Fertonani et al., 2009).

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186 Increasingly, environmental friendly water-based processes are being developed to extract
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187 pectins from apple pomace in order to reduce chemical reagent utilisation and to minimize the

188 environmental impacts. The water-based extraction may be combined with physical and/or
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189 enzymatic treatments to facilitate the extraction of pectins. For example, the aqueous
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190 solubilisation of pectins up to 19.75% is obtained with extruded pomace compared to 3.68%

191 for non extruded material. Moreover, the extrusion provides more solubilising effects (up to
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192 1.4 fold) than the classical acidic extraction at pH 1.8 and 85 °C when the specific mechanical

energy (SME) is higher than 130 kWh t-1 (Hwang, Kim, & Kim, 1998). The combination of
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194 homogenisation and enzymatic treatments with a fungal β-glucanase gives low yield

195 compared to the conventional acidic extraction (4.6% vs. 7.7%). In addition, the isolated

196 pectins exhibit lower content of galacturonic acid and higher degree of esterification

197 compared to the chemically-extracted pectins (Min et al., 2011). The extraction with cellulase

198 (pH 4.5, 50 °C, 180 min), acting on cellulose/xyloglucan networks, is more efficient to extract

199 pectins and soluble fibre yielding up to 18.7% of soluble fibre (Li, He, Lv, & He, 2014).

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200 Non conventional water-based technology such as subcritical water extraction has been used

201 for the recovery of pectin from apple by-products. The extraction by hot compressed water or

202 subcritical water is an hydrothermal process based on the miscibility, dielectric constant, ionic

203 product, electrolytic solvent power, viscosity properties of the pressurised water at

204 temperature above its boiling point at ambient pressure and below critical point (Tc: 375 °C,

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205 Pc: 22.1 MPa, ρc:320 kg m-3). The technology has been applied at moderate temperature

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206 (140-160 °C) and short time (5-15 min). At optimum temperature (140 °C) and optimum

207 extraction time (5 min), the extraction yields of pectic polysaccharide and galacturonic acid

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208 attain 17.55% and 8.46% respectively. Compared to commercial pectins, the molecular

209 weight and the galacturonic acid content are lower while ash and neutral sugars are higher

210 (Wang & Lü, 2014).

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211 Generally, conventional technologies are time consuming and have low yields. Ultrasound
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212 waves generate micro-cavitations in the liquid extraction that produce mechanical disruption

213 of cell wall to favour the release of its contents. The ultrasound-assisted extraction (UAE) has
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214 been carried out with pulsed sonication at 1-1.2 Wcm-2 and allows increasing the pectin yield
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215 by 28% compared to the conventional procedure (Panchev, Kirchev, & Kratchanov, 1988).

216 The microwave-assisted extraction (MAE) has been carried out during the extraction of pectin
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217 from apple pomace. The process is based on the use of microwave energy to rapidly heat

solvents in contact with sample in order to partition analytes from the sample matrix into the
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219 solvent. MAE dramatically reduces reaction time (20.8 min) at optimal conditions ( pH 1.01,

220 ratio solid-liquid of 0.069, microwave power of 499.4 W) compared to the conventional

221 extraction method up to 240 min (Li et al., 2014; Wang et al., 2007).

222 The pulsed electric field based on the electroporation in cells has been carried out to improve

223 the extraction of apple pomace pectins. A yield of 14.12% is attained by the application of

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224 electric field intensity of 15 kVcm-1, electric pulse number of 10 at pH 3, 60 °C (Yin, Fan,

225 Liu, Yu, & He, 2009).

226 The influence of extraction mode on yield and characteristics of pectins from apple pomace is

227 highlighted in Table 3. The subcritical water extraction shows obvious effect on the quality of

228 extracted pectins. Isolated pectins are highly esterified (60.23-85.99%) and have low content

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229 of galacturonic acid (<50%). The molecular weight of the polysaccharides is lower compared

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230 to the conventional acidic extraction showing that subcritical water induces degradation or

231 hydrolysis of the pectic polysaccharides. The extraction by enzymatic hydrolysis is not

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232 efficient but gives nearly pure pectic polysaccharides rich in galacturonic acid and high

233 molecular weight. Sonication produces degradation (low gel strength) and desesterification of

234 pectins (65.8% vs. 71.1% for the control).

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235 From the economical point of view, the conventional method is time and energy consuming.
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236 For example, 240 min are required to attain a pectin yield of 10.3% whereas 2 min and 40 min

237 are sufficient to reach the maximum yield respectively for MAE (14.9%) and UAE (16.4%).
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238 The MAE is more cost-effective compared to UAE. Assuming that the consumed energy is
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239 equal to the power field multiply by the extraction time, the energy associated per g of pectins

240 at maximum yields are 4.43 KJ and 50.53 KJ for MAE and UAE respectively (Li et al., 2014).
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241 Concerning the purification of pectins, environmental friendly methods have been proposed

as alternative to the alcoholic precipitation process. The ultrafiltration has been used to
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243 separate apple pectin on the basis that 68% of the pectin have molecular weights over 300

244 kDa whereas a minority has molecular weight below 5 kDa (Qiu, Tian, Qiao, & Deng, 2009).

245 In a recent patent, the ultrafiltration method is combined with two subsequent nanofiltrations

246 on membranes with molecular weight cut-off (MWCO) of 0.1 kDa and 0.2 kDa applying

247 0.14-0.15 MPa pressure to purify pectins from apple pomace (Lv, Dong, & Ma, 2012). The

248 advantage of ultrafiltration technologies is to reduce chemical utilisation. However, the high

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249 viscosity of the product may limit their utilisation at industrial scale and reduce lifetime of the

250 membranes.

251 Pectins from apple pomace have often light brown colour. A process producing colourless

252 acidic pectins by separation of phenolic compounds is achieved by extraction with diluted

253 mineral acid and adsorption of phenolic constituents by a hydrophobic styrene–

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254 divinylbenzene copolymerisate (Schieber et al., 2003). The advantage of the process is the

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255 combined recovery of pectin and polyphenols.

256 Recently, pectins have been isolated in an environmental friendly way by protein precipitation

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257 based on charge neutralisation of pectin regions using sodium caseinate. The maximum pectin

258 precipitation is obtained at pH 3.5 when the pectin acquires a negative charge while the

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protein is positively charged, promoting their attractions. (Garna, Emaga, Robert, & Paquot,
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260 2011). The advantage of the method is to isolate pectins with less neutral sugars due to the
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261 fact that the purification methods are more specific toward charged polysaccharides.

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263 Hemicelluloses
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264 Hemicelluloses are heteropolymers containing pentoses (β-D-xylose, α-L-arabinose), hexoses

265 (β-D-glucose, α-D-galactose, β-D-mannose) and uronic acids (α-D-glucuronic, α-D-4-o-

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266 methylgalacturonic and α- D -galacturonic acids). The hydroxyl groups of some sugars are
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267 partially substituted with acetyl groups. Hemicelluloses from apple are composed of a mixture
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268 of xyloglucans, arabinoxylans and mannans. Xyloglucans are the most studied hemicelluloses

269 present in the apple pomace. They represent up to 18% of the cell wall and are composed of

270 similar amounts of three repeating units containing xylose, glucose, galactose and fucose

271 residues (Renard, Lemeunier, & Thibault, 1995).

272 The conventional extraction process of xyloglucans is achieved by soaking and mixing the

273 apple pomace in alkaline solutions such as sodium hydroxide (NaOH), potassium hydroxide

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274 (KOH) and lime solutions (Ca(OH)2). The main factors influencing the extraction yield have

275 been determined as the alkali concentration and the duration of extraction. Increases of the

276 extraction time and the concentration of alkali improve the hemicellulose yields. However,

277 low yields as 0.53-2.04% of treated apple pomace have been obtained (Renard et al., 1995).

278 An enzymatic depectination pretreatment prior to the extraction of xyloglucans has no effect

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279 on yield but affects the molecular weight of xyloglucans. Pectins from the enzymatically-

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280 depectinated apple pomace are found to be of lower molecular weight than those from the

281 non-depectinated pomace due to the depolymerisation by cellulase in the commercial

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282 pectinase (Watt, Brasch, Larsen, & Melton, 1999). The yield of the extraction of

283 hemicelluloses by concentrated alkali (4 mol L-1 NaOH) after an acidic extraction of the

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pectinic polysaccharides remains relatively low up to 12.9% (Kosmala et al., 2010). The
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285 sequential extractions and fractionations of apple hemicelluloses increase the yield up to 37%
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286 (21.1% soluble in 8.4% lithium chloride/ dimethylsulfoxide (LiCl/DMSO) and 15.9% in 1

287 mol L-1 KOH and 4 mol L-1 KOH). The alkali fractions contain mainly xyloglucans with
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288 molecular weight of 150-200 kDa (Ray, Vigouroux, Quémener, Bonnin, & Lahaye, 2014).
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289 Addition of hydrogen peroxide during the alkaline extraction also improves the productivity.

290 A yield of up to 85% has been achieved after solubilisation at 50 °C during 480 min with 3%
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291 hydrogen peroxide at pH 12.5 (Hu, Liu, & Quan, 2011).

Non conventional method like ultrasound-assisted alkaline extraction has been evaluated for
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293 the isolation of xyloglucan from apple pomace. The ultrasonication allows speeding up about

294 three times the extraction compared to the traditional alkaline method. The most relevant

295 variable is the quadratic of liquid/solid ratio. The optimum combination is determined as a

296 liquid/solid ratio of 34.4:1, a KOH concentration of 3.3 mol L-1 and an ultrasound-assisted

297 extraction time of 150 min. (Fu, Tian, Li, Cai, & Du, 2006).

298

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299 Oligosaccharides

300 Oligosaccharides are oligomers which are composed of 3-10 monosaccharide residues

301 structurally linked by glycosidic bonds that are readily hydrolysed to their constituent

302 monosaccharides either by acids or specific enzymes (Kumar, Pushpa, & Prabha, 2012).

303 Production of oligosaccharides containing a mixture of pectin-derived oligosaccharides (POS)

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304 and neutral oligosaccharides has been carried out with apple pomace. The latter is suspended

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305 in solution containing pectinase or cellulase. Enzymatic treatments of apple pomace yield in

306 large amount of small pectins with molecular weight inferior to 10 kDa. The product contains

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307 mainly galacturonic acid (49-64 mol %), arabinose (14-23 mol %), galactose (6-15 mol %)

308 and minor amounts of rhamnose, xylose and glucose. After an ethanolic precipitation

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concentrated colloids (9.7-19.6 g L-1) are obtained with 60% of acidic polymers (Mehrlander,
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310 Dietrich, Sembries, Dongowski, & Will, 2002).
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311 Applying the dynamic high-pressure microfluidisation technology in order to produce pectic

312 oligosaccharides improves the yield. The optimal operating conditions are determined as
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313 temperature 63 °C, pressure of 155 Mpa and 6 cycle pass. The maximum yield of POS from
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314 the apple pectin solution (1.84%) is up to 32.92% (Chen et al., 2013). Compared to the

315 enzymatic process, the POS obtained by microfluidisation have higher content of neutral
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316 sugars (58.53%) and low content of galacturonic acid (29.56%).

Another class of oligosaccharides as xylo-oligosaccharides (XOS) has been obtained by

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318 enzymatic treatment using mixture of xylanase at mild conditions (50 °C and pH 6). The yield

319 based on the reducing sugar release is low (6%) (Mazzaferro, Cuna, & Breccia, 2011).

320 In a multi-added-value approach, the co-production of lactic acid and oligosaccharides from

321 apple pomace by sequential saccharification and fermentation is proposed. The oligomeric

322 carbohydrates are composed of a mixture of glucooligosaccharides, galactooligosaccharides,

323 xylooligosaccharides, arabinooligosaccharides and oligogalacturonides. After separation of

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324 the lactic acid by ion exchange, oligomers are refined by a two-step nanofiltration-diafiltration

325 and concentration membrane treatments. They obtained refined product with purity of 67.7%

326 (Gullón, Gullón, Sanz, Alonso, & Parajo, 2011).

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328 Cellulose

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329 Cellulose is a linear homopolymer consisting of regio- and enantioselectively β-1,4-glycosidic

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330 linked D-glucopyranose units. In apple pomace, cellulose represents the major constituent (up

331 to 43%). However, there are few studies on its utilisation. The fractionation of cellulose from

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332 apple pomace generally consists of combined alkaline extraction in the presence of hydrogen

333 peroxide or sodium hypochlorite. A cellulose fraction in the form of hydrogel has been

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obtained using dilute sodium hydroxide and hydrogen peroxide from apple pomace. The gel is
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335 a pseudo-plastic fluid. Its flow properties are similar to those of furcellaran, guar and xanthan
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336 gums. Freeze drying and milling affect its hydrophilic properties, but the particles

337 nevertheless show a tendency to wet and re-disperse easily (Walter, Rao, van Buren,
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338 Sherman, & Kenny, 1977). After a mild alkaline degradation of apple pomace, α-cellulosic
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339 fraction of approximately 26% of the untreated dry matter also has been obtained (Walter,

340 Rao, Sherman, & Cooley, 1985). The treatment of apple pomace with sodium hypochlorite
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341 and hydrolysis with 6% hydrochloric acid at 100 °C during 50 min allows the production of

microcrystalline cellulose with a high yield up to 69.5% (Guo & Luo, 2011). In a multi-
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342
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343 product approach, microcrystalline cellulose can be obtained by the combination of a

344 fermentation process and a blanching process to co-produce L-malic acid (Sun et al., 2008).

345

346 Lignin and phenolic compounds

347 Lignin is a complex macromolecule composed of methoxylated phenol units linked by ether

348 and carbon bonds. The presence of lignin in apple pomace favours its utilisation in the

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349 production of many value products such as organic acids, ethanol and aroma compounds

350 (Gassara et al., 2012). However, presently, there are no studies on the extraction and use of

351 lignin from apple pomace. According to Vishtal and Kraslawski (2011), the major obstacle to

352 the development of lignin fractionation is linked to the recovery and purification of lignin

353 from the product stream and heterogeneity and reactivity of lignin.

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354 The only one publication on apple pomace is related to the non conventional method of lignin

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355 extraction prior to the quantification. The microwave-assisted extraction has been applied to

356 apple pomace in order to quantify the lignin and is reported to be more efficient than the

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357 traditional refluxing. A lignin content of 33% has been determined compared to 27% for the

358 traditional method (Gassara et al., 2012). This technology may open a new perspective for the

359
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production of lignin from apple pomace for new emerging applications.
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360 Apple by-products contain other minor polyphenolic compounds with valuable antioxidant
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361 properties. These phytochemicals are present in the cell wall as free or bound phenolic forms.

362 In the insoluble forms, phenolic compounds are covalently bound to the cell wall structure as
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363 hemicelluloses and lignin. Phenolic acids like hydroxycinnamic acid form ether linkage with
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364 lignins. Procyanidins are bound to polysaccharides of the cell wall. In apple pomace, the

365 major phenolic compounds belong to the class of dihydrochalcones (phloridizin), flavanols
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366 (catechin and epicatechin) and hydroxycinnamic acid (chlorogenic acid). Flavonols i.e.

hyperin, quercetin and quercetin glycosides are present in apple pomace and peels.
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367
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368 Anthocyanins (cyaniding-3-galactoside) are mainly present in peels (table 2).

369 In order to improve extraction of phenolic compounds and to release bounded forms of

370 phenolic glycosides, apple pomace is recently used as substrate for solid state fermentation of

371 rot fungus (Phanerochaete chrysosporium). The extracellular production of lignolytic

372 enzymes degrades lignocelluloses materials therefore facilitates phenolic compound

373 extraction. The polyphenol contents of acetone extract after fermentation increase up to 3.5-

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374 fold compared to non fermented pomace (Ajila, Brar, Verma, Tyagi, & Valéro, 2011; Gassara

375 et al., 2012).

376 Conventional extraction processes of phenolic compounds from apple pomace consist of

377 maceration or soxhlet extraction with organic solvent such as ethanol, methanol, acetone,

378 ethyl acetate or dichloromethane. The choice of the solvent has great influence on the

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379 extraction and the quality of product. For example, 60-70% acetone in water is more efficient

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380 to extract phenolic compounds yielding up to 0.280 g compared to 50% ethanol and 50%

381 methanol in water with yields of 0.201 g and 0.204 g gallic acid equivalent per 100 g defatted

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382 apple seed respectively) (Fromm, Loos, Bayha, Carle, & Kammerer, 2013). The acetonic

383 extract contained higher total phenols, flavonols and phloretin glycosides compared to that of

384
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ethanolic extract (Wijngaard, & Brunton, 2010).
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385 However, the use of water for the extraction of phenolic compounds is currently proposed as
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386 an alternative green solvent. The objective is to decrease process costs and to increase process

387 safety. An aqueous extraction at room temperature allows the extraction of 67% of the total
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388 phenolic compounds, 72% of the total flavonoids and 51% of proanthocyanidins. Compared
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389 to the conventional methanolic extraction, aqueous extraction is efficient to isolate flavonoid

390 compounds. Nevertheless, the total phenolic compound contents are comparable to those of
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391 the conventional maceration method. At pilot scale, aqueous fractionation of 1 kg of dried

apple pomace yields extracts with 2.566 g of gallic acid equivalent, 6.696 g of quercetin and
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392
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393 0.837 g of catechin (Reis, Rai, & Abu-Ghannam, 2012).

394 Another proposed green solvent is the subcritical carbon dioxide (CO2). However, addition of

395 co-solvent like ethanol or methanol is required to increase polarity of subcritical CO2. The

396 optimum conditions have been determined as pressure of 54.6-57 MPa, temperature of 55.7-

397 58.4 °C, 20% of ethanol and 40 min using apple pomace as starting material. Nonetheless, the

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398 conventional ethanolic extraction is more efficient to isolate phenolic compounds compared

399 to the subcritical CO2 (Adil, Cetin, Yener, & Bayindirli, 2007).

400 Conventional processes are often time and energy consuming. Alternative technologies as

401 ultrasound-assisted extraction (UAE) have been demonstrated to save energy and to speed the

402 extraction. Forty minutes are sufficient to increase the yield by 15% in a water-based solvent

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403 compared to the long conventional maceration (480 min). At optimal conditions (intensity of

0.764 W cm-2, 40 °C, 40 min), 0.560 g catechin equivalent per 100 g of dry matter are

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404

405 obtained compared to 0.487 g catechin equivalent per 100 g dry matter for conventional

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406 maceration (Pingret, Fabiano-Tixier, Le Bourvellec, Renard, & Chemat, 2012).

407 Microwave-assisted extraction (MAE) has been proposed in the same perspectives of

408
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improvement of the time and cost-efficiency of phenolic compound extraction. MAE can
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409 increase the speed of the extraction up to 29-fold compared to conventional maceration or
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410 soxhlet methods (Rezaei, Rezaei, Haghighi, & Labbafi, 2013). Pressurised liquid extraction

411 (PLE) has been applied to recover phenolic compounds. The extraction method does not
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412 influence the phenolic compound profiles compared to those of conventional method
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413 (Grigoras, Destandau, Fougère, & Elfakir, 2013).

414 From energy consumption point of view, UAE is cost efficient compared to the MAE. Based
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415 on the calculation with data in literature the consumed energies per g (power field multiply by

time extraction) at maximum yield are 363.1 KJ and 568.4 KJ for UAE and MAE respectively
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416
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417 (Pingret et al., 2012; Rezaei et al., 2013).

418

419 Development state and current applications of apple by-product

420 The current state of uses and fractionation processes of fibre and phytochemicals from apple

421 by-products are outlined in the figure 2. Table 4 presents recent patents on apple pomace.

422

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423 Apple pomace and fibre concentrate

424 Potential applications of fibre concentrate reside in its low-caloric value and functional

425 properties such as water holding capacity, viscosity, gelation and sensory properties like

426 colors and aromas. Its use is at industrial development and processed by J. Rettenmaier Söhne

427 (Germany), Herbafood Ingredients GmbH (Germany), Maruha Nichiro Foods Inc. (Japan),

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428 Starwest Botanicals Inc. (USA), Tree Top Ingredients (USA) among main manufacturer.

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429 In food, apple pomace is often used as flour substitution in bread and other bakery products

430 like cakes, cookies, muffins, biscuits and baked scones (Masoodi, Chauhan, Tyagi, Kumbhar,

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431 & Kaur, 2001; Rupasinghe, Wang, Pitts, & Astatkie, 2009; Sudha, 2011). Apple pomace

432 increases fibre content in end-products and brings a natural colorant and flavouring avoiding

433
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the use of artificial source of colorant and flavour (Sudha, 2011).
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434 An incorporation of apple pomace at high proportion (up to 35%) in bread formulation affects
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435 the rheological and pasting properties of dough due to the pectin-rich dietary fibre

436 (Ktenioudaki, O’Shea, & Gallagher, 2012). At low proportion (2%), the incorporation of
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437 apple pomace with low content of pectins in breads and bakery products has been reported to
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438 improve dough properties like water absorption, stability and tenacity i.e. dough resistance to

439 extension. However, there is a significant change of the colour of baked products
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440 supplemented with apple pomace. The crumb and crust of bread are darker compared to those

of wheat based bread (Bchir, Rabetafika, Paquot, & Blecker, 2014).

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441
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442 In cakes, addition of apple fibre increases the batter viscosity up to 5-fold for 5-15% of wheat

443 flour replacement. The particle size of apple pomace affects the viscosity of batter and the

444 physical characteristics of cakes. The addition of apple pomace with fine particle size does not

445 significantly change the cake quality (Masoodi, Sharma, & Chauhan, 2002). The texture of

446 cakes becomes harder with increasing levels of apple pomace and induced browning of the

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447 crumb and crust colour. Nevertheless, a replacement at 20% is acceptable (Sudha, Baskaran,

448 & Leelavathi, 2007).

449 Fibre concentrate from apple pomace has been incorporated in extruded ready-to-eat snacks

450 and wheat chips (Kayacier, Yüksel & Karaman, 2014; O’Shea, Arendt, & Gallagher, 2014).

451 Addition of apple pomace is found to limit starch digestion and modify the structure of

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452 snacks. The addition of apple pomace in the formulation decreases the hardness of the

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453 extruded snacks and affects the acoustic properties of the end-product. A high quality snack is

454 obtained with optimal extrusion conditions and apple pomace inclusion determined to be die

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455 head temperature at 150 °C, screw speed of 69 rpm and apple pomace addition of 7.7%.

456 (O’Shea et al., 2014). In wheat chips, the addition of apple fibre modifies the colour and the

457
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crispiness of the snack food and depends on the frying temperature (Kayacier et al., 2014).
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458 In biscuit formulation, a substitution of flour up to 15% increases the water absorption (58.60-
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459 71.80%), the development time (from 3.43 min to 5.53 min) and the stability of dough. Apple

460 pomace can be incorporated into biscuits in the concentration of up to 5% without change of
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461 the sensory quality of the products (Kohajdová, Karovicová, Magala, & Kuchtová, 2014).
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462 In meat product, the incorporation of apple pomace at levels of up to 15% in mutton nuggets

463 stabilises the meat emulsion and improve the cooking yield. The addition of apple pomace
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464 decreases the hardness of end products. Sensory evaluation illustrated a reduction in texture

and flavour properties. However, incorporation of apple pomace at 5% level in nuggets

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465
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466 maintained the physico-chemical and sensory properties within the range of acceptability

467 (Huda, Parveen, Rather, Akhter, & Hassan, 2014).

468 Apple pomace fibre also has been used for the preparations of quince-based jelly and

469 smoothie beverage (Royer, Madieta, Symoneaux, & Jourjon, 2006; Sun-Waterhouse,

470 Bekkour, Wadhwa, & Waterhouse, 2014). The particle size of the apple fibre influences the

471 rheological properties of the beverage.

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472 In non food, apple fibre has been evaluated for the remediation of metal in contaminated soil

473 and water, as biosorbent or as polymer blends (Chand, Shil, Sharma, & Pakade, 2014;

474 Chiellini, Cinelli, Imam, & Mao, 2001; Robinson, & Chandran, 2002).

475

476 Apple peels, apple seeds and phenolic compounds

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477 Apple peel by-products have been largely evaluated as functional food ingredient and as

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478 nutraceuticals owing to the bioactivity of their phenolic compounds (Massini, Rico, Martin

479 Diana, & Barry-Ryan, 2013; Thilakarathna, & Rupasinghe, 2013; Wolfe & Liu, 2003). Apple

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480 peels have been used as functional ingredient in healthy foods like bakery product and could

481 be used as alternative dietary fibre source in various selected functional foods. The addition of

482
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apple peels in muffins increased the total dietary fibre from 1.3% (w/w) to 7.6% (w/w) and
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483 the antioxidant capacity of the bakery products (Rupasinghe, Wang, Huber, & Pitts, 2008).
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484 The production of ingredient from apple peel has been patented (Liu, 2013; Rupasinghe,

485 Wang, & Thilakarathna, 2013). Apple polyphenolic extracts are available on asian markets
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486 and are currently used as food additive and nutritional supplements (Shoji, Akazome, Kanda,
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487 & Ikeda, 2004). Polyphenols isolated from apple peels can be used as natural antioxidant to

488 stabilize fish-oil (Sekhon-Loodu, Warnakulasuriya, Rupasinghe, & Shahidi, 2013). Apple
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489 polyphenols have been assessed as antioxidant in meat products showing that they are 3.3-

fold more effective than the conventional butylated hydroxytoluene (Yu et al., 2013). The
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490
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491 numerous health benefits of apple peels and apple polyphenols such as antioxidant,

492 antihypertensive, anti-cancer, anti-diabetic and hypolipidemic activities could provide new

493 perspectives for their commercial utilisation.

494 Concerning the apple seed by-products, the occurrence of the potentially toxic cyanogenic

495 glycosides limits their utilisation. Potential application may be the recovery of the phloridzin

496 phenolic compound for the preparation of natural pigment (Fromm et al., 2013).

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497 In food packaging, apple peel could be used to prepare edible films by high-pressure

498 homogenisation with glycerol (Sablani et al. 2009).

499

500 Pectins

501 In food, the principal use of pectins is related to their ability to form a solid gel depending on

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502 the molecular size and the degree of esterification. Their industrial production is processed

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503 among many others by Herbafood Ingredient GmbH (Germany), Naturex (France),

504 Herbstreith & Fox (Germany), Starwest Botanicals Inc. (USA), Cargill (USA) and Yantai

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505 Andre Pectin (China). According to European rules, commercial pectins for food products

506 must contain more than 65% of galacturonic acid per dry weight, and more than 74%

507
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according to American pharmacopoeia (Ovodov, 2009). Industrial acidic extraction gives
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508 high-methoxyl pectins which have the ability to gel in the presence of sugar and acid media.
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509 Jams and preserves are the main food applications. Low-methoxyl pectins gel in the presence

510 of calcium and require less sugar so that they are specially designed to dairy products and diet
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511 foods. The gelation properties of low-methoxyl pectins can be enhanced by amidation
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512 (Ovodov, 2009). Recent research on pectin from apple pomace highlights its integration into

513 the diet and functional foods and the influence of its incorporation in end-product qualities.
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514 High methyl ester pectins and amidated low methyl ester pectins from apple pomace have

been selected as gelling agents in a functional food formula. The apple specific flavours have
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515
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516 been suggested to improve the consumer acceptance of the product (Haghighi & Rezaei,

517 2013). In other applications, apple pectin can be added to bread formulation up to 0.5%

518 without negating dough properties (Pecivova, Jurikova, Buresova, Cerna, & Hrabé, 2011).

519 Apple pectin has been evaluated to replace the shortening fat in cookies. The replacement of

520 fat up to 30% reduces the cookie spread diameter and increases the moisture content. Cookies

521 have tender texture and lighter surface colour compared to those prepared with fat (Min, Bae,

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522 Lee, Yoo, & Lee, 2010). Moreover, apple pectin exhibits lipase inhibition activity and could

523 be used in anti-obesity formulation (Kumar & Chauhan, 2010).

524 Due to their biodegradability, biocompatibility, edibility, and versatile chemical and physical

525 properties (such as gelation, selective gas permeability, etc), pectin is suitable polymeric

526 matrix for the elaboration of edible films intended as active food packaging (Espitia, Du,

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527 Avena-Bustillos, Soares, & McHugh, 2014).

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528 Pectin has applications in the cosmetic and pharmaceutical industries as gelling agents,

529 thickeners and as carriers for drug delivery (Srivastava & Malviya, 2011).

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530

531 Hemicelluloses

532
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Hemicelluloses have potential applications in various fields like foods, cosmetics,
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533 pharmaceuticals and polymers. They are applicable as gel materials, films, coatings and
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534 adhesives in technical and pharmaceutical fields. In food, hemicelluloses are used as

535 stabilising, viscosity-enhancing and gelling agents. Xyloglucan is able to interact with
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536 cellulose and can be used as surface treatment for cellulosic materials in dyeing. Xyloglucans
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537 have applications in textile industry, cosmetics, wet-end additives, papermaking and in-situ-

538 gelling preparations (Ebringerova, 2006).

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539 Up to now, there is no industrial development of hemicelluloses from the apple by-product.

There are still economical and technological limitations due to low yields, heterogeneity and
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540
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541 low purity of products, formation of degradation products and co-extraction (lignins) that

542 needs various purification steps. For the alkaline process to be industrially feasible, the

543 recovering of NaOH in the hydrolysate and its reuse to extract a new batch is important (Wafa

544 Al-Dajani & Tschirner, 2008). The ultrafiltration technology has been tested to improve

545 purification of hemicelluloses and allow the recovery of alkali. The low cost hydrothermal

546 may be applied to the apple pomace in order to extract the hemicellulose fraction.

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547

548 Oligosaccharides and miscellaneous

549 Xylooligosaccharides have great potential as prebiotics and can be incorporated into food

550 products as fortified food and functional food. The incorporation of xylooligosaccharides in

551 food products is reported mainly in various products i.e. soymilk, dairy products, coffee, fruit

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552 drink, pastries and jellies (Aachary & Prapulla, 2011).

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553 Cellulose can be used in various forms in food application i.e. fat substitute, texturiser,

554 emulsifier and bulking agent in low caloric foods. The commercial sources of cellulose are

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555 derived from wood pulp and cotton. In the pharmaceutical industry, microcrystalline cellulose

556 is commonly used as an excipient. In the field of polymers, nanocrystalline cellulose has been

557
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obtained from apple pomace with 35% crystallinity. Purification and isolation have been
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558 carried out by chlorite bleaching followed by sulfuric acid hydrolysis in order to convert the
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559 nanofibers to nanocrystalline whiskers (Takahashi, 2007).

560 Industrial productions of oligosaccharides and cellulose from apple pomace are not reported.
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561 However, the new chemopreventive properties of the pectic oligosaccharides stated by Li et
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562 al. (2013) may open new opportunities in prebiotic market.

563
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564 Conclusions and future prospects

Various by-products are available from apple processing including pomace, peels and seeds.
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565
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566 According to processes, the profile and the composition of the two predominant bioactive

567 components namely dietary fibre (pectin, hemicelluloses, cellulose and lignin) and phenolic

568 compounds (flavanols, flavonols, phenolic acid, dihydrochalcones and anthocyanins) are

569 different. A great diversity of low-cost raw materials is available offering many industrial

570 opportunities.

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571 The production of fibre concentrate and pectin is the most economical way for its utilisation

572 and is presently at commercial development. Fibre and pectin derived from apple by-products

573 are currently used as food ingredients and functional foods. Pectin is also used in

574 pharmaceutical industries as drug carriers and excipients. Polyphenol extracts are available on

575 asian market as additive in healthy food and as nutritional supplements.

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576 The extraction of the hemicellulosic fraction, either as polysaccharides or as oligosaccharides

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577 is another way to generate new products from the apple by-product but there are technological

578 challenges at industrial scale due to low yields. Efforts have been made to enhance

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579 productivity using non conventional technologies such as microwave and ultrasonication

580 methods. There are still limitations with the classical alkaline extraction that needs multiple

581
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steps for the recovery of a pure product. Cellulose and lignin (up to 50% of apple by-product)
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582 are scarcely investigated and may open new opportunities of apple pomace in non food
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583 application as an alternative to existing petroleum-based products.

584 In the perspective of biorefinery concept, various fractionation processes need to be

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585 developed for a global use of apple by-product core constituents. Recent developments are
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586 focused on environmental friendly hydrothermal and bioconversion technologies to produce

587 valuable products such as pectin, oligosaccharides and phenolic compounds. The pectin
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588 fraction receives the top interest and is explored for new functional properties in non-food

applications. This interest also comes from the existence of a feasible industrial technology.
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589
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590 Increased attention has been given to the phenolic fraction of apple by-products for the

591 formulation of functional foods. The numerous health benefits of apple peels and apple

592 polyphenols such as antioxidant, antihypertensive, anti-cancer, anti-diabetic and

593 hypolipidemic activities could provide new perspectives for their commercial utilisation.

594 The development of the other fractions (hemicelluloses, cellulose and lignin) is hindered by

595 the complexity of processes and the occurrence of other fraction-rich agro-food wastes. Future

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596 investigations should meet technological, environmental and economical constraints i.e. large-

597 scale feasibility, low environmental impacts and profitability. This could be achieved by

598 simplifying purification operation steps and by trying to integrate processes in existing value

599 chain or industrial installation. The environmental footprints of the involved technologies

600 could be minimized by developing new green solvents and green technologies. Research on

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601 novel properties and functionalisation will also open new opportunities from apple by-product

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602 fractions mainly in pharmaceutical or prebiotic market.

603

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604 Acknowledgements

605 This review paper is prepared in the framework of WagrALIM WALAID project funded by

606 the Walloon Region of Belgium.

607

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608 References

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966 Figure list

967 Fig. 1: By-products from apple processing

968 Fig. 2: Current state of the use and fractionation process of dietary fibre from apple pomace

969

970 Table list

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971 Table 1: Proximate composition of apple by-products from various processes

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972 Table 2: Phenolic contents of apple by-products (mg/kg DM) and seed (mg/kg defatted DM)

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974 pomace

975 Table 4: Recent patents on apple by-products

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Table 1: Proximate composition of apple by-products from various processes (% dry matter)

Apple by- Soluble Insoluble Cellulose Hemicellu- Lignin Pectins Proteins Lipids Ash Reference

PT
products dietary fibre dietary loses

(SDF) fibre (IDF)

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Pomace from 4.1-14.3 56.5-81.6 3.1-3.7 1.6-4.5 0.6-1.9 Figuerola, Hurtado,

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juice industry Estévez, Chiffelle &

Asenjo (2005)

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Pomace from 43.6 24.4 20.4 11.7 Narwiska &

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juice industry Kwasniewska (2005)

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Pomace from 20.2-26.4* 20.0-29.9* 13.8-17.1* 9.2-12.8 2.8-4.1 - 1.5-1.7 Gullón, Falqué, Alonso,

cider industry & Parajó (2007)

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Pomace from 0.0 64.6 38.9 13.5 12.2 2.9 7.1 2.9 1.2 Aguedo et al. (2012)

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syrup industry
EP
Peels 30.5-32.1 8.1-11.2 3.16-3.23 10.23- 4.46- Rupashinghe et al.

11.10 4.86 (2008)

C

Peels 5.8 42.1 2.7 2.7 2.4 Henriquez et al. (2010)

AC

Seeds 3.92-4.32** 38.8-49.5 20.7-24.3 4.3-5.2 Tian, Zhan, & Li (2010)

*By calculation

**Total dietary fibre

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Table 2: Phenolic contents of apple by-products (mg kg-1 DM*) and seed (mg kg-1

defatted DM*)

Pomace from Pomace from Pomace from Peel/skin Seed

juice industry cider industry syrup industry
Phenolic acids
Protocatechuic 36.8-263.9
Chlorogenic 33-79 96.1-602.4 396.1 330-620 3279.1-1932.3
Caffeic 8.2-18.3 nd 4.7-36.6

PT
Other acids 4.7-9.0 63.3-609.0 121.4-465.7
Flavanols
(-)-Epicatechin 140-190 167.5 76.7 334-494 4.2-51.6
Procyanidin B2 93-160 92.1-287.1 18.5-68.8

RI
Trimer C1 + tetramer 49.7-1316.2
Catechin 9.4-14 33.3 780-860
Other flavonols 43.5-305.5

SC
Dihydrochalcones
Phloretin-2’- 0.7-1.4 19.7-351.4 8-13 284.2-1334.3
xyloglucoside
Phloridzin 159.4-594.7 114.9 371-549 3256.3-22351.8
Other 11.4-115.8

U
dihydrochalcones
Flavonols
AN
Hyperin 112.6-232.0
Isoquercitrin+rutin 57.3-137.3
Reynoutrin 41.7-76.3
Avicularin 90.5-255.2
M

Quercitrin 87.1-186.3 8.2

Quercetin 3.5-23 115.0 2
Quercetin glycosides 521-681 123.3-188.6
Anthocyanins
D

Cyanidin-3- 510-1275
galactoside
TE

Reference Schieber, García, Valles, & Aguedo et al. Rupasinghe Fromm, Bayha,
Keller, & Lobo (2009) (2012) et al. (2008) Carle, &
Carle (2001) Kammerer
(2012)
*dry matter
C EP
AC
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Table 3: Influence of extraction technology on yield and characteristics of pectins

from apple pomace

Technology Conditions Yield GalA DE (%) Mw Reference

(wt% dry (wt% dry (g mol-1)
weight) weight)
Conventional Extraction temperature : 97 °C 16.6 67.14 52.5 1666.3 Kumar &
acidic Extraction time : 30 min Chauhan,
extraction pH: 2.5 (citric acid) (2010)

PT
Solid liquid ratio: 1/50
Conventional Extraction temperature: 85 °C 14.4 50.4 - 181000 Hwang et al.
acidic Extraction time: 30 min (1998)
extraction pH: 1,8 (HCl)

RI
Solid liquid ratio: 1/20
Water based Extraction temperature: 25 °C 19.7 53.1 49700 Hwang et al.
extraction with Extraction time: 60 min (1998)

SC
extrusion Soli liquid ratio: 1/20
pretreatment SME (specific mechanical
energy): 176 kWh t-1)
Combined Homogenisation: 3 min 4.6 69.3 69 231700 Min et al.
physical and Autoclave: 121 °C - 10 min (2011)

U
enzymatic Enzymatic extraction
extraction (Viscozyme)
AN
Extraction temperature : 40 °C
Extraction time : 60 min
Hot Extraction temperature : 140 °C 17.5 48.20 60.23 64200 Wang & Lü
compressed Extraction time: 5 min (2014)
M

water Solid liquid ratio : 1/14

extraction
Subcritical Extraction temperature: 150 °C 16.68 40.13 85.99 53402 Wang, Chen, &
water Extraction time:5 min Lü, (2014)
D

Solid liquid ratio: 1/30

Ultrasound Intensity 1-1.2 W cm-2 13.3 58.5 66.4 - Panchev et al.
TE

assisted Extraction time: 45 min (1988)

extraction 0.5% nitric acid
Extraction temperature: 80°C
Solid liquid ratio: 1/20
Microwave Extraction time: 20.8 min 15.1 - - - Wang et al.
EP

assisted pH: 1.01(HCl) (2007)

extraction Power microwave: 499.4 W
Solid liquid ratio: 1/14.5
C
AC
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Table 4: Recent patents on apple by-products
Product Patent number Applicant Object Reference
Dietary fibre CN101756119A Weihai Jianfang Production of apple dietary Fang (2010)
Institute of Medicine fibre by ultrasonic
emulsification
CN101664165B Yantai Andre Pectin Production of non-pectin Zhang et al. (2010)
Co., Ltd. soluble fibre by alkaline
extraction
CN102187984B Chengdu University Production of soluble fibre by Wei, Guo, & Huang

PT
expanding and enzymatic (2011)
methods
WO/2013/069028 Council of scientific & Separation of seeds from fruit Bhushan et al. (2013)

RI
industrial research pulp/skin/twigs
CN103229993A Univ Shaaraxi Science Decolouration by Chen & Li (2013)
& Tech alkaline/ozone extraction

SC
WO/2013/053618 Agrana Juice Holding Production of apple pomace Riedl (2013)
Gmbh
Pectin CN1844162 Tianjin Noao Sci & Extraction of pectins by Liu (2006)

U
Tech Development enzymatic and chemical
Co., Ltd. methods
AN
CN101891839 Northwest A&F Extraction of pectins with hot Lu, Wang & Zhang
University water (2010)
WO/2011/077172 Donchenko, Vasiliev Extraction and hydrolysis of Donchenko, Vasiliev
& Vasiliev pectin & Vasiliev (2011)
M

CN102731680 Lv Weixue Method of pectin extraction Lv, Dong & Ma

combined with nanofiltrations (2012)
WO2014029006 Leahy Orchards Inc. Extraction of pectin and fibre Doucet (2014)
D

from apple peel

TE

Cellulose CN101153293 Shanxi Microorganism Production of microlite fibrin Sun et al. (2008)
Institute, Shanxi from the residue post
Apple Research extraction of L-malic acid
Development Center
EP

CN101367878 Wu Maoyu Production of sodium Wu et al. (2009)

carboxymethylcellulose
Oligosaccha- PL399275A1 Politechnika Lodzka Preparation of prebiotic Ambroziak,
rides formulation from apple Pogorzzelski,
C

pomace Wilkowska, Motyl, &

Czyzowska (2013)
AC

Phenolic US6620452B1 American fruits and Phenolic extract from fruits Haddad, Shure, & Liu
compounds flavours and vegetables (2003)
WO2011140655 Dalhousie University Phenolic compounds from Rupasinghe, &
apple skin Robertson (2011)
US8337909B2 Board of trustees of Extraction of phloridzin from Howard, White, &
the university of apple seeds Prior (2012)
Arkansas
US8551554B2 Cornell Research Production of apple peel Liu (2013)
Foundation Inc. powder
EP2575841A2 Dhalousie University Production of apple skin Rupasinghe, Wang, &
extract Thilakarathna (2013)
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Apple

Processing

Juice, cider, syrup, Canning, saucing,

spirit industry drying, fresh-cut

PT
Pressing Peeling
industry

Pomace (pulp, Peels

RI
peel, seed, stem)
13%
25-30%

SC
Sieving

Seeds
U
AN
4-7%

Fig. 1
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APPLE BY-PRODUCT

DIETARY FIBRE PHYTOCHEMICALS

PROCESS Drying/ Grinding/ Acidic extraction/ Alkaline Acidic Bleaching/ No Solvent/aqueous

Washing/ Hot water extraction/ extraction/ hydrolysis/ Alkaline available extraction
Bleaching Enzymatic extraction/ Enzymatic Enzymatic extraction/ study
Alcohol precipitation/ hydrolysis hydrolysis Fermentation
Ultrafiltration

PT
PRODUCT Fibre concentrate Pectins Hemicelluloses Oligosaccharides Cellulose Lignins Phenolic
extract

RI
DEVELOPMENT Industrial scale/ Industrial scale/ Laboratory scale Laboratory Laboratory scale/ No available Industrial scale/
STATE Patented Patented scale/Patented Patented study Patented

Food ingredients Food ingredients Food ingredient/ Functional food/ Food ingredient/ Non-food Functional food/
USE &

SC
(bakery, meat, snacks, (jams, beverage, fruit Non-food Non-food Non-food (chemicals, Non-food
POTENTIAL beverage, yoghurt)/ paste, sauce, yoghurt)/ (chemicals, (pharmaceutical, (pharmaceutical, pharmaceutical,(pharmaceutical,
APPLICATIONS Functional food/ Functional food/ pharmaceutical, cosmetic) cosmetic, polymers) cosmetic)
Non-food Non-food cosmetics, polymers)
(pharmaceutical, (pharmaceutical and polymers)
technical) cosmetics, polymers)

U
PRODUCER J. Rettenmaier und Söhne Herbafood Ingredient Apple poly
(Germany); Herbafood GmbH (Germany); company (USA);
Ingredients GmbH Naturex (France); Asahi Breweries
AN
(Germany); Maruha Nichiro Herbstreith & Fox Ltd (Japan);
Foods, Inc. (Japan); (Germany); Starwest Andy Biotech
Starwest Botanicals, Inc. Botanicals, Inc. (USA); (Xi’an)Co, Ltd
(USA); Tree Top Cargill (USA); Yantai (China)
Ingredients (USA) Andre Pectin (China)
M

Fig. 2
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TE
C EP
AC
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Highlights

The diversity of apple by-product compositions is highlighted.

The recent fractionation processes of fibre and phenolic core components are reviewed.

The development state and current applications of apple by-products are discussed.

Future trends and challenges of apple by-product uses are discussed.

PT
RI
U SC
AN
M
D
TE
C EP
AC