Beruflich Dokumente
Kultur Dokumente
Chemistry
Food Chemistry 100 (2007) 736–741
www.elsevier.com/locate/foodchem
Received 18 April 2005; received in revised form 18 April 2005; accepted 18 April 2005
Abstract
Dietary fibre encompasses a huge variety of macromolecules, exhibiting a wide range of physicochemical properties. Citrus fibre can
be obtained from different industrial sources and different kinds of citrus. The chemical components of fibre (pectin, lignin, cellulose and
hemicellulose), together with other compounds, such as flavonoids, were analysed in nine different industrial sources. Final fibre com-
position was more dependent on the industrial process than on the type of citrus. The chemical changes gone by citrus fibre showed losses
of functional values; i.e. soluble dietary fibre and ascorbic acid content decreased when waste products were transformed into fibres. The
water-holding and lipid-holding capacities of analysed citrus fibres suggested a non-linear behaviour of these properties for the analysed
citrus fibres.
2005 Published by Elsevier Ltd.
Vries, & Furda, 1988). This is important, considering that sinensis (L.) Osb.), as raw material for industrial processes,
the requirement for dietary fibre intake must be balanced, were obtained from commercial orchards located in South-
i.e. the water-soluble fraction should represent between East of Spain.
30% and 50% of the total dietary fibre (Eastwood, 1987;
Spiller, 1986). Moreover, citrus fruits have better quality 2.2. Samples
than other sources of dietary fibre due to the presence of
associated bioactive compounds (flavonoids and vitamin The citrus industrial by-products obtained from differ-
C) with antioxidant properties, which may provide addi- ent types of industrial process were the following:
tional health-promoting effects (Benavente-Garcı́a, Cas- Samples CIB-1, 2, 3 and 4 were obtained as off-products
tillo, Marı́n, Ortuño, & Del Rı́o, 1997; Marı́n, Frutos, from an industrial process of flavonoid extraction, in which
Pérez-Alvarez, Martı́nez-Sánchez, & Del Rı́o, 2002). aqueous and hydroalcoholic solvents were used. CIB-5 cor-
Chemical and physical properties of citrus fibres have responds to peels obtained from the chemical peeling dur-
been widely studied (Gorinstein et al., 2001; Griguelmo- ing the satsuma ‘‘segments’’ canning process. CIB-6, 7, 8
Miguel & Martı́n-Bel, 1999). Many authors have described and 9 were obtained from the citrus juices industry as res-
citrus dietary fibre content (Schieber, Stintzing, & Carle, idue from the extraction process performed by using the
2001), while others have mainly focussed on their flavonoid ‘‘in line’’ extraction system from FMC (Food Machinery
concentrations (Coll, Coll, Laencina, & Tomas-Barberan, Corporation, USA).
1998). Other chemical properties have been extensively
reviewed by Fernández-López et al. (2004). However, no 2.3. Analytical methods
exhaustive studies combining the above-mentioned analysis
have been reported to study both the effect of the process to 2.3.1. Proximate analyses
obtain fibre and the effect of previous industrial processes. Ash was determined according to method 923.03 of
This work describes the chemical composition of citrus AOAC (2000).
by-products from three of the most important fibre Total carbohydrates were determined by the Luff–Schorl
sources: wastes from chemical companies (whose interest method, according to the reference of the Journal Official
lies in the extraction of natural compounds, such as des Comunantes Européenes, n L. 155/32.
flavonoids), wastes from canning companies (whose main Fats were determined according to method 960.39 of
activity is canning citrus ‘‘segments’’) and wastes from AOAC (2000).
citrus juice production. Moreover, the chemical changes Proteins were determined according to method 955.04 of
produced due to the processing of citrus wastes into fibre AOAC (2000).
are studied, together with an evaluation of chemical prop-
erties, such as total antioxidant activity, and physical 2.3.2. Compounds of functional value
properties, such as LHC (lipid-holding capacity) and The content of ascorbic acid, expressed in mg/l, was
WHC (water-holding capacity). obtained by means of method no. 43056 of the AOAC.
For the quantification of flavonoids, an ODS-C18
2. Material and methods (250 · 4.6 mm i.d.) analytical column was used with an
average particle size of 5 mm, using water:acetoni-
2.1. Plant material trile:methanol:acetic acid (15:2:2:1) as the eluent with a
flow rate of 1 ml/min at 30 C. The absorbance change
Sour orange (Citrus aurantium L.), satsuma (Citrus was monitored at 280 and 350 nm with a Hewlett Packard
unshiu (Mak) Marc., grapefruit (Citrus paradisi Macf), mod. HP 1100 UV/Vis diode array detector (Castillo,
lemon (Citrus limon (L.) Burm f.), and sweet orange (Citrus Benavente-Garcı́a, & Del Rı́o, 1994).
738 F.R. Marı́n et al. / Food Chemistry 100 (2007) 736–741
The citrus industrial by-products (CIB-1 to CIB-9) were The chemical composition of the citrus industrial by-
processed for fibre extraction using the following proce- products (Table 1), according to the analysed parame-
dure: samples were vacuum-packed as fresh raw material ters, seems to be more dependent on the industrial
in 2 kg pouches and promptly frozen to 30 C until fur- source than on the citrus species used. By-products
ther use. After thawing (24 h/2–5 C) the material was obtained from the chemical industries (CIB-1, 2, 3 and
scalded in a water bath to remove potential pathogenic 4) showed lower contents of pectin and flavonoids, and
microorganisms (vegetative cells). Afterwards, the fibre higher contents of lignin and ash, than by-products from
was pressed using a helical press to remove excess liquid food industries (CIB-5, 6, 7, 8 and 9). This may easily be
prior to drying. Drying was carried out in an oven at explained by the fact that, in the chemical industry,
50 ± 5 C during 24 h to improve the fibre shelf life without hydroalcoholic solvents are used during the process,
addition of any chemical preservative. A grinder mill and which are able to extract both, flavonoids and pectins.
sieves were used to obtain a powder particle size of less On the other hand, by-products from the food industry
than 0.2 mm. The final product was a powder with 7% showed 3- to 10-fold higher amounts of total flavonoids
moisture, as described by Fernández-López et al. (2004). than by-products from the chemical industry. By-
Table 1
Chemical composition of different citrus by-products
Ash Sugar Fat Protein Flavonoid Pectin Lignin Cellulose Hemicellulose
(% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW)
CIB-1 13.22 ± 0.26 3.52 ± 0.14 1.58 ± 0.08 8.82 ± 0.42 2.70 ± 0.08 3.52 ± 0.27 12.52 ± 1.11 39.00 ± 3.12 8.32 ± 0.79
CIB-2 11.03 ± 0.29 8.01 ± 0.23 0.55 ± 0.03 12.87 ± 0.90 1.51 ± 0.02 6.54 ± 0.56 14.73 ± 1.32 20.74 ± 1.92 6.57 ± 0.56
CIB-3 10.03 ± 0.15 8.50 ± 0.20 1.57 ± 0.06 7.33 ± 0.33 3.06 ± 0.06 2.58 ± 0.22 13.54 ± 1.26 30.53 ± 2.35 11.04 ± 0.98
CIB-4 8.09 ± 0.41 8.02 ± 0.36 0.52 ± 0.02 12.51 ± 0.87 3.04 ± 0.03 8.53 ± 0.68 11.56 ± 0.98 26.57 ± 2.01 5.59 ± 0.42
CIB-5 5.05 ± 0.22 10.07 ± 0.54 1.59 ± 0.09 7.50 ± 0.21 5.09 ± 0.05 16.01 ± 1.21 8.59 ± 0.76 22.55 ± 2.22 6.01 ± 0.56
CIB-6 2.52 ± 0.15 6.52 ± 0.48 1.51 ± 0.11 7.00 ± 0.44 12.54 ± 0.62 13.00 ± 1.06 7.56 ± 0.54 23.06 ± 2.11 8.09 ± 0.81
CIB-7 2.54 ± 0.05 9.01 ± 0.87 3.09 ± 0.12 8.72 ± 0.36 4.52 ± 0.10 22.53 ± 1.95 7.55 ± 0.66 36.22 ± 3.24 11.05 ± 1.09
CIB-8 2.56 ± 0.10 9.57 ± 0.22 4.00 ± 0.15 9.06 ± 0.38 4.50 ± 0.15 23.02 ± 2.12 7.52 ± 0.59 37.08 ± 3.10 11.04 ± 1.05
CIB-9 2.55 ± 0.09 6.04 ± 0.41 1.52 ± 0.05 6.55 ± 0.32 11.00 ± 0.54 12.07 ± 1.12 7.51 ± 0.62 24.52 ± 2.00 7.57 ± 0.66
The results are expressed as an average ±ES (n = 7).
F.R. Marı́n et al. / Food Chemistry 100 (2007) 736–741 739
products from the canning industry (CIB-5) showed are separated by means of a prefinisher tube, determining
lower contents of flavonoids than samples CIB-6, 7, 8 different tissue compositions of wastes.
and 9 and higher than CIB-1, 2, 3 and 4. This might During the processing of citrus by-products into fibre,
be because the canning industry uses hot chemical peel- the raw material undergoes two critical steps: scalding
ing with NaOH. Under these conditions, the flavonoid (which includes washing) and drying. CIB-1 and CIB-7
skeleton open to the chalcone form, becoming more sol- were selected to evaluate the effect of the described process.
uble and leaving a solid matrix. CIB-1 is the most abundant by-product from the chemical
The pectin content of food industry by-products (CIB-5, industry, and CIB-7 has a pale yellow colour that may be
6, 7, 8 and 9) was 2- to 10-fold higher than those obtained more convenient for food formulations. In general terms,
from the chemical industry. In CIB-1, 2, 3 and 4, pectin contents of ash, sugar, protein, flavonoid and pectin
contributed to the total amount of chemical fibres in a per- decreased, while the contents of fat, lignin, cellulose and
centages ranging from 4% to 16% while, in the food indus- hemicellulose increased after this treatment (Table 2).
try by-products (CIB-5, 6, 7, 8 and 9), the percentage The most relevant effect due to processing is observed on
ranged from 25–30%. pectin and lignin contents. Pectin levels decreased by 58%
Lignin in by-products originating from the chemical and 35% compared to the original amount in CIB-1 and
industry, contributed up to 20–30% of the total cell wall CIB-7, respectively. On the other hand, lignin levels
components of fibre. Lignin and ash showed higher con- increased up to 89% and 46% with respect the initial values
tents in these by-products compared to those originating found for CB-1 and 7, respectively.
from the food industry. These fractions are less soluble The processing of by-products into fibre also affects
and, therefore, hydroalcoholic solvents should not extract those parameters known to determine the nutritional func-
them; this produces a concentration effect on the studied tional value of a product. In the studied samples, losses in
by-products. soluble dietary fibre, flavonoids, ascorbic acid and total
The highest content in the chemical components of fibre antioxidant activity (TAA) were observed while insoluble
corresponded to CIB-7 and 8, which are the pulp fraction dietary fibre levels increased (Table 3). Losses in soluble
obtained from lemon and orange juice production, respec- dietary fibre may be explained by pectin lost as a conse-
tively. CIB-7 and 8 showed a total amount of chemical quence of the washing effect of scalding. On the other hand,
fibre constituents of approximately 77% DW (dry weight). the increase in insoluble dietary fibre may be explained by a
On the other hand, the peel fraction (CIB-6 and 9), concentration effect, due to the former scalding step. Other
together with CIB-2, showed the lowest values of the four valuable compounds, such as flavonoids, drop slightly
analysed polymers. In this case, two different waste-streams while ascorbic acid practically disappears from the pro-
from the same fruit and same industrial process resulted in cessed material. Values of ascorbic acid in CIB-1 and
different compositions. This could be due to the fact that CIB-7 were extremely low when compared with that
the ‘‘in line’’ extraction system (FMC, USA) performs an reported by other authors (Gorinstein et al., 2001).
extraction by squeezing after incisions have been made in However, these studies were done on pulp and peel frac-
the polar areas of the fruit. Afterwards, the pulp and juice tions obtained by peeling fresh fruits. In the present study,
Table 2
Effect of the transforming process on citrus fibre composition
Ash Sugar Fat Protein Flavonoid Pectin Lignin Cellulose Hemicellulose
(% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW) (% of DW)
CIB-1 13.22 ± 0.26 3.52 ± 0.14 1.58 ± 0.08 8.82 ± 0.42 2.70 ± 0.08 3.52 ± 0.27 12.52 ± 1.11 39.00 ± 3.12 8.32 ± 0.79
CIB-1 Fibre 6.57 ± 0.10 2.54 ± 0.10 1.86 ± 0.07 7.55 ± 0.33 2.47 ± 0.06 1.59 ± 1.02 23.79 ± 1.85 40.51 ± 3.64 10.07 ± 0.99
CIB-7 2.54 ± 0.05 9.01 ± 0.87 3.09 ± 0.12 8.72 ± 0.36 4.52 ± 0.10 22.53 ± 1.95 7.55 ± 0.66 36.22 ± 3.24 11.05 ± 1.09
CIB-7 Fibre 2.54 ± 0.09 2.50 ± 0.08 6.01 ± 0.23 5.50 ± 0.12 4.22 ± 0.02 15.04 ± 1.12 11.04 ± 0.88 39.02 ± 3.55 12.01 ± 1.11
The results are expressed as an average ±ES (n = 7).
Table 3
Effect of transforming process on citrus fibre functional compounds and properties
Soluble Dietary Insoluble Flavonoid Ascorbic TAA
Fibre (% of DW) Dietary Fibre (% of DW) mg/g Ac mg/g mg/g
CIB-1 6.75 ± 0.50 56.00 ± 5.24 27.01 ± 0.84 0.21 ± 0.01 20.32 ± 0.40
CIB-1 Fibre 3.10 ± 0.22 74.62 ± 6.99 24.20 ± 0.63 ND 18.15 ± 0.12
CIB-7 23.31 ± 1.76 54.03 ± 4.15 45.19 ± 1.03 5.64 ± 0.11 60.07 ± 1.03
CIB-7 Fibre 17.15 ± 1.43 64.56 ± 6.32 40.22 ± 0.2 0.42 ± 0.01 47.34 ± 0.66
The values are expressed as an average value ±ES (n = 3).
ND: Not detected.
740 F.R. Marı́n et al. / Food Chemistry 100 (2007) 736–741
0,30
25%, 40%, 25% and 0.7% DW, respectively in CIB-1 (sour
orange), and eriocitrin, hesperidin, diosmin and luteolin-7- 0,25
O-rutinoside, at concentrations of approximately 37%,
48%, 4% and 10%, respectively in CIB-7 (lemon). Sour
0,20
orange flavonoids have lower relative antioxidant poten-
tials than have lemon flavonoids (Marı́n et al., 2002;
0,15
Marı́n, Martinez, Uribesalgo, Castillo, & Frutos, 2002;
Rice-Evans, Miller, & Paganda, 1997). For instance, narin-
gin has a TEAC (trolox equivalent antioxidant capacity) of 0,10
citrus by-products as putative sources of dietary fibre. Griguelmo-Miguel, N., & Martı́n-Belloso, O. (1999). Comparison of
However, there are few publications regarding direct appli- dietary fibre from by-products of processing fruits and greens and from
cereals. Lebensmittel-Wissenschaft Und-Technologie-Food Science and
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et al., 2004; Lario et al., 2004). Their organoleptic charac- dietary fibres, and consequences of processing on human physiology.
teristics may mask the typical flavour of citrus. Further- Food Research Institute, 33, 233–245.
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enhance carcinogenesis. Mutation Research, 443, 93–110.
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