Transformation of Vegetable Waste Into Value Added Products

Bioresource Technology 87 (2003) 167198
Review paper
Transformation of vegetable waste into value added products:

(A) the upgrading concept; (B) practical implementations
G
unther Laufenberg
a,*
, Benno Kunz a, Marianne Nystroem
Department of Food Technology, University Bonn, Roemerstr. 164, D-53117 Bonn, Germany
Department of Chemical Technology, Lappeenranta University of Technology, Postbox 20, FIN-53851 Lappeenranta, Finland
Abstract
Waste can contain many reusable substances of high value. Depending on there being an adequate technology this residual
matter can be converted into commercial products either as raw material for secondary processes, as operating supplies or as ingredients of new products. Numerous valuable substances in food production are suitable for separation and recycling at the end of
their life cycle, even though present separation and recycling processes are not absolutely cost ecient.
In Part A a need statement is visualisedbased on a holistic concept of food productionfor the vegetable industry, recording
occurrence, quantities and utilisation of the residual products. A literature survey, covering more than 160 articles from all over the
world, plus our own investigations summarises the latest knowledge in the above-mentioned eld and outline prospects for future
economic treatment of vegetable co-products.
The main goal of a clean production process is demonstrated by three practical implementations in Part B:
1. Upgrading of vegetable residues for the production of novel types of products: multifunctional food ingredients in fruit juice and
bakery goods.
2. Bioconversion via solid-state fermentation: vegetable residues as an exclusive substrate for the generation of fruity food avours.
3. Conversion of vegetable residues into operating supplies: bioadsorbents for waste water treatment.
The investigations are promising with regard to future application in the mentioned industrial branch. The outlined concept can
be naturally transferred to several areas of industrial food production. The intentions of this research area are located at the development of techniques, which full the conditions of environmental protection with costs to a minimum. The prospect of several
new niche markets is worthwhile indeed.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Green productivity; Vegetable waste treatment; Clean production; Valuable substances; Bioadsorbents; Upgrading; Recycling;
Bioavours; Multifunctional food ingredient; Review
Part A
1. Introduction
A thing is right when it tends to preserve the integrity, stability and beauty of the biotic community.
It is wrong when it tends to do otherwise.
(Aldo Leopold)
Corresponding author. Tel.: +49-228-734-274; fax: +49-228-734429.

E-mail address: g.laufenberg@uni-bonn.de (G. Laufenberg).
Todays society, in which there is a great demand for

appropriate nutritional standards, is characterized by
rising costs and often decreasing availability of raw
materials together with much concern about environmental pollution. Consequently there is a considerable
emphasis on the recovery, recycling and upgrading of
wastes. This is particularly valid for the food and food
processing industry in which wastes, euents, residues,
and by-products can be recovered and can often be
upgraded to higher value and useful products.
The food industry produces large volumes of wastes,
both solids and liquids, resulting from the production,
preparation, and consumption of food. These wastes
pose increasing disposal and potentially severe pollution
0960-8524/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
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168
G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198
problems and represent a loss of valuable biomass and

nutrients. In the past they often have been dumped or
used without treatment for animal feed or as fertilizers.
In the last few years, however, owing to the increasing
necessity to take into consideration aspects aimed at
preventing pollution of the environment as well as for
economic motives, and the need to conserve energy and
new materials, new methods and policies for waste
handling and treatment have been introduced in the
recovery, bioconversion, and utilization of valuable constituents from food processing wastes. Besides their
pollution and hazardous aspects, in many cases, food
processing wastes might have a potential for recycling
raw materials or for conversion into useful products of
higher value as a by-product, or even as raw material for
other industries, or for the use as food or feed/fodder
after biological treatment. Particularly, the bioconversion of food processing residues is receiving increased
attention regarding the fact that these residual matters
represent a possible and utilizable resource for conversion to useful products (Martin, 1998, p. 316).
1.1. Clean production strategy
Clean production can be considered so far as a strategic
element in manufacturing technology for present and
future products in several industrial branches. Demand is
focused on the development of cost eective technology,
the optimisation of processes including separation steps,
alternative processes for the reduction of wastes, optimisation of the use of resources and improvement in production eciency (Paul and Ohlrogge, 1998).
Hence current industrial waste management techniques can be classied into three options: source reduction via in-plant modication, waste recovery/recycle
or waste treatment by detoxifying, neutralising or destroying the undesirable compounds.
The rst two options plant modication and waste
recovery/recycle represent the most promising waste
management strategies. Indeed waste recovery is a particularly attractive option. Signicant environmental
and economic benets can accrue from separating industrial wastes with the objective of recycling/reusing
these valuable components and/or the bulk of water.
Promising concepts include pervaporation in hybrid
processes (Hausmanns et al., 1999) or the upgrading of
vegetable residues to create a secondary use for the
waste products (Laufenberg et al., 1999).
It has become apparent that the current practices of
pollution control and waste management cannot completely meet the increasingly stringent requirements for
the reduction of environmental contamination. Therefore the manufacturing industry has to include the
optimisation of product-integrated environmental protection into strategic planning, research and development. Beside these strategies green productivity can play
an important role. This paper will report on the occurrence, quantities and current utilisation routes for solid
vegetable waste, the transformation into value added
products and the practical implementation represented
by three possible applications.
1.2. The Holistic concept of food production
Present R&D in food technology is unthinkable
without taking environmental aspects into account. A
responsible management of scarce resources is needed
especially in view of tighter living spaces. Based on these
considerations the holistic concept of food production,
shown in Fig. 1 has been developed. What does it mean?
This approach tries to connect diering goals, such as
highest product quality and safety, highest production
eciency and the integration of environmental aspects
into product development and food production. Within
the concept every factor and aspect should be taken into
account in a coherent manner.
The recycling of residues is important to every manufacturing branch and includes high developing potential. A systematic reduction of product losses and
emissions is protable under both economical and ecological aspects.
Concepts like the dierentiation and separate treatment of waste water streams and a task oriented
by-product management support this trend, in this
connection special attention is drawn to the recovery of
valuable substances or product losses and internal process water recycling.
A Greenpeace brieng published on the web (Kruszewska and Thorpe, 1995) denes clean production in a
similar way.
The goal of clean production is to full our need
for products in a sustainable way i.e., using renewable, non-hazardous materials and energy
Fig. 1. The holistic concept of food production.
eciently while conserving biodiversity. Clean production systems are circular and use fewer materials
and less water and energy. Resources ow through
the productionconsumption cycle at slower rates.
In the rst place, a clean production approach
questions the very need for the product or looks
at how else that need could be satised or reduced.
Clean production implements the precautionary
principleit is a new holistic and integrated approach to environmental issues centred around
the product. This approach recognises that most
of our environmental problemsfor example
global warming, toxic pollution, loss of biodiversityare caused by the way and rate at which we
produce and consume resources. It also acknowledges the need for public participation in political
and economic decision-making.
Fig. 2 exhibits suggestions for a sustainable economy,
beside the preventative approach waste reduction and
recycling is the other most important goal in future.
1.2.1. Development of clean production processes
The outlined system approach results in an operational program, which is not dened by technological
areas, but by short, medium and long term goals.
Short term goals
Waste reduction and recycling of valuable substances, by-products and residues.
Enlargement and adjustment of existing technology
to the application area in particular (e.g., hybrid processes).
Outcome: a reduction of emission and risk.
Medium term goals
Development and application of new and ecient
production processes.
Adding value to by-products.
Outcome: higher environmental responsibility for the
companies is accompanied by competitive advantages.
Fig. 2. Circular structure of a sustainable economy (source: adapted

from Stahel Walter R. The Product-life Institute, Geneva).
169
Long term goals

Step by step implementation of environmentally benign manufacturing.
Development of innovative products.
Outcome: Innovative food products like functional/
designer food will open new market segments and additionally meet clean/green productivity objectives.
1.2.2. Challenge for the vegetable/beverage industry

Considering the vegetable industry the mentioned
goals could be fullled by the usual approaches such
as minimisation, disposal, feeding, fertilisation/composting, closed loop production, or conversion.
At present there are few possibilities for the utilisation or recycling for most of these wastes, the residues
are thus disposed or fed to animals. Transport costs and
sales problems due to the low quality of the residual
matter have led to alternative utilisation concepts, like
the use as a building material, or conversion concepts
like composting and biogas production. Incineration has
been largely investigated but not strongly pursued due
to the low caloric value 1 and high water content. An
electric power station in Nimwegen/NL has recently
started to incinerate 40 t of dried coee grounds from an
instant coee production plant. Besides the low combustion value, a crucial point for all vegetable residues,
the formation of o-odours, bothering the nearby residents, appears to be another serious problem (Tagesschau, 1999).
Focused on the feeding concept there are further
problems mentioned in the literature. Not every animal
can take every food/residue. Laufenberg et al. (1996)
described that protein concentrate made of potato fruit
water could only be fed to cattle due to the high potassium content, Clemente et al. (1997) found that olive
cake is not recommended for feeding because of its
low digestibility. Sugarcane bagasse has a high lignin
content of 22%, which forms a protective association
with cellulose, thereby causing low digestibility for animal foodstu (Purchase, 1995).
According to a survey of the United States Department of Agriculture (USDA) estimating and addressing
Americas Food losses (Scott Kantor et al., 1997), about
50 million US$ annually could be saved alone in solid
waste disposal costs for landlls if 5% of processing,
retail, food service and consumer food losses in 1995
were recovered (total amount of loss was 43:54 109 kg
that year!).
1
Energetic utilisation is only recommended if the caloric value is
beyond 11,000 kJ kg1 waste (Kuper-Theodoritis, 1996), which is even
not the fact for fat-containing residues. It has to be doubted if 18,840
kJ kg1 olive press cakes (Vlyssides et al., 1999) are protable. AbuQudais (1996) classied the combustion of olive cake as technically
inecient and economically unacceptable.
170
1.2.3. End of pipe solution?

The waste to be treated is already produced, a precautionary approach is possible to a certain extent, but
beyond that the vegetable industry, and especially beverage industry, will always produce residues. The upgrading concept tries to add value to the by-products
and residues. This medium term goal results in the creation of innovative products like
dietary bres as matrices for avours, dyes or antioxidants,
pectin and gelling agents with dened properties
using synergetic eects,
designer dietary bres for application in bread or beverages,
bioavours produced by bioconversion of waste
material or smart technology like
eective and low cost bioadsorbents, which can be
easily desorbed or biodegraded after use,
hybrid processes combining adsorption and membrane processes for an advanced wastewater treatment and internal process water recycle.
Thus the introduced concept is a further step towards environmentally benign manufacturing. The
concept does not present any immediate patent solutions or recipes, because industrial food production
is an interactive process, which needs to full all
three conditions, quality, eciency and environmental
protection as aforementioned. The upgrading concept
is a continuing development and research strategy,
keeping in mind this interrelated character of production.
Instead of just blaming the industry to develop a so
far unknown standby preventative solution for the
waste, the outlined concept tries to combine economical
aspects too. The result is a step by step waste reduction
with simultaneously rising productivity, not obtained by
restrictions but by opportunities, advantages are summarised in Table 1.
Consequently the concept follows a three steps approach:
1. Evaluation as state of the art, visualising vegetable
waste in its occurrence, quantities and current utilisation routes.
2. Introducing the upgrading concept.
Table 1
Advantages for industry and environment

Closed loop of valuable constituents

Preservation of resources
Discovery of niche markets
Environmental protection combined with
Reduced waste disposal costs
3. Technical implementation by three selected examples.
2. Need statement: the vegetable waste situation

2.1. Vegetable waste quantities in several countries
The scale of the problem is illustrated by looking at
the total amounts of waste materials produced by different states. Table 2 is a list of waste quantities mentioned in the literature.
2.2. Strategies and utilisation routes: state of the art
Special attention was given to publications, which
focus on ideas beyond fodder/feed and composting/fertilisation.
Not covered in this literature survey are
liquid vegetable waste streams,
any solid or liquid waste stream related to animal
production, slaughtering, meat and meat product
processing.
Vegetable residues mostly contain considerable
amounts of potentially interesting compounds. Due to
legislation and environmental reasons the industry is
more and more forced to nd an alternative use for the
residual matter. The recovery of high value compounds
is an elegant way to reuse waste streams, while being
economically interesting on the other hand. Several fruit
and vegetable residues are listed in Table 3.
In the last decade the interest in the alternative use of
waste streams beyond disposal or fertilisation has increased drastically. Further to rising disposal costs the
economic interest has appeared as well. A new niche
market for residual matter recently appeared in chocolate production. After a four years discussion the EC has
dropped the purity law for chocolate. The European
Parliament decided on March 8th 2000, that chocolate
manufacturing industry is allowed to add up to 5% other
fat types besides cocoa fat to their chocolate products
(ZDF.MSNBC, 2000). One of the legalised cocoa butter
substitutes is mango kernel, which contains 12% fat
(Nanjundaswamy, 1997).
The utilisation of a waste stream as raw material for
new products needs to be economically attractive as
aforementioned. The selection of high value products
reaches from natural bioavours over food colours to
biocontrolling agents for food preservation.
A real bulk application for vegetable wastewith
minimised further treatment stepscould be the use as a
bioadsorbent for the pre-treatment of aromatic waste
waters. Activated carbon being used so far is relatively
expensive. In order to obtain cheaper adsorbents,
171
Table 2
Waste quantities in dierent countries (selection)
Country/state
Quantity and waste type
Germany, 1997 (Henn, 1998)
380,000 t/a organic waste only from potato, vegetable and fruit processing
1,954,000 t/a spent malt and hops (breweries)
1,800,000 t/a grape pomace (viniculture)
3,000,000 t/a crude bre residues (sugar production)
100,000 t of wet apple pomace (25,000 t dry apple pomace) remain if 400,000 t
of apples are processed into apple juice (Henn and Kunz, 1996)
Belgium, 1992 (Lucas et al., 1997)
105,000 t/a biowaste (vegetable, garden and fruit waste)

280,000 t/a estimations due to legislation of separate household collection
Thailand, 1993 (Prasertsan and Prasertsan, 1996) palm oil

production
386,930 t/a empty fruit bunches

165,830 t/a palm press bre
110,550 t/a palm kernel shells
1,000,000 t/a cassava pulp (1994, Sriroth et al., 2000)
Spain, 1997 (Clemente et al., 1997)
>250,000 t/a olive pomace
EEC, 1996 (Dronnet et al., 1998a)
14,000,000 t/a sugar beet pulp (dry matter!)
Portugal, 1994 (Carvalheiro et al., 1994)
14,000 t/a tomato pomace
Jordan, 1999 (Haddadin et al., 1999)
36,000 t/a olive pomace
Malaysia, 1996 (Hussein et al., 1996) palm oil production
2,520,000 t/a palm mesocarp bre

1,440,000 t/a oil palm shells
4,140,000 t/a empty fruit bunches
Australia, 1995 (Tran and Mitchell, 1995)
400,000 t/a pineapple peel
USA
300,000 t/a grape pomace in California only (1994) (Nakata, 1994)

9,525 t/a cranberry pomace (1998) (Zheng and Shetty, 1998)
200,000 t/a almond shells (1997) (Toles et al., 2000)
3,300,000 t/a orange peel in Florida (1994) (Manthey and Grohmann, 1996)
lignocellulosic materials have been studied. Low cost

and simplicity of the modication methods are also
desirable for applications (Peternele et al., 1999).
Another branch for a further use of vegetable residues is their availability as a source of potential phytochemicals. Olive pomace is used as a nematodes
controlling agent for tomatoes (Rodriguez-Kabana
et al., 1995), citrus waste streams are used in horticulture
(Widmer and Montanari, 1995) and mandarin peel
avonoids are interesting due to their fungistatic activity
(Chkhikvishvili and Gogiya, 1995) which may be applied to naturally protect vegetables and fruits from
moulding. The limonoid compounds in citrus peel and
seeds have recently been found to have important
pharmacological properties as well as potential in the
use as an insect antifeedant for agricultural crops
(Manthey and Grohmann, 1996).
Despite the studies cited and their potentially promising results, no systematic investigation on potential utilisation routes and innovative concepts has
been completed yet. Furthermore mechanisms for improved yields of existing recycling strategies are not
known.
The improved utilisation of vegetable waste, outlined

here, should lead to a more ecient use of resources
and less negative environmental impact (Sriroth et al.,
2000).
3. The upgrading concept

Important factor for the upgrading process is the
development of a procedure using technical standard
equipment. Goal of the upgrading is a product with
desired, reproducible properties designed under economical and ecological conditions.
Most of the vegetable residues consist mainly of
water and cellulose and have a poor microbiological
quality because of numerous spoilage bacteria on the
surface, particularly if stored in the production unit
prior to use; thus they quickly decompose in an uncontrolled way. A pre-treatment step in the form of inoculation with lactic acid bacteria may produce a more
stable substrate, which should be dried to further enhance shelf and storage life. An alternative to the fermentation is the acidication by acids like citric, acetic
or ascorbic acid. For sensorial reasons and because of
172
Table 3
Current utilisation concepts for vegetable pomace (selection)
Pre-treatment
Results
Application/secondary use
Reference
Almond shells
M: grinding, C: phosphoric acid

pre-treatment, P: heat activation
B: SSF Candida, Sacch., Torula
spp., P: drying
Superior to commercial carbons in metal

uptake, 8592% with organic solutions
Crude protein three times higher, fat 1.52
times higher, vitamin C two times higher,
minerals and bres content higher
Enhanced bre content in food, Sensorial
tests: moderately liked
Better results by adding SO2 and Vitamin C
Op: wastewater treatment, metal and organics adsorption

O: ethanol, Ff
Toles et al. (2000)

Joshi and Sandhu (1996)
Fi: pie lling, oatmeal crackers
Carson et al. (1994)
O: avours, volatile aldehydes for chemical

industry
Almosnino and Belin (1991)
O: Fine chemicals, polyphenols

Fi: avour extract
Lu and Foo (1997)

Bundschuh et al. (1988), Bundschuh et al. (1986)
Christen et al. (2000)
Apple pomace
Apple pomace
P: drying, M: powdering
Apple pomace
Apple pomace
Apple pomace, Pepper
peels
Apple pomace, cassava
bagasse
B: degradation of linoleic acid by

intrinsic enzyme system of pomace
C: CO2 avour extraction, fractionated precipitation

M: grinding, B: SSF with 4
Rhizopus strains
Apple pomace, spent malt

grain
M, B: SSF with Thamnidium

elegans
Apricot seeds
B: enzymatic degradation
Banana pith waste (banana

stem marrow)
Blackcurrant and apple
pomace
M, P: drying, grinding
Carrot pomace
C, M, P
M: grinding, B: SSF lactic acid

hygenisation with L. farciminis
Highest avour production with amaranth

plus mineral precursor and apple/cassava/
soybean
Highest product yields with ratio of 3 to 1
(AP to SMG), precursor peanut oil further
improved yield
Protein substitute only after degradation of
cyanogenic glycosides
Parameters: agitation time, adsorbent dosage, pH-value, initial conc.
Fibres (60%) are useful for binding Cd
(>30%) and Pb (>40%). Blackcurrant pomace binding capacity was higher than for
apple. Ca binding was low, good for food
application
In bread: improved nutritional value, freshness, water binding capacity, sourdough
functions, positive on porosity
M, P
Carrot pomace, citrus

and pineapple peels and
pomace
Carrot residue, orange
waste, mango peel and
stone
Cauliower leaves, cabbage
leaves
B: SSF A. niger mass multiplication
Citrus by products and

wastes
B: 1. cellulolytic degradation by
A. niger, 2. Torulopsis utilis, P: 3.
drying
M, P
Fi: food supplement c-linolenic acid,

O: pharmaceutical application
Stredansky et al. (2000)
Fi: substitute for marzipan, oil for bitter

almond oil, protein enhancer
O: dye removal in wastewater treatment
Tuncel et al. (1998)
Fi: dietary bre in food, nutritional value

and healthy food, binding metals, O: binding
capacities for toxic metals potential for
adsorption?
Namasivayam and Kanchana

(1992)
Borycka and Zuchowski (1998)
Dietary bre enhancement in bread, sourdough substitute in rye and white bread
Filipini and Hogg (1997)
Fi: cake, dressings, pickles, Fi: bread
O: biocontrol agent in cultivation of melons
Ohsawa et al. (1995), Ohsawa

et al. (1994)
Henn and Kunz (1996), Henn
(1998)
Mukherjee and Sen (1998)
Ff: Layers hen diet
Zia-ur-Rehman et al. (1994)
Protein content rose from 14.5% to 22.6%
Ff: cattle and poultry
Majid et al. (1995)
Inuencing the texture and viscosity of the

beverage
Fi: clouding agent in beverages
Sreenath et al. (1995)
Carrot pomace
Carrot pomace
Fi: food avours
Development of the upgrading process, good

results for stabilisation of several properties
Biocontrolling agent against Fusarium oxysporum on muskmelon, especially citrus
pomace (20%)
Egg size and production enhanced with
carrot and orange, neutral with mango stone
Fi: multifunctional ingredient in beverages
Residual matter/co-product
Citrus peel
Citrus residues, apple pomace, sugar beet pulp
B: enzymatic, cellulolytic and

pectinolytic hydrolysis, microbial conversion
M, P
Cocoa pod husk, bean

shells and germ
Corncob shreds, wheat
straw, wood chips
Corncobs
M: chopping, B: SSF with

Phaenerochaete chrysosporium
and C. versicolor
Pectin extraction, phytochemicals
Pectin and protein extraction, germ oil with

high oleic and linoleic acid content
Corncob shreds and wheat straw showed 70
75% adsorption rate for textile dyes. In SSF
both substrates have been degraded and dyes
metabolised. Wood chips did not work for
adsorption nor SSF
Cranberry processing waste

Fruit pomace
Galgal peel (citrus pseudolimon)

Grape pomace
M: powdering, C: pectin extraction

M: grinding, P: drying
Grape pomace
Grape pomace
Combination of the antioxidential potential of polyphenols in

grape pomace with the dietary
bre matrix
Grape pomace, Carrot pomace
M: grinding, P: drying, B: SSF,

UASB reactor
Hawthorn pulp (Mexican

fruit)
Jack fruit, pineapple (skin,
stem, leaf) and mango
waste (skin, kernel)
Lemon peel and pulp, olive,
apple and grape pomace
Mandarin fruit waste
Pectin extraction
C, M, P
Determination of nutritional value, several

analyses
C, P
Interactions of dietary bres with Fe and Ca
C: avonoid extraction
Mango kernel
C, M
Mango peel
High fungistatic activity towards Phoma

tracheiphila, causing citrus malsecco
Flour substitute with moderate sensory acceptability, higher calories and protein
Pectin extraction
Cu ion adsorption is lignin and cellulose

dependent, simple modications necessary,
packed bed investigations
Investigated new dietary bre compositions
for the application in food
Nutritional value improved, physiological

properties inuenced
Future idea to use the carrier function of
dietary bres as a matrix for other technologically useful substances (antioxidants,
avours, dyes, emulsiers) plus improvement
in nutritional value (bre, vitamins)
Widmer and Montanari (1995)
Fi: stabiliser, thickening agent, gelling agent,

soluble bre, Ff: protein rich pod husk
Op: bioadsorbents for wastewater treatment,
O: soil conditioner after SSF
Nambudiri and Shivashankar

(1985)
Nigam et al. (2000)
O: general use in wastewater treatment
Tsai et al. (1998)
Op: alternative bioadsorbents for wastewater

treatment
Odozi and Emelike (1985),

Hawthorne Costa et al. (1995)
O: SSF, fungal inoculate production

Fi: health quality improvement by adding
bre product
Fi: as stabilisers, thickening agent, jellies, etc.
Zheng and Shetty (1998)

Borycka (1996)
Fi: dietary bre supplement, insoluble is

major fraction
Fi
Grohmann and Bothast (1994)
Attri and Maini (1996)

Valiente et al. (1995)
Martin-Carron et al. (1997)
Both bre enhancement and antioxidants in

food, carrier idea
Saura-Calixto (1998)
O: substrate in bioreactor UASB, Fi: bread

improver, sourdough substitute, dietary bre
and b-Carotene enhancer
soluble bre
Fi: possible application as food ingredients
Lucas et al. (1997)
O: possible adsorbents, Fi: importance for

human nutrition
O: natural fungicide in citrus fruit cultivation
Higareda et al. (1995)
Corncobs and onion skin
M, P: drying, pyrolysis, C: ZnCl2

as activator
M, P

soluble bre, O: several applications
O: Pectin, liquid biofuel, substrate for bioconversions
Haque et al. (1997)
Torre et al. (1995)
Fi: for biscuits
Chkhikvishvili and Gogiya

(1995)
Arogba (1999)

soluble bre
Srirangarajan and Shrikhade

(1976)
173
174
Table 3 (continued)
Pre-treatment
Results
Reference
Mango peel and stone
15% pectin in the peel, 20-fold avour

concentrate can be recovered from peel,
stone kernel is rich source of carbohydrates,
protein and fat (12%).
Fi and O: pectin, Kernel fat: use in soap

manufacturing or as cocoa butter substitute,
potential for the preparation of sweetmakers
Nanjundaswamy (1997)
Oat, corn rice, soybean

hulls; pea pods, wheat and
corn bran
Oil palm shells
M: peeling, purifying, milling,

P: drying
Fi: Z-trim, a fat replacer and texturizing

agent, lowering the calorie content of food
and bre enhancer
O: activated carbon for adsorption in
chemical industry
Inglett (1998)
Olive cake
ZnCl2 015% impregnation produces decent

microporous carbons
Fat oxidation during drying process, hexane
extraction was on no inuence on oxidation
Lipase can degrade the fat in olive cake
In mixtures with several chemicals
Liquid and solid fractions

Phytotoxic if used as an exclusive substance,
in combination with chemicals potential
nematodes controller
Analysis used for possible sec. use: nitrogen
value low, amino acid composition well
balanced (except lysine), soluble sugars and
organic acids
Degradation of lignin, crude protein enhancement from 5.9% to 40.3%
Stirred tank and packed bed investigations,
parameters are agitation, pH-value, initial
conc., high adsorption rates with a selectivity
towards the heavy metals
Transferable to garlic or fruit waste
New technology in dietary bre production
Olive pomace
Main component is fibre > 70%.

C: extraction, P: drying, chemical analysis
Olive pomace
P: drying, M: grinding, B: delignication, saccharication

M, C
Onion skin
Onions, cull
Orange and mango skin,
apple pomace, wheat bran
Orange peel
Orange peel
M, C: extraction
M: grinding, powdering, P: drying
M: washing followed by leach
liquid treatment, B: pectinolytic
enzyme treatment to recover
soluble solids
M, P: cutting, drying, grinding
Palm kernel husk
M, C
Dye removal with cellulosic material, parameters: initial conc. of dye important,
particle sizes of adsorbent, pH-value
Pb is preferably adsorbed to Zn
Palm oil mill waste
Quantities and potential usage
Peanut and walnut shells
Peanut skin
M, C
Rich in tannin, possible use in wastewater

treatment
two types untreated and treated peanut skin
Wastewater treatment concept for the pectin

production industry. Material balance developed
Hussein et al. (1996)

Gomes and Caponio (1997)
O: lipase use in chemical, food and pharmaceutical industry

O: nematodes controlling agent for tomato
cultivation, potential phytochemical
Cordova et al. (1998)

Vitolo et al. (1998)
Rodriguez-Kabana et al. (1995)
Clemente et al. (1997)
Ff: fodder enhancement
Haddadin et al. (1999)

treatment
Kumar and Dara (1981), Bankar

and Dara (1982)
Fi: onion oil avour

Fi: General application for dietary bre
enhancement
O: pectin wastewater treatment
Brose (1993)
Larrauri et al. (1999)
Op: dye removal in wastewater treatment
Namasivayam et al. (1996)

treatment
O: empty fruit bunches for mushroom cultivation, decomposed rest as fertiliser, Op:
palm press bre for pulp and paper, Op:
palm kernel shell as activated carbon
O: heavy metal ions removal in wastewaters
Omgbu and Iweanya (1990)

treatment
El-Nawawi and Heikal (1996)
Prasertsan and Prasertsan (1996)
Randall et al. (1974)

Randall et al. (1975)
Olive cake, sugarcane bagasse

Olive oil industry waste
Olive pomace
M, P: drying, pyrolysis, C:
ZnCl2 , CO2 , as activators
P: drying, C: extraction with
hexane
B: SSF
C, M
Major analysis of several compounds
Pineapple cannery waste
P: heat treatment, M: centrifugation, B: ethanol fermentation
Pineapple peel
B: SSF Aspergillus foetidus ACM

3996
Potato peel
M, P
Potato starch waste, carrot

pomace
M, P, B
Spent malt
B: Ceratocystes mbriata
Sugar beet pulp, cereal

bran
M and P: free ferulic acid from

pectin, B: SSF with two microorganisms
P, C, B
Continuous fermentation substrate, high

syrup reduces fermenter size, enhances
ethanol production
Substrate is superior to rice or wheat bran,
16.1 g citric acid per 100 g dry waste: 62.4%
yield
Baking experiments showed that potato peel
is superior to wheat bran in minerals content,
water holding capacity and lack of phytate
Potato fruit water: protein content, peel and
pulp: bre content, especially soluble fraction, carrot pomace: colour stabilisation,
nutritional value, preservation, viscosity
Good utilisation potential for the formation
of bioavours even without precursors, substrate screening with several waste types was
done
1. A. niger to transfer ferulic into vanillic
acid, 2. Pycnoporus cinnabarius into vanillin
Sugar beet pulp
C: washing with ethanol,

P: drying, M: milling
Sugar beet pulp
C, M, P: saponication or pretreatment with formaldehyde or

epichlorohydrin
Sugarcane bagasse, bark

and onion skin
Sugarcane bagasse
M, C
C: lignin extraction
Sugarcane bagasse, pecan

shells
P, P, C: grinding, pyrolysis,
phosphoric acid activation
Sunower heads
Tomato pomace
M: grinding, B: fungal cultures,

pure and mixed
Tomato skins and seeds

Urban organic waste
P: drying, C: extraction
B: mesophilic fermentation
Comparable eciency to commercial activated carbons in decolourisation of raw

sugar
Pectin extraction
Increasing the protein and lignin content,
hence digestibility by micro-organism cultures
Proteins, minerals, and dyes (lycopenes)
Volatile fatty acids as possible avours
Martin-Cabrejas et al. (1995)

Nigam (1999)
Fi: citric acid, O: pharmaceuticals
Tran and Mitchell (1995)
Fi: bread bre improvement
Toma et al. (1979)
Fi: multifunctional ingredient in general,

focus on bread and beverages
Laufenberg et al. (1996)
Fi: general application, O: pharmaceutical

industry
Fischbach et al. (2000)
Fi: vanillin as a food avour, O: avour

compound for chemical use
Asther et al. (1997)
Fi: dietary bre, esp. soluble. Two novel

food ingredients were developed, FF: enzymes for use in feeds
Fi: dietary supplement in cookies
Broughton et al. (1995a,b)
zboy (1999)
K
oksel and O
Op: heavy metal removal in wastewater

treatment
Dronnet et al. (1997, 1998a,b)

treatment
O: heavy metal bioadsorbent for wastewater
treatment
Op: GACs
Kumar and Dara (1982)

Peternele et al. (1999)
Ahmenda et al. (2000a,b),
Pendyal et al. (1999)

soluble bre
Ff: feed stu or fodder enhancement
Wang et al. (1997)

Carvalheiro et al. (1994)
Ff, Fi: biocolorants

Fi or O: chemical industry
Al-Wandawi et al. (1985)

Sans et al. (1995)
175
Sugar beet pulp
Special attention to exploit the hemicellulotic

fraction, gum arabic substitute and fat
replacer has been developed
Coarse (600 lm) and medium (355 lm)
particle sizes showed good cookie properties.
Corn grids gave better colour. In sensory
evaluation cookies with up to 6% sugar beet
were even favoured against plain cookies
Due to the pre-treatment increasing ionexchange capacities and reduced hydration.
Epichlorohydrin treatment seems to be most
ecient, even if sorption/desorption cycles
are suggested
seven heavy metals tested
Parameters: pH-value, ionic strength, temp.
Fi: sugar source, bre enhancement insoluble/soluble, pectin

Op: liquid fuel production
Pear and kiwi pomace
B: biodegradation of hemicellulosic fraction by L. edodes
M: grinding, C: alkali treatment
Wheat straw, corn stalks
Wheat straw, insoluble

straw xanthane
Wool bre
M, P: washing, drying, C:
petroleum ether degreasing
M: debranning, polishing
Wheat bran
C: chemical, M: mechanical, P: physical, B: biotechnical; Ff: fodder/feed, Op: operational supply, Fi: food ingredient, O: other and (): no data available.
Balk
ose and Baltacioglu (1992)
Op: heavy metal cations removal in wastewater treatment
Kumar et al. (2000)
SSF is superior to SMF for biodegradation,

mechanical characteristics of the papers were
improved
>90% removal eciency in heavy metal
solutions, 7595% in tannery wastewater
Parameters: fast rate uptake, no temp.
dependency
Op: wastewater treatment adsorbent
Giovannozzi-Sermanni et al.
(1995)
Dexter and Wood (1996)
Fi: multifunctional food ingredient with

specied physicochemical and nutritional
properties
Op: paper and pulp bre resource (lignin)
Gupta et al. (1993)
Porous carbohydrate ingredients with carrier

function to encapsulate avours
Analysis of the nutritive potential, cauliower leaves best nutritive score
Fi: Natural vanilla avour

O: bioplastics with special properties
Fi: dietary bre enhancement, avour encapsulation and application in various food
Ff: for ruminants
Results
CO2 avour extraction
M, P, B
Vanilla shells
Vegetable raw materials
Vegetable residues (not
specied)
Vegetable waste, 24 types
Patent
Pre-treatment
Table 3 (continued)
Schutz et al. (1982)

Feil (1995)
Zeller (1999)
Reference
176
the inuence on colour stability an application of the

latter ascorbic acid would be most useful for food applications.
Hence almost any recycling process will start with the
steps pre-treatment (ensiling), drying, size deduction and
fractionation.
The overall recycling strategy, described in Fig. 3, is
designed in a modular manner, thus subdivided into
substance characterisation, denition of objectives,
product and process design and application and optimisation. The result is a nal product which is optimised, in regard to the requested product properties, in
the exhibited way a multifunctional food ingredient.
The rst phase is mainly the substance characterisation, based on these data the optimal recycling and
application areas and possibilities are worked out. Particle classication, chemical analysis and physicochemical properties are the important steps.
Following the denition of objectives will enclose the
desired properties of the future food ingredient as well
as the food to be applied to. At this point a decision has
to be made about the use in theory. Based on these key
properties advantages will arise for technological benet, health or taste of a product.
Product and process design covers product and dispersion properties as well as their changes depending on
the process parameters. Obvious examples are desirable
or undesirable interactions between the food ingredients
in general or during processing and interactions with
surrounding and processing factors.
The range of possible interactions is enormous, thus a
concentration on the valuable ingredients as well as on
the desired technological, sensorial and physiological
properties is useful. A continuous control and improvement of the upgrading process and product can be
gained by prototype development, denitions of partial
qualities as well as incorporation of feed back circles.
At the application phase food product and newly designed food ingredient will be combined. At this interaction point the estimated use and practical application
in a real food system meet each other. Quality related
properties of the new product have to be assessed and
compared with similar products being already on the
market. Hence a successful launch may be forecasted.
The sensorial quality is the most important criteria
for a multifunctional food ingredient applied in a new
product. Since sensorial, technological and nutritional
quality of the new product is compared to a so-called
gold standard, the optimisation is nearly completed.
Final investigations into product properties will answer
questions, which are useful to point out the consumers
benet or even the unique selling position. The latter is
often science based and hence measurable.
Instead of producing a multifunctional food ingredient the goal could be alternatively the bioconversion
into a food avour or the development of an operational
177
Fig. 3. Strategy for the development of multifunctional food ingredients made of vegetable residues: the upgrading concept (modied after Henn
(1998)).
supply like a bioadsorbent. Hence dierent objectives

will aect the product and process conception and the
application phase.
In the following the theoretical description of the
upgrading concept will be veried at three implementation examples.
Part B
understood as natural ingredients taking over food additive functions during processing and/or add a further
benet to the nal product.
Several research groups have been working on the
development of multifunctional ingredients from vegetable residues and its application in dierent food
products. The crude bre content combined with at least
one other property enables them to full several functions in food as exhibited in Table 4. A couple of quality
4. Target state: Selected practical implementations

4.1. Novel types of products: multifunctional food ingredients
Let your food be your rst medicine
(Hippocrate, 377 B.C.)
A promising possibility for the utilisation of organic
residues in the frame of green productivity is the development of innovative products. In the mentioned
context multifunctional food ingredients have to be
Table 4
Food properties and quality inuenced by multifunctional food ingredients (Laufenberg et al., 1996)
Operating areas of multifunctional food ingredients due to food
properties and quality
(1) Nutritional and healthy quality, e.g. vitamin content, dietary
bre content
(2) Food product structure, e.g. porosity, network structure
(3) Sensorial properties, e.g. texture/structure, mouth feel, freshness
(4) Physical properties, e.g. density, viscosity
(5) Processing properties, e.g. water binding ability, emulsifying
properties
178
Belloso, 1999), and cakes, dressings and pickles (Ohsawa

et al., 1995). New approaches try to use the dietary bre
as a matrix for the encapsulation of antioxidants (SauraCalixto, 1998) or avours (Zeller, 1999), using both the
physiological eects and the technological advantages in
the form of a controlled release.
Almost every avour company is nowadays interested in microscopically encapsulated aromas, which do
not escape directly but under precisely dened circumstances, for example under mechanical stress such as
chewing the chewing gum or at a certain temperature
while baking cake mixtures (Stock, 1999; Schr
oder,
1999).
Beside the application as a texturing or gelling agent
the fat replacement function in diet food is an important advantage of bres. Recently new food additives
have been developed on the basis of vegetable residues
(Broughton et al., 1995a,b; Inglett, 1998).
The high crude bre content of the vegetable pomace, see Table 5, suggests its utilisation as a crude
bre bread improver. One reason for the low dietary bre uptake is the non-acceptance of whole meal
determining food properties can be governed by the

application of these food ingredients. The raw material
mostly used is carrot pomace (Filipini and Hogg, 1997;
Henn and Kunz, 1996; Henn, 1998; Lucas et al., 1997;
Ohsawa et al., 1994; Ohsawa et al., 1995; Laufenberg et al.,
1996), followed by citrus waste (Sreenath et al., 1995;
Widmer and Montanari, 1995), grape or apple pomace
(Borycka, 1996; Carson et al., 1994; Lucas et al., 1997;
Saura-Calixto, 1998; Masoodi and Chauhan, 1998),
sugar beet pomace (Broughton et al., 1995a,b; K
oksel
zboy, 1999), orange, mango and apple peel
and O
(Larrauri et al., 1999), mango kernel our (Arogba,
1999) (as a wheat our substitute), potato peel (Toma
et al., 1979), sugarcane bagasse (Clarke, 1995) or mixtures of oat, rice, corn hulls and pea pods (Inglett, 1998).
They are applied in pie llings (Carson et al., 1994),
crackers (Carson et al., 1994; Joshi and Sandhu, 1996),
bread (Filipini and Hogg, 1997; Lucas et al., 1997;
Ohsawa et al., 1994; Clarke, 1995), cookies (Clarke,
zboy, 1999), beverages (Henn and
1995; K
oksel and O
Kunz, 1996; Henn, 1998; Laufenberg et al., 1996; Sreenath et al., 1995), jam (Grigelmo-Miguel and Martin-
Table 5
Content and composition of dietary bre of some residues (Laufenberg et al., 1996; Martin-Cabrejas et al., 1995; Torre et al., 1995; Seibel and
Hanneforth, 1994)
Residues
Fibre
Pectin
Lignin
Cellulose
14.2
3.2
10.7
15.69
2225
6
18.2
13.7
43a
32
25.8
50.9
45.8
69.4
18.7
28.2
26.0
65.7
7.25
25.23
12.02
4.10
90.1
54.5
84.7
35.4
7.1
22.7
19.8
3.7/15.5 (Haddadin
et al., 1999)a
5.4
19.1
17 (Hawthorne Costa
et al., 1995)
3.2
5.5
2.9
37.2/35.4 (Haddadin
et al., 1999)
18.4 (Haddadin et al.,

1999)
43.9
73
36.3
7.6
6.2a
7.05
16
5.2
13.8
16
15.8
9.4
6.4
Soybean shells
Sugar beet pulp
64.6
75.3
56.9
50.1
7.7
25.2/22.1 (K
oksel and
zboy, 1999)
O
15 (Tuncel et al.,

1998)
30 (Purchase, 1995)/26
(Broughton et al.,
1995b)
23/27.2 (K
oksel and
zboy, 1999)
O
White wine pomace
58.6
56.3
2.3
1.85 (K
oksel and
zboy, 1999)/4.56
O
(Broughton et al.,
1995b)
41.2 (Torre et al.,
1995)/53.6 (Valiente
et al., 1995)
Total
Insoluble
Soluble
Apple pomace
Barley pomace
Carrot pomace
Cocoa pod husks/bean
shells (Nambudiri and
Shivashankar, 1985)
Corncobs
62.5
65.3
29.6
36.3
48.3
62.1
18.9
Kiwi pomace
Lemon peel
Lemon pulp
Olive cake
Pea pots
Peach pomace (Pagan
and Ibarz, 1999)
Pear pomace
Potato peel (Toma
et al., 1979)
Potato pulp
3.9 (Torre et al., 1995)/

5.5 (Valiente et al.,
1995)
Results expressed as percentage of original dry matter, (): no data available.

a
As hemicellulose.
products in large parts of the population. An enrichment of dierent products with crude bre compounds
can thus raise the dietary bre uptake, if the food
products are not modied too much. The macromolecular structure of the bre must not be changed
during the transformation of the residue into a food
compound, and the bre material has to be of food
grade.
In bread and bakery goods, as well as in pastry, cereals and dairy products, the investigated carrot pomace
works as a stabiliser. Beside crude bre it is rich in provitamins, colour and natural acids. It takes over several
functional properties mentioned in Table 4, additionally
substitutes sourdough in bread, is acidifying agent,
preservative or antioxidant in several food products
(Filipini and Hogg, 1997; Lucas et al., 1997; Ohsawa
et al., 1994, 1995; Toma et al., 1979; Masoodi and
Chauhan, 1998).
In beverages, carrot pomace or citrus waste will stabilise the natural colour, improve the vitamin and bre
content, enhance the viscosity (mouthfeel) (Laufenberg
et al., 1996; Henn and Kunz, 1996; Henn, 1998), and
enrich or adjust the cloudy appearance (Sreenath et al.,
1995). The organoleptic and chemical properties oer a
widespread use in healthy and functional drinks and
selected fruit juices.
Several series of experiments were done to determine
the inuence of dierent pre-treatment/preservation
methods on the physicochemical properties of carrot
pomace when applied in food. Therefore common
acidifying agents, i.e., citric, acetic or ascorbic acid, were
applied to stabilise and preserve the fresh pomace, as
well the carrot pomace was fermented by Lactobacillus
farciminis.
Processing of the vegetable residue can be done by
fermentation with lactic acid bacteria leading to a
suitable transformation of low molecular materials
like sugars and to a microbial stabilisation, because
enterobacteriaceae and moulds present on the po-
179
mace are inhibited by the lactic acid formed. This

eect is already used for several vegetables including carrots with the task of preservation, e.g.
pickles. The pomace is fermented by Solid-StateFermentation, which does not need as much free
liquid phase as submerged fermentation and thus
makes downstream processing of the crude bre
product easier and cheaper. After lactic acid fermentation of carrot and grape pomace the product
is rich in crude bre, shows an acidic pH and can be
used as a bread improver and for crude bre enrichment of bakery goods.
Afterwards the pomace was treated with common
drying operations, i.e., spray, freeze or oven drying. It
could be determined that the colour stability was mostly
improved by the addition of ascorbic acid (avoids the
formation of free radicals), which improves the nutritional value too. Fermented samples were superior to
non-fermented samples as clouding agents and showed a
good shelf life too.
The ideal dietary bre should meet specic requirements, residues own natural properties, this relation
could be tailored during the dierent processing steps, as
exhibited in Fig. 4.
Currently there is a great variety of raw materials
from which dietary bres are obtained such as wheat
or rice, etc. Useful alternatives/substitutes could be
gained from vegetable residues like orange peels, mango
peels, grains, soybean or oat hulls, cereal bran, etc.
(Larrauri et al., 1999), fruit pomace (Borycka, 1996),
grape pomace (Martin-Carron et al., 1997; Valiente
et al., 1995), pear and kiwi pomace (Martin-Cabrejas
et al., 1995), wheat bran (Dexter and Wood, 1996), or
sugar beet pulp (Broughton et al., 1995a,b; K
oksel and
zboy, 1999).
O
Several treatments could be performed to improve the
functionality of the insoluble bre, which is the main
component of the residual matter, mentioned in Table 5,
as
Fig. 4. Natural properties of vegetable waste (average) and food properties and quality being inuenced by multifunctional food ingredients.
180
partial delignication of lignocellulose by alkaline

H2 O2 treatment,
extrusion,
encapsulation with soluble bre to produce a product
with better textural properties,
enzymatic modication to improve sensorial properties.
mental benets the quality of the wines is improved,

resulting in higher prices for these wines and special
recommendations in wine guide journals (Kriener,
1999).
Saura-Calixto (1998) produced a dietary bre rich in
associated polyphenolic compounds combining in a
single material the physiological eects of both dietary
bre and antioxidants. Fibre matrices could act as
support for biocolourants made of anthocyanins from
olive cake (Clemente et al., 1997), lycopenes from tomato skins (Al-Wandawi et al., 1985) or b-carotene
from carrot pomace (Henn and Kunz, 1996). Phenolic
compounds are powerful antioxidants and may possess
potential pharmacological properties, already widely
used with green tea catechins (Nwuha et al., 1999) or
ferulic acid extracted from sugar beet pulp (Couteau and
Mathaly, 1998) which could make them desirable ingredients in the developing market of functional foods
for health. Bioavonoids like hesperidin, naringin or
rutin are able to normalise capillary permeability and
vascular brittleness, therefore they are frequently called
vitamin P factors. Hesperidin is applied in vein medication, acts antiviral in ue therapy and owns articial
sweetener properties; hydrated naringin is 300 times
Dietary bre from cereals are more frequently used

than those from fruits, although fruit bres have better
quality due to higher total and soluble bre contents,
lower phytic acid contents, colonic fermentability and
water and oil holding capacities. The latter is of particular interest for the carrier function of dietary bres
which has been already used for antioxidants (SauraCalixto, 1998), encapsulation of avours (Zeller, 1999)
or dyes (Filipini and Hogg, 1997; Henn, 1998). There is
a future need to develop processes for the preparation of
fruit bres that minimise the losses of associated natural
bioactive compounds which may exert higher health
promoting eects than the dietary bre itself. The higher
concentration of health promoting avonoids compared
to traditional wine growing is often mentioned in connection with ecological viniculture. Besides environ-
Table 6
Content of several relevant compounds in vegetable residues (Al-Wandawi et al., 1985; Clemente et al., 1997; Henn, 1998; Larrauri et al., 1999; Lu
and Foo, 1997; Saura-Calixto, 1998)
Residue
Plant phenols (avonoids, phenol carboxylic acids)

Colourless
Apple pomace
Carrot pomace
Chokeberry
pomace
Cocoa bean shells
Elderberry pomace
Grape pomace
Grape skins
Grape fruit peel
Green tea
Honeysuckle
pomace
Mango peel
Olive press cake
Orange peel
Red beet pomace
Sugar beet pulp
Tomato skins
Coloured
b
0.724% (Lu and Foo, 1997); 350.6 mg/kg , FA 8.0 mg/kg

(Lucarini et al., 1999)
b-carotenea 3 mg/kg
Anthocyanins 9.1 g/kg (Mariassyova et al., 1999b)
Tannins 3.1%a
Leucoanthocyanidin (Nambudiri and Shivashankar, 1985)

Anthocyanins
Anthocyanins
Carotenoids
2%a ; 11.7%a (Zeller, 1999)

2535%a (Anon., 1999)
Naringin 0.071.7%b
10.121.6%a; c

5.5%a
0.3%b
Hesperidin 1.32.4%b /1.72%a (Manthey and Grohmann,
1996); Nobiletind 32% (Manthey and Grohmann, 1996)
Carotenoids
Anthocyanins
Carotenoids
Betanine 414.3 mg/kgb (Mariassyova et al., 1999a)
FA 0.36% (Couteau and Mathaly, 1998)/8 g kg

(Thibault et al., 1998)
210.8 mg/kgb FA 3.7 mg/kgb (Lucarini et al., 1999)
Lycopenesb 120 mg/kg (Al-Wandawi et al., 1985), 80 mg/kgb

(Lucarini et al., 1999)
FA ferulic acid.
a
Related to dry mass.
b
Related to fresh good.
c
Depending on the tea species and seasonal changes. Tea avonoids are catechin, gallocatechin, epicatechin, epicatechin gallate, epigallocatechine,
epigallocatechin gallate, the latter of which is always the largest fraction (Chu and Juneja, 1997).
d
In orange peel oil solids (hexane extracted).
sweeter than saccharose, neohesperidin almost 2000

times.
The array of dierent compounds existing in a diversity of free and bound forms is considerable, see
Table 6. Grape skin extract in powder form is commercially available as a natural food colorant. Besides
the bluered colour the food will be enriched with
healthy polyphenols (Anon., 1999). The fermentation
of dietary bre increases digestibility, shelf life and
preserves the bioactivity of the components. It is often
recommended as a hygienisation step prior to drying
and milling (see above).
The use of bres from new origins that are currently not fully exploited and the possibility of modifying the bres, by chemical, enzymatic and/or
physical treatments, combining them with other components and enhancing their nutritional and sensory
characteristics, will probably widen the elds of application for dietary bres. Thus this market shows a
reasonable utilisation potential for vegetable residues,
adding value to by-products, most of which are regarded as waste to be discharged so far (Theobaudin
et al., 1997).
Several residues have already been characterised by
their pectin content, as shown in Table 5. Pectins are
linear polymers of a-D -galacturonic acid in which the D galacturonic acid units are linked by 1 ! 4 glycosidic
linkages. Pectic substances have an important inuence
on food texture and are used in products like jams, jellies, dairy products, beverages, pastries and confectioneries. More and more they are used in pharmaceutics
and cosmetics as well. Pectin is located in the cell walls
of vegetables and fruits, commercially and environmentally interesting is the use of residual matter as
a potential pectin source. The gelation mechanism of
pectins is mainly governed by their degree of esterication (DE). Commonly, two types of pectin gels are distinguished. The rst type made from high methoxyl
pectins (DE beyond 50%) form gels in an acidic environment and in the presence of sucrose. The second type
of pectin gel is composed of low methoxyl pectins (DE
below 50%). These pectins form gels in presence of alkaline earth elements, especially calcium. In both cases
gelation and gel properties depend on many factors,
including pH, temperature, DE, sugar, calcium, and
pectin content (Tuncel et al., 1998).
The presence of up to 30% pectin in dried residual
matters like sugar beet pulp, carrot pomace, potato pulp
or lemon peel and its availability in large quantities have
made extraction worthwhile. Several other sources of
pectin are reported beside the mentioned ones in Table
5, e.g., citrus peel (Widmer and Montanari, 1995), citrus, apple and sugar beet pulp (Grohmann and Bothast,
1994), cocoa husk (Nambudiri and Shivashankar, 1985),
galgal (citrus fruit) peel (Attri and Maini, 1996), hawthorn (Mexican fruit) peel (Higareda et al., 1995),
181
mango peel (Srirangarajan and Shrikhade, 1976) or

sunower heads (Wang et al., 1997).
However, no pectins have ever been extracted
from vegetable residues with gel forming properties comparable to those of pectins extracted from
apple pomace. Turqouis et al. (1999) recently developed
an alkaline extraction process for pectin from sugar
beet pulp and potato pulp. A high gelling ability
was proved using 2% extract from sugar beet and potato pulp with 172 mg CaSO4 H2 O per g extracted
product.
Kahlert (1999) tried to overcome the low gelling
properties by the combination of gelling agents using
their synergetic eects. A lot of structuring substances
like cellulose, pectin, carrageen, agar-agar, alginate can
be taken from vegetable waste and composed to new
multifunctional food ingredients and act as stabilisers,
thickeners, fat replacement, etc. Pectins of dierent origin could be mixed due to the requested application and
properties, examples are mentioned in Higareda et al.
(1995), Nambudiri and Shivashankar (1985), Srirangarajan and Shrikhade (1976), Wang et al. (1997) and
Widmer and Montanari (1995).
4.2. Bioconversion via solid-state fermentation: the generation of avours
The tongue cannot be betrayed permanently.
(K
oster, E. International FoodTec Congress,
Cologne/D 1994, giving a lecture about natural
and synthetic food additives.)
Biological conversion processes of fruit processing
wastes into various value added products through solidstate fermentation (SSF) has been of major interest to
many laboratories around the world. SSF deals with the
utilisation of water-insoluble materials for microbial
growth and metabolism, and it is usually carried out in
solid or semi-solid systems in the near absence of free
water or reduced water content compared with submerged fermentation (SMF). Many of the potential
products from fruit and vegetable residues have been
developed using the SSF technique, and such products
include ethanol, methane, lactic acid, citric acid, mushrooms, enzymes and food ingredients (Zheng and
Shetty, 1998). As shown in Table 9 most of the research
in SSF of residual matter has been done in the last seven
years. Still there is a lack of proper modelling and
process parameters.
The world market of aroma chemicals, fragrances
and avours has world-wide a growth rate of 45% per
year. In 1995 it was worth 9:6 109 US$ and in 2000
it is expected to be 12 109 US$ (Hartman, 1996).
Because of a higher consumer acceptance there is an
increasing economic interest in natural avours.
182
The European Community guidelines 88/388/EWG

and 9/71/EWG subdivide avours/aromas into six
categories, the rst of which is describing regulations for the food labelling natural avour. Natural avours are chemical substances with aroma
properties which are produced from feedstock of
plant or animal origin by means of physical, enzymatic or microbiological processing (Huber and
Fo
a, 1999).
The microbial synthesis of these natural avours is
generally carried out by SMF. Due to the high costs of
this currently used technology on an industrial scale
there is a need of developing low cost processes even for
cheaper molecules like benzaldehyde (US$ 198 per kg
(Sigma, 2000)). This could be achieved by exploration of
the metabolic pathways and by alternative technology
such as SSF (Feron et al., 1996).
Suitable for SSF is every vegetable waste in principle.
In case of bioavour production the SSF of residual
matter is a fairly new technology of waste utilisation,
based on a very old preservation method, which bioconverts secondary raw materials to natural avours, as
shown in Table 11.
The microbial synthesis on solid substrates oers
some advantages compared with conventional SMF
such as
Table 8
Selected avours and selling prices in US$ per kg
Flavour/aroma
Description
Synthetic
Natural
c-Deca lactone
d-Deca lactone
1-Octen-3-ol
2-Heptanone
Benzaldehyde
Ethyl butyrate
Isoamyl acetate
Peach, fruity
Coconut, creamy
Mushroom
Cheesy, spicy
Almond
Fruity, pineapple
Banana, fruity,
sweet
Banana, fruity,
pineapple
Roses
Raspberries
Vanilla
Vanilla
75.00
130.00
184.00
39.00
31.00
31.00
31.00
1400.00
5500.00
198.00
55.00
31.00
31.00
345.00
31.00
58.00
31.00
410.00
2050.00
3000.00
685.00
Isoamyl butyrate
Phenethyl alcohol
Raspberry ketone
Vanillin
Vanillic acid
Source: Flavors & Fragrances 2000, Aldrich Milwaukee WI USA,

(Sigma, 2000).
The conditions of the SSF-process are well adapted

to the requirements of moulds, which represent about
60% of the micro-organisms used in avour production.
The higher space-time yield leads to smaller reactor
volumes compared with SMF. The SSF reactor with
the same yield as an SMF reactor can lead to a three
times smaller amount of investment costs (Vollbrecht,
1997).
by benzaldehyde, used in an amount of more than 1000

t/a. Vanillin is currently synthesised from petrochemical
substances like guajacol, or lignin, both of which are
produced as co-products of pulp manufacture in huge
amounts. The microbiological production is based on
the precursors eugenole or ferulic acid, the latter often
found in vegetable residues and pomaces in reasonable
amounts. So far there are only few eective bioconversion processes available, hence an industrial application
is limited.
Tables 7 and 8 are an overview of prot margins
possible provided that an eective production path is
found. Table 9 lists recent progress in SSF of vegetable
residues, obviously most research in avour fermentation via SSF was done in the last seven years.
In order to introduce an economically competitive
biological process, three major drawbacks must be
overcome:
Most important avour is currently vanillin, the annual world-wide use exceeds 12,000 t/a, 20 t of which are
produced from natural extract (equivalent to 1800 t of
vanilla beans) (Asther et al., 1997). Vanillin is followed
II(I) The high costs of the substrate (e.g., molasses).

I(II) The low product concentration (about 2% for acetonebutanoleisopropanole (ABI) fermentation
because of solvent toxicity).
Table 7
Selected avours, production rates and selling prices
Flavour
Feed conc.a
Selling price in US$/kg
Year
Vanillin
230 mg/l (Asther et al., 1997)

560 mg/l (Thibault et al., 1998)
6 g/l
5.22 mg/kg DM
6.25 mg/l (Christen et al., 1997)
2 g/l
17 g/l
Natural extract 4000 (Asther et al., 1997)
1996
1998
1992
1999
1997
1994
1991
1996
c-Deca lactone
Isoamyl acetate
b-Phenethyl alcohol
2-Heptanone
Ethyl butyrate
() No data available.
a
Related to biotechnical production.
Biotechnical 6000
Biotechnical 2500
Synthetic 39
Biotechnical 180
183
Table 9
Flavours and bione chemicals produced by SSF of vegetable residues (selection)
Year
Residual matter
Description/conversion principle
Product
1991
Apple pomace (Almosnino and Belin, 1991)
Volatile aldehydes, alcohols
2000
Apple pomace, spent malt grains (Stredansky et al., 2000)
1998
Carrot, citrus, pineapple pomace (Mukherjee and Sen, 1998)

Cassava bagasse, apple pomace (Christen
et al., 2000)
Enzyme system to degrade the precursors

linoleic and linolenic acid
T. elegans CCF 1456 degraded the substrate
in a ratio of 3 to 1 (AP to SMG), precursor
peanut oil even increased the yield
Aspergillus spp. Mass multiplication
2000
1997
1994
1998
Cassava bagasse, wheat bran and sugarcane

bagasse (Christen et al., 1997; Bramorski
et al., 1998)
Citrus, apple, sugar beet pomace (Grohmann and Bothast, 1994)
Cranberry pomace (sh oal) (Zheng and
Shetty, 1998)
2001
Linseed cake, castor oil cake, olive press

cake, sunower cake (Laufenberg et al.,
2001)
1998
1999
Olive cake, sugarcane bagasse (Cordova

et al., 1998)
Olive pomace (Haddadin et al., 1999)
1995
Pineapple waste (Tran and Mitchell, 1995)
1997
1997
Potato waste (Lucas et al., 1997)

Sugar beet pulp, cereal bran (Asther et al.,
1997)
Tomato pomace (Carvalheiro et al., 1994)
1994
Four strains of Rhizopus, two residues and

two precursors, mixed substrate combinations
C. mbriata, ability to generate fruity aromas in dependence on the substrate used
Microbial conversion by enzymatic hydrolysis
Trichoderma viride, Rhizopus CaCO3 was
added as neutraliser, water for aw adjustment
Moniliella suaveolens, Trichoderma harzianum, Pityrosporum ovale and Ceratocytis
moniliformis form decalactones (problems
with phenolic components)
Lipase degrading fat in olive cake
Four micro-organisms, delignication, saccharication with Trichoderma spp., biomass formation with Candida utilis and
Saccharomyces cerevisiae
A. foetidus produces citric acid 16.1 g/100 g
DM and 3% methanol
Amylases
Commensalism of two micro-organisms degrading the substrate
Co-cultures of Trichoderma reesei and
Sporotrichum sp. are degrading cellulose and
hemicellulose fraction
c-Linolenic acid was produced in a yield of

5.17 g per kg dry substrate; with peanut oil
precursor 8.75 g per kg DM
Biocontrolling agent in cultivation of melons
Volatile carbons as avours; acetaldehyde,
ethanol, propanol, esters
Banana avour and fruity complex avours,
up to 10-fold higher production compared
to ripe bananas
Pectin, substrate, liquid biofuel
Polymeric dye decolourising isolate for
wastewater treatment, extracellular enzymes
Acceptable yields on olive press cake and
castor oil cake. d- and c-decalactone (up to
1 g per kg DM) are produced
Enzyme product applied in bakery goods,
confectionery, pharmaceuticals
Crude protein enriched from 5.9% to 40.3%.
Source for animal fodder
Pharmaceuticals, food industry, preserving

agent
Bakery goods, breweries, textile industry
Flavour vanillin
67% less cellulose, 73% less hemicellulose,
enhanced lignin and protein content
DM dry matter.
(III) The high product recovery costs (distillation has

been used in the past).
The provision of substrates makes up about 63% of
the total costs of ABI production, therefore a variety of
alternative compounds have been checked out for their
ability to replace the now expensive molasses (Duerre,
1998). The high raw material costs could be drastically
reduced by using vegetable co-products as substrates,
see Table 9. Christen et al. (2000) mixed various proportions of vegetable residues and added selected
precursors to additionally inuence metabolism and
product concentration. They found that the volatile
carbon production by fungi can be signicantly inuenced, leading to manifold enhanced production rates.
Remaining problem besides the production of a certain avour is its isolation and purication (down
stream processing), which is again strongly dependent
on the produced concentration of the biochemical.
Therefore research groups have been looking for combined solutions of highly concentrated production and
on-line separation (Kunz, 1999).
A pilot plant for acetone and butanol fermentation in
Starrein/Austria is described in (Duerre, 1998), the operational start was planned for spring 1998. As substrates have been used agricultural starchy materials
like low grade potatoes, potato cutting waste, potato
pulp and fruit water from starch production, maize and
rye. The product separation is done by gas stripping
with heating of the euent to 70 C and condensation
of the solvent/water vapours.
Membrane based systems such as reverse osmosis,
perstraction, pervaporation and membrane evaporation,
as well as liquid/liquid extraction, adsorption and gas
stripping have been compared by Duerre (1998) towards
their employment in downstream processing, but there
is no precise statement as to the most suitable one.
Membrane systems show a high selectivity for solvents,
184
but might suer from clogging and fouling, liquid/liquid

extractions might form emulsions, reducing their eectiveness, gas stripping does not lead to complete removal
of solvents and adsorption materials are quite expensive.
The raw material costs for the latter adsorption materials could be drastically reduced by the use of bioadsorbents made of vegetable waste, which is explained in
detail below.
The restrictions might be overcome by the combination of SSF with hollow bre contained liquid
membranes for the production and separation of volatile food avours like isoamyl acetate or 1-octen-3-ol
(mushroom), recently described in Laufenberg and
Cussler (1999).
The bioconversion of vegetable residues is economically attractive only if high value products are produced.
The market prices for biotechnically produced bulk
chemicals are fairly low, e.g., 0.53 per kg butanol, 0.44
per kg acetone or 0.40 per kg ethanol (prices in US$ in
1980 (Duerre, 1998)). The selling prices for bioavours
are many times higher, as shown in Table 8. Highlights
are of course fruity/owery avours like peach, rose or
vanilla, but also for banana, produced by Ceratocystis
mbriata as a complex bioavour with improved quality, the fermented avour will reach higher market prices.
The variety of vegetable residues as substrates could
be even broadened by using co-cultures of microorganisms, called commensalism. C. acetobutylicum for
example is unable to degrade cellulose, but in co-culture
with a mesophilic cellulolytic Clostridium spp. even cellulose-enriched rice hulls, orange peel or sugar beet pulp
could be metabolised (Duerre, 1998). The research
group of Asther et al. (1997), Bonnin et al. (1999) and
Lesage-Meessen et al. (1999) employed a co-culture of
Aspergillus niger and Pycnoporus cinnabarius to transform ferulic acid from sugar beet pulp via vanillic acid
into vanillin.
Ferulic acid is found associated with the cell wall of
very few dicots, including sugar beets (0.36% related to
dry weight) (Broughton et al., 1995a,b; Couteau and
Mathaly, 1998) and many monocots like wheat or maize
(12% related to dry weight) (Asther et al., 1997; Dexter
and Wood, 1996). It is ester-linked to pectic sidechains
in beets and ether-linked to lignin in cereals. Besides
sugar beet pulp carrot pomace contains of reasonable amounts of pectin, thus of ferulic acid. For
olive press cake and corncobs a lignin content of 35%
rsp. 17% indicates high precursor rates too, see Table 5;
remarkable amounts of ferulic acid are mentioned
for palm press bre by Prasertsan and Prasertsan
(1996).
Almosnino and Belin (1991) described the use of the
intrinsic enzyme system of apple pomace for the biotransformation of fatty acids into potential avours. By
the use of these lipolytic enzymes the precursors linoleic
Table 10
Isoamyl acetate formation depending on the substrate used (based on
(Christen et al., 1997))
Residual matter
Isoamyl acetate formation

in lmol l1
Wheat bran/no supplement

Sugarcane bagasse/no supplement
Cassava bagasse/no supplement
Spent malt/no supplement (Fischbach
et al., 2000)
Wheat bran plus leucine
Sugarcane bagasse plus leucine
Cassava bagasse plus leucine
Not detectable
Not detectable
0.45
0.8
2.1
9.5
48
and linolenic acid were converted into alcohols and

volatile aldehydes. A possible substrate to use instead of
the precursors would be olive cake with its amounts of
74.0% oleic acid, 11.7% linoleic acid and 0.8% linolenic
acid (Clemente et al., 1997). Thus a mixture of these
residues would result in a useful substrate for a bioconversion of avours. The addition of SO2 and ascorbic acid combined with micronization of the pomace
enhanced the avour yield signicantly up to 90%. The
addition of ascorbic acid may be replaced by a lactic
acid bacterial fermentation of the pomace, which will
enhance shelf life of the pomace and possibly avour
yield.
A few other studies have shown the importance of the
media in the specic development of a dened aroma
(Christen et al., 1994, 1997; Meza et al., 1998). They
found that adding a nitrogen source enhances the formation of total volatiles up to 10 times, which is 10-fold
higher than that of ripe bananas too, as listed in Table
10.
Cassava bagasse with leucine supplement seems to be
the optimal substrate for banana avour production.
Spent malt appears to be an even better substrate for
total volatile carbon formation. Fermentation with this
substrate has reached almost double production yields
without any additional supplement. Biomass development and isoamyl acetate formation proles are shown
Fig. 5. SSF of spent malt with C. mbriata (Fischbach et al., 2000;

Laufenberg et al., 1999).
185
(Laufenberg et al., 1996). Further investigations have

not been published yet.
4.3. Vegetable residues as operating supplies: bioadsorbents for wastewater treatment
Realising the maximum potential using the minimum amount of material.
Fig. 6. Generation of isoamyl acetate by SSF of spent malt (Fischbach

et al., 2000; Laufenberg et al., 1999).
Table 11
Potential product substrate combinations (Fischbach et al., 2000;
Laufenberg et al., 1999)
Substrate
Flavour
Micro-organism
Apple pomace, spent

malt, spent hops,
carrot pomace
Ethyl butyrate
(pineapple), ethyl
pentanoate (apple),
isoamyl acetate
(banana)
Vanillin
C. mbriata
c-decalactone
(peach)
Yarrovia lipolytica
1-Octen-3-ol
(mushroom)
c-decalactone,
6-pentyl-a-pyrone
(nutty)
c-decalactone
P. pulmonarius
c-decalactone,
d-decalactone
(coconut)
Pyrazine
(roast avour)
P. ovale, Ceratocystis moniliformis
Sugar beet pulp

(Asther et al., 1997;
Bonnin et al., 1999;
Lesage-Meessen
et al., 1999)
Ricinus oil cake
(Feron et al., 2000;
Ferreira et al., 2000)
Castor oil cake

(Laufenberg et al.,
2001)
Sunower seed cake
(Laufenberg et al.,
2001)
Olive press cake
(Laufenberg et al.,
2001)
Soybean coarse meal
Pycnoporus
cinnabarius, A. niger
M. suaveolens,
T. harzianum
T. harzianum
Bacillus subtilis
in Figs. 5 and 6. First experiments have shown that

spent malt has a good utilisation potential as a substrate
for the production of fruit avours. A substrate
screening including spent malt, rape seed oil cake, soybean coarse meal and dierent kinds of sugar beet pellets and chips was done, where spent malt reached the
highest product yields, see Table 11. Therefore, the
following experiments were carried out using spent malt
as an exclusive substrate.
Additional optimisation of the media could be
reached by the combination of spent malt with potato
pulp consisting of remaining 6.1% (w/w) raw protein
To view vegetable waste recovery processes as potential goldmines is typically overly optimistic, as the
costs of extraction and purication of the components
generally reduce the prot margins available to levels
that are barely economic, as already described. For this
reason further eort is focused on the creation of bioadsorbents with improved functionality, using their
natural content of adsorptive components or enhancing
their adsorption rate by combination of favoured raw
materials.
Adsorption is almost always a process involving a
uid and a solid. This solid can adsorb mere traces of
solute, making this method especially useful for dilute
solutions, including those streams requiring treatment
for pollution control. Molecules adsorb on virtually all
surfaces, the amount they adsorb is roughly proportional to the amount of surface. As a result, commercial
adsorbents are extremely porous with surface areas
typically of several hundred square metres per gram. In
general the energy intensive and sophisticated material
requiring treatment tends to be more expensive than
other separations.
Adsorbents are conveniently divided into three classes: inorganic materials, synthetic polymers and carbons. Inorganic materials vary widely. Activated
alumina with polar surface is used as a desiccant, as well
as silica gel. Clays are used as inexpensive adsorbents for
some petroleum based applications, mostly they are used
once then discarded. Fullers earth is used to purify oils.
The most important class of inorganics is probably the
zeolites, a subclass of molecular sieves, their specic pores
are located within small crystals. Adsorbents based on
synthetic polymers, like ion exchange or acrylic ester
polymers are commonly used in wastewater treatment.
Most interesting in this connection are carbons. The
carbons have non-polar surfaces that are used to adsorb
non-polar molecules, especially hydrocarbons. They are
manufactured from both organic and inorganic sources,
and can be used to recover solvents, to lter gases or to
purify water. Overall carbons make a broad and important class of adsorbents (Cussler, 1997).
Conventional methods for treating wastewater containing dyes, aromatic compounds or heavy metals are
coagulation, occulation, reverse osmosis, nanoltration and pervaporation (Paul and Ohlrogge, 1998), and
activated carbon adsorption, the latter of which is
combined with membrane processes like nanoltration
186
(Eilers and Melin, 1999; Nicolet and Rott, 1999) or

ultraltration (Lenggenhager and Lyndon, 1997) as
well.
The mentioned processes do not show signicant efciency or economic advantage. Low cost treatment
methods have therefore been investigated for a long
time. A number of low cost adsorbents have been tried
for wastewater treatment like wool bres (Balk
ose and
Baltacioglu, 1992), microbial biosorbents (Xie et al.,
1996), pillared clays (Baksh et al., 1992), coir pith
untreated (Namasivayam and Kadirvelu, 1996) or activated (Namasivayam and Kadirvelu, 1997), banana pith
(Namasivayam and Kanchana, 1992), orange peel
(Namasivayam et al., 1996), peanut and walnut shells
(Randall et al., 1974), modied onion skin (Bankar and
Dara, 1982; Kumar and Dara, 1981) corncobs (Hawthorne Costa et al., 1995; Tsai et al., 1998), the combination of onion skin with corncobs (Odozi and Emelike,
1985), peanut skin (Randall et al., 1975), palm kernel
husk (Omgbu and Iweanya, 1990), pecan (Ahmenda
et al., 2000a,b) and almond shells (Toles et al., 2000),
sugarcane bagasse (Kumar and Dara, 1982) or functionalised lignin extracted from sugarcane bagasse
(Peternele et al., 1999). Suitable is even black currant
and apple dietary bre because of its binding capacity
for cadmium and lead (Borycka and Zuchowski, 1998).
Furthermore Namasivayam et al. (1996) mentions peat,
biogas waste slurry, Shukla and Sakhardande (1990)
used cotton and jute bres, bamboo pulp and saw dust.
The pre-treatment methods for these materials dier,
reaching from chemical extraction of lignin (Peternele
et al., 1999) to adding chemicals and further pyrolysis
(Hussein et al., 1996; Toles et al., 2000; Ahmenda et al.,
2000a,b) as included in Table 14, polymerisation
(Bankar and Dara, 1982; Kumar and Dara, 1981;
Randall et al., 1975) or just cutting, drying and grinding
(Namasivayam and Kanchana, 1992; Namasivayam
et al., 1996), see Table 15.
Adsorbents attach atoms, molecules, ions and radicals from their surrounding gaseous or liquid phase onto
their surface. Due to the loose binding forces the layer
thickness on the surface is monomolecular. Adsorption

happens on the interface, therefore an important criterion for the eectiveness of an adsorbent is its surface
area. Several methods are available to reach as large as
possible surface area like ne grinding, chemical or
biochemical modication, or creating a specic structure. Hence there is an relation between the natural
properties of vegetable material and the requirements
for high quality adsorbents which could be matched
during adaptation processing, as visualised in Fig. 7.
Besides a large surface area the optimum adsorbent
has to possess adequate surface chemistry and pore size
distribution to adsorb targeted species. Macropores lead
the component to the micropores where the actual adsorption takes place. Hence the macropores are important for diusion velocity and adsorption kinetics. The
ratio of micro and macropores and total surface area
can be inuenced by ZnCl2 addition to the residual
matter. Hussein et al. (1996) described that an addition
of ZnCl2 solution (10 w/w%) to oil palm shells resulted
in enhanced surface area from 950 to 1200 m2 g1 and
25% micropores, which are important for adsorption
capacity.
Granulated active carbons (GAC) with moderate
surface area (300 m2 g1 ), as the case for sugarcane
bagasse plus binder corn syrup, exhibit a good pore size
distribution and relatively low surface charge which
explains their good sugar decolourising capacities (Ahmenda et al., 2000b). Compared to the latter the surface
area of unpyrolysed sugar beet pulp is fairly low, see
Table 12. Physical and chemical activation changes the
Table 12
Surface areas of selected carbon adsorbents
Residual matter
Surface area in m2 g1
Pecan shells (Ahmenda et al., 2000a,b)

Oil palm shell (Hussein et al., 1996)
Sugarcane bagasse and corn syrup
binder (Ahmenda et al., 2000b)
Sugar beet pulp (Dronnet et al., 1997)
1200
1200
300
3
Fig. 7. Natural properties of vegetable waste (average) and expected product prole for carbons in wastewater treatment.
adsorption behaviour of the raw material strongly,

Table 14 exhibits a selection of used residues.
Toles et al. (2000) investigated the adsorptive properties of air-activated almond shells towards several
organics and copper. The almond shell carbon could
remove more than 400% of Cu2 from the solution
compared to commercial carbon Norite RO3515. The
organic adsorption of almond shell carbon was lower
compared to Filtrasorbe 400, ranging between 84% and
92% of the Calgone carbon total adsorption. Convincing as well is the cost estimation: commercial carbons are produced for US$ 3.30 per kg, almond shell
carbons for US$ 2.45 per kg. Johns et al. (1998) compared seven commercial GAC with GACs made of residual matter mentioned in Table 14. Both CO2 and
steam activated nutshell carbons consistently removed
more total organics than the commercial GACs.
The soybean hull based GACs showed three or four
times higher copper adsorption compared with all other
commercial or co-product based GACs.
Eective adsorption is as well feasible without physical or chemical activation. Table 15 is a selection of
vegetable residues used as bioadsorbents for wastewater
treatment so far. The raw material has only been cut,
dried, and ground before the experiments; important
inuencing parameters arise.
A rst series of experiments was done with three
dierent residues, checking their ability to adsorb
aromatic wastewater components by Laufenberg and
Filipini (2002). Vanillin, representing a substance of
oecotoxic relevance together with benzaldehyde, phenol
and humic acid, has been tested in aqueous solution.
The adsorbing conditions were determined while
changing the inuencing process parameters. As bioadsorbents the residues carrot pomace, corncob, and sugar
beet pulp, dried and ground to the particle sizes 125180
and 7101500 lm were used.
In a second test series carrot pomace and sugar beet
pulp were inoculated with L. farciminis and fermented
for 20 h. This pre-treatment step was supposed to enhance the shelf life of the fresh pomace and to partly
degrade the components. The tests should reveal if there
is any correlation between the targeted metabolism of
lactic acid fermentation and the adsorbent capacity.
Current research in this area is versatile, employing
several residues and experimental conditions, and focused on dierent operational modes. In the following
structure and dierentiation is given by subdividing the
whole material via the varying process parameters.
4.3.1. Residues, combinations, and synergies

The natural composition of the residual matter decisively inuences the adsorption capacity. Kumar et al.
(2000) found better removal eciency for insoluble
straw xanthate (8299%) than for alkali treated straw
187
(7787%) while treating heavy metal solutions. Laufenberg and Filipini (2002) determined for the adsorption
rate in order of carrot pomace > corncob > sugar beet
pulp. Carrot pomace adsorbed vanillin best at pH 4,
corncob at pH 7 and sugar beet pulp at pH 10.
Kahlert (1999) found that the combination of gelling
agents, using synergetic eects, improves the technological properties towards a widespread application in
food. These facts may enhance the adsorption capacity
and eectiveness too. Odozi and Emelike (1985) combined corncob (lignin and furfural source) and red onion
skin (source of phenolic compounds) and could enhance
the adsorption rate by 20%. The ideal adsorbents should
be rich in lignin and rich in phenols, therefore very
eective residue combinations would be lignin-rich
grape pomace (45%), olive cake (37%), corncob (17%)
or apple pomace (18%) combined with polyphenol
rich green tea waste, mango, orange or grapefruit
peel (Manthey and Grohmann, 1996), see Tables 5 and
6.
A selectivity for special substances may be reached by
combining residues with dierent binding mechanisms.
Some residues preferably adsorb components by complex formation, others by physical adsorption depending
on the lignin content, as described in Torre et al. (1995).
Peternele et al. (1999) describe synergetic eects while
treating wastewater mixtures. The eect was explained
by competition towards the binding sites. The following
selectivity scale was found in adsorption tests for the
divalent metals by Dronnet et al. (1997): Cu2 P
Pb2 Cd2 Zn2 > Ni2 > Ca2 .
In dependency to the application a variety of options
arise. Dierent residue types may be combined, possibly
pre-treated biochemically, or adsorption promoters like
fat and/or fatty acids may be added. Clemente et al.
(1997) suggested olive pomace as a suitable substrate for
adsorption. The natural fat content may even enhance
the eciency by promoting the monolayer formation.
4.3.2. Particle size

Particle sizes range between 53 and 1500 lm as
exhibited in Table 15. So far only little dependency between particle size and adsorption rate could be identied. Ho and McKay (1999) could determine a reduced
sorption capacity for colour removal with rising particle
size of sugarcane bagasse pith due to reduced surface
area; as well did Liversidge et al. (1997) with colour
adsorption on linseed cake.
Furthermore the suspension behaviour of particles in
solution is a limiting factor to the process. Contact area
is reduced if the particles sediment too fast. With most
of the investigations the eect was compensated by agitation. Laufenberg and Filipini (2002) have used the
polymer Galactomannan (carob our, molecular weight
310,000 g mol1 ), a food thickening agent and stabiliser,
188
Table 13
Surface area reduction in dependency of particle size, determined for carrot pomace
Particle size (lm)
Mean d (lm)
Density (g cm3 )
Volume (m3 )
Surface (m2 )
Surface (m2 kg1 )
Surface (m2 g1 )
032
3263
6390
90125
125180
180250
250355
355500
500710
7101000
10001400
14002000
16
47.5
76.5
107.5
152.5
215
302.5
427.5
605
855
1200
1700
1.43
1.41
1.39
1.4
1.39
1.39
1.39
1.37
1.37
1.35
1.35
1.34
1.71573E)14
4.48921E)13
1.87531E)12
5.20372E)12
1.48559E)11
4.16298E)11
1.15948E)10
3.27263E)10
9.27587E)10
2.6181E)09
7.23823E)09
2.05795E)08
3.21699E)09
2.83529E)08
7.35415E)08
1.4522E)07
2.92247E)07
5.8088E)07
1.1499E)06
2.29658E)06
4.59961E)06
9.18633E)06
1.80956E)05
3.63168E)05
131.118
44.792
28.212
19.933
14.152
10.038
7.134
5.122
3.619
2.599
1.851
1.316
0.131
0.044
0.028
0.019
0.014
0.010
0.007
0.005
0.003
0.002
0.001
0.001
Fig. 8. Design considerations for future packed bed adsorption: (a) vertical adsorber with high volume packed bed (b) ring adsorber and (c)
horizontal thick layer adsorber.
to keep the particles in suspension. Besides the suspension behaviour the enhanced surface area is an important parameter for the adsorption. Table 13 determines
the reduction in surface area per kg carrot pomace in
dependency of the particle sizes. Between the corn
classes 16 and 1700 lm the surface area is reduced by the
factor 100.
Further experiments should determine the eect of
particle size on adsorption rate. Another possibility to
enhance the contact area could be the xation of the
bioadsorbents in a packed bed as suggested in Fig. 8.
4.3.3. Adsorbent dosage
At least 2 g residual matter per liter solution was used
in all experiments. An increase of the metal binding with
rising sugar beet pulp concentration was naturally observed by Dronnet et al. (1997). While changing the
adsorbent dosage from 3.64 to 14.55 g l1 the totally
removed amount of metal was higher, but the slope was
regressive. Nevertheless the concentration of sugar beet
pulp needed for total saturation of all available carboxyl
functions by Cu2 was not reached. The authors determined that the complete binding of Cu2 by carboxylates would occur for an adsorbent dosage of 50 g l1 .
Laufenberg and Filipini (2002) simultaneously varied

adsorption time and adsorbents dosage. Their optimum
adsorbent dosage was determined as 20 g l1 with a
contact time of 5 min.
4.3.4. Removed component

Most experiments were determined treating dye solutions of dierent origin or heavy metal solutions,
preferring combinations of copper, cadmium, lead, zinc,
chrome, and nickel. So far only Laufenberg and Filipini
(2002) have removed organics from aqueous solution.
4.3.5. Initial concentration

The initial substance concentration to be treated is
naturally dependent on its solubility in aqueous solution, it ranges from 5 to 740 mg l1 . For vanillin it could
be determined that all applied residues adsorbed 10 or
20 mg l1 vanillin with a similar adsorption rate (Laufenberg and Filipini, 2002). The total vanillin uptake
increased with an increased initial concentration, although the percentage removal decreased. The following
example will clarify:
189
Table 14
Physically and chemically activated carbons made from vegetable residues as a feedstock (selection)
Material/
adsorbents
Particle size
Almond shells
(Toles et al.,
2000)
benzene, toluContinuously
Room temp.
80 mg l1
ene, 1,4-distirred 24 h
oxane, CuCl2 ,
acetone methanol, acetonitrile
Characterisation and preparation. ZnCl2 addition of 10 w/w% resulted in higher surface area of 1200 m2 g1 and 25%
micropores, which are important for adsorption capacity
Oil palm shell

(Hussein et al.,
1996)
Sugarcane bagasse, pecan
shells, rice hulls
and strawa
(Ahmenda
et al., 2000a,b;
Pendyal et al.,
1999)
Rice straw,
soybean hull,
sugarcane bagasse, peanut,
pecan and walnut shells and
seven commercial GACs
(Johns et al.,
1998) (molasses
as binder)
Adsorbent
dosage (g l1 )
Removed
component
Initial conc.
Agitation type
and time
10 20 mesh
size
1240 mesh
10
Sugar decolourisation
Batch test without agitation
<5 mm, pelletised, activated

with CO2 or
steam, physical
and chemical
activation
100
Benzene,
toluene,
1,4-dioxane,
acetonitrile,
acetone,
methanol
80 mg l1
500 rpm, 24 h
10
Cu2 , Cd2 ,
Zn2 , Ni2 ,
ionic strength
0.03
0.25 mmol of
each metal
250 rpm, 2 h
pH-value
67
Temp.
23 C
As binders were used sugarcane molasses, sugar beet molasses, corn syrup, coal tar pitch. These binders are necessary to enhance the physical and
chemical properties of the resulting carbon, whilst the adsorption behaviour is still dictated by the residual matter used.
Solution
Adsorbent
dosage (g)
Bound
chemical
Percentage
removal
10 g
Cu2 l1
20 g
Cu2 l1
5.0 g
Cu2
7.5 g
Cu2
50
37.5
This equilibrium eect is described in several publications (Kumar and Dara, 1981; Bankar and Dara,
1982; Dronnet et al., 1997; Laufenberg and Filipini,
2002).
4.3.6. Agitation type and contact time
Dierent methods are applied ranging from no agitation (soft mixing at the beginning), over gently mixing
to continuously stirring for 24 h. Very often the particles
are not very stable and tend to leak. Randall et al. (1975)
described the problem while employing peanut skin for
the adsorption of cupric ions; due to the leaking it lost
most of the tannin, too. They suggest a pre-treatment

mixing 1 kg peanut skin with 10 l 0.2 N H2 SO4 and 500 g
35% formaldehyde, stirring it for 2 h at 50 C. Due to
the polymerisation the separated liquid is clear. The
treated peanut skins were more stable, showed no sign
of disintegration even when immersed in water for long
periods. Untreated peanut skins were soft and tended to
disintegrate, producing very ne particles which were
dicult to lter.
A contact time of ve minutes is sucient to adsorb
7585% of the chemical (Laufenberg and Filipini, 2002);
Bankar and Dara (1982) found in equilibrium experiments the maximum sorption for Ca2 and Mg2 within
5 min as well.
4.3.7. pH-value
A clear pH dependency was identied, changing with
the chemical adsorbed. Best adsorption results were
achieved for vanillin at an acidic pH, the sequence is
pH 4 > pH 7 > pH 10 (Laufenberg and Filipini, 2002).
190
Namasivayam and Kadirvelu (1996) determined an alkaline pH as a promoter for the adsorption of heavy
metals and alkalis on coir pith, the eect is further described for heavy metal adsorption on wool bres
(Balk
ose and Baltacioglu, 1992), on lignin from sugarcane bagasse (Peternele et al., 1999), and the carbonisation of oil palm shells (Hussein et al., 1996). For acid
or dye removal the pH should be acidic as described for
orange peel (Namasivayam et al., 1996), or banana
pith (Namasivayam and Kanchana, 1992). Dronnet
et al. (1997) realised that positively charged metals are
attracted to negative charges on the adsorbing pomace,
the eect becomes stronger in alkaline solutions.
Torre et al. (1995) investigated the adsorption behaviour of grape and olive pomace and lemon peel towards Fe3 , Fe2 and Ca2 . They found with increasing
pH an increase of bound mineral, in addition they determined that the quantity of polyvalent cations bound
by dietary bre materials increases with a higher level of
mineral addition, which is in compliance with other results. Binding isotherms of Zn2 increased as the initial
pH of the suspension varied from 3.5 to 7.2. As the pH is
lowered, the overall surface charge on sugar beet pulp
becomes less negative which reduces the attraction of
positively charged metal ions (Dronnet et al., 1997,
1998a,b).
4.3.8. Targeted metabolism

Giovannozzi-Sermanni et al. (1995) found with a
targeted metabolism of Lentinus edodes on wheat straw
and corn stalks changing material properties. The micro-organism, mainly degrading the carbohydrates,
changed the lignin ratio and availability of the raw
material, which resulted in a higher lignin extractability
for alkaline cooking. These observations match with
results obtained by Peternele et al. (1999). Lignin is a
potential adsorbents, hence a targeted metabolism of the
vegetable waste prior to the application as a bioadsorbents will enhance its adsorption capacity; see in this
connection Table 5 and the diering lignin content of
vegetable residues.
Similar eects are described by Carvalheiro et al.
(1994). Their aim was to enhance protein and lignin
content of tomato pomace to improve its digestibility as
a fodder. After SSF for 10 days with a co-culture of T.
reesei and Sporotrichum sp. the cellulose and hemicellulose content was decreased by 67% and 73% respectively, on the other hand the lignin and protein
content rose manifold. A targeted metabolism towards
an enhancement of certain components, i.e., lignin or
cellulose, and thus changed particle properties is feasible.
A targeted metabolism may even govern the ratio
lignin:cellulose (cellulose is used as a chromatography
adsorbent as well) towards the compound to be sepa-
rated. Cellulosic material predominately adsorbs alkaline components as determined by Nawar and Doma
(1989) for the basic dye sandocryl orange. The high afnity of the orange dye to cellulosic material like rice
hulls or orange peel is the result of ionic interactions
between the cationic centres on the dyestu and acidic
sites, mostly carboxylate groups, on the bres.
The adsorption rate is decisively inuenced by the
method of acidication, as aforementioned. Hydrochloric acid enhances the capacity due to a shift of pHvalue, but the metabolism of selected micro-organisms
additionally inuences the particle character (e.g., different conguration of carbohydrates and lignin fraction and/or degradation in total). This targeted
metabolism is superior. The fermented samples did not
need any pH adjustment, were stable in shape and initial
pH and tended to adsorb more substance than the HCladjusted samples (Laufenberg and Filipini, 2002).
4.3.9. Surface area

Ahmenda et al. (2000a,b) described a low surface area
for their soft materials sugarcane bagasse, rice hulls and
straw independently of chemical or physical activation.
They found that the total surface area does not correlate
with adsorption eciency and suggested pore size distribution as well as surface charges play an important
role too. It seems that the low surface area of untreated
residues does not have the major eect on the adsorption process (Tables 12 and 13), other parameters may
be stronger as expected, see Fig. 7. Removal rates in
Table 15 up to 90% are convincing.
4.3.10. Binding mechanisms

Kumar et al. (2000) observed that basic groups of
straw and straw xanthate interact with Cr3 via an ion
exchange route. For each Cr3 exchanged, one equivalent of Na is released into the solution, hence the solution became alkaline.
Laufenberg and Filipini (2002) noted a clear tendency
of the pH-adjusted carrot pomace and sugar beet pulp
to return to its initial pH after a certain time due to the
ion exchange mechanism. Kumar and Dara (1981) tested the binding capacity of polymerised onion skins
towards several heavy metals in aqueous solutions.
During their equilibrium experiments they determined
that in all studied cases the nal pH of the metaladsorbent-solution was always less than the initial pH.
This eect indicates that, as the metal ions are bound on
the substrate, hydrogen ions are released into the solution. The authors concluded that the onion skin substrate probably acts as an acid-form ion exchanger. The
theory was conrmed for other materials like sugarcane
bagasse (Kumar and Dara, 1982; Dronnet et al., 1997),
onion skin (Bankar and Dara, 1982), onion skin and
Table 15
Vegetable residues as bioadsorbents: inuencing process parameters
Particle size
(lm)
Adsorbent
dosage
(g l1 )
Removed component
Initial concentration
Agitation type/time
pH-value
Temp. (C)
Ionic strength
Apple/black currant
pomace (Borycka and
Zuchowski, 1998)
Banana pith (Namasivayam and Kanchana, 1992)a
Carrot pomace and sugar
beet pulpb (Laufenberg and
Filipini, 2002)
Coconut coir pith
(Kadirvelu et al., 2001)
Corncobs (Hawthorne
Costa et al., 1995)
Corncobs, wood chips,
wheat straw (Nigam et al.,
2000)
Corncobs mixed with onion
skin (Odozi and Emelike,
1985)c;d; e
Linseed cake and peat
(Liversidge et al., 1997)
6 180 and
7101500
10 and
20
Cd, Pb, Ca, low 3040%
531000
0.56
Textile dyes, up to 80%
20100 mg l1
140 rpm/20200 min.
2"11#
30 2
125180 and
7101500
10 and
20
Vanillin, humic acid
10 and 20 mg l1
4", 7, 10#
23 2
531000
2.5, 5, 6,
9
30
Hg2 , Pb2 , Cd2 , Cu2 ,

Ni2 73100%
Cu2
126, 709, 996 mg l
No agitation/5, 10,
20 min, and 1, 8, 24
h
Batch mode
2#10"
6 103 ; 0:5 104 mole l1
Continuous/15 min.
35
3, 0.3, and 0.2

mm3
100
200500 mg l1
Soaking for 48 h
20, 30 or 48
<200
10
Several red, blue and

black dyes; 7075% removal
Ni, Mg, Zn, Pb, Cd, Ca,
Hg, Mn-cations
0.1, 0.5 and 0.9

mol l1
142740 mg l1
Continuous/24 h
"6 and
higher,
lower #
Room temp.
1801000
502000 mg l1
120 rpm/90 min.
30"50#
strange!
10
Basic blue 4195% removal, acid blue 148, reactive red 184
Hg, Cd, Ni, Zn, Cr, Pb
45100 mg l1
211
Powdered
40
Ca2 , Mg2
Dyes, 7392%
410", less
#
3"12#
210
Gently agitated/10
min.
140 rpm/2090 min
30, 50, 100
75500
0.420 103 mg l1 Ca2 ,

0.21200 mg l1 Mg2
1060 mg l1
29 2
>500
525 mg l1
<1000
10
Pb2 6080%, Zn2 13

24%
Cu2
10 mg l1
6 or higher
Room temp.
160, 300, and

1200
10
Sandocryl orange 98%

and lanasyn black 78%
50 mg l1
Gently agitated/30
min
15"120 min
Room temp.
200500
1.82,
7.27,
14.55
5
Ca2 , Pb2 Cd2 , Zn2 ,

Ni2 , Ca2 , 72% removal,
10 min
Cd2 , Pb2
0.01 M solution
Constantly stirred/2
h
Black 36,
orange 2
11
3.57"
25 1
16 mmol dm3
Shaking/8 h
"5 or 6"
30, 40, "50
"0.5 and 1.0

mol dm3
Onion skin, sugarcane

bagasse, bark (Kumar and
Dara, 1981)f ; c
Onion skins (Bankar and
Dara, 1982)c; g
Orange peel (Namasivayam
et al., 1996)
Palm kernel husk (Omgbu
and Iweanya, 1990)c
Peanut skins (Randall
et al., 1975)c
Rice hulls, peat and activated carbon (Nawar and
Doma, 1989)c
Sugar beet pulpd;f (Dronnet et al., 1997, 1998a,b)
Sugarcane bagasse
(Peternele et al., 1999)d
Material/adsorbents
191
20
15
1000
17 on average
Residue or main component
Mechanism
Sugar beet pulp; responsible are the

galacturonosyl units of the pectic chains
(Dronnet et al., 1997, 1998a)
Soybean hulls, peanut shells, sugar cane
bagasse, rice straw (Johns et al., 1998)
Ion exchange
Corncobs (Hawthorne Costa et al.,

1995): carboxylate groups
Straw and straw xanthane (Kumar
et al., 2000)
(") increased adsorption, (#) decreased adsorption, () no data available.

a
With increasing agitation time there was a decrease in diusion layer thickness.
b
Targeted metabolism has led to dierent pH values and material properties.
c
Did additional column tests.
d
Selectivity scale, synergistic eects.
e
20% higher adsorption rate on average due to column test and combination of residues.
f
Selectivity for the ions are depending on the type of pomace too and absolute adsorption rate increased with higher initial concentration.
g
Preferred adsorption of Ca2 .
Constantly/up to 60
min
0.25 1.5
150"1000#
Sugarcane bagasse pith

(Ho and McKay, 1999)
Wheat straw and insoluble
straw xanthate (Kumar
et al., 2000)
Wool bres (Balk
ose and
Baltacioglu, 1992)
Ni, Cu, Zn, Cd, Hg, Pb

70%
50200 mg l1
25 or 50, no
eect
3.6
Continuous/15 min
37.3 mg l1 Cr 64 mg l1 others
0.5 mg l1
25 1
50300 mg l1
Basic red 22 and acid red

114
Cr3 , Cr6 Cr, Pb, Cu,
Ni, Fe, Mn, Zn
2080"
Agitation type/time
Initial concentration
Adsorbent
dosage
(g l1 )
Particle size
(lm)
Material/adsorbents
Table 15 (continued)
Table 16
Physicochemical mechanisms for the uptake of components from solutions
Removed component
pH-value
Temp. (C)
Ionic strength
192
Ion exchange, chelation,

and coordination, but
without modication also
surface precipitation
Ion exchange
Ion exchange
corncobs (Odozi and Emelike, 1985), peanut skins

(Randall et al., 1975), palm kernel husks (Omgbu and
Iweanya, 1990) or pure corncobs (Hawthorne Costa
et al., 1995). Since the latter residue is mainly lignin and
cellulose based several residual matters, e.g., olive cake
or white wine pomace, could be taken into account for
future adsorption of dyes, heavy metals and chemicals,
see Table 5.
Certain mechanisms for the uptake of components
from solutions are discussed according to the type of
substrate used (Dronnet et al., 1997). An overview of
binding mechanisms is given in Table 16. Some simple
chemical or physical modications may improve the
adsorbent behaviour of these materials several times.
Modication reactions include crosslinking and/or
functionalisation to enhance the adsorbent stability and/
or capacity (Peternele et al., 1999).
4.3.11. Packed bed design
Adsorption is much more eective in a packed bed
than in a stirred tank, which is an equivalent to countercurrent ow in extraction. A packed bed will permit
faster mass transfer and higher conversion. Assumed is
that a large volume of solution is to be fed through a
small bed of adsorbing solid. The bed is completely
uniformly packed and the ow moving evenly, without
dispersion and independent of the beds radius. Hence in
the packed bed the concentration in the solid is in
equilibrium with the high feed concentration. In stirred
tank loaded solid reaches equilibrium with depleted solution which is less than with the feed solution. Therefore yields are much less eective (Cussler, 1997).
The results of several investigations match with the
described relations. Namasivayam et al. (1996), Namasivayam and Kanchana (1992) and Peternele et al.
(1999) realised that an increase in the initial substance
concentration increased the amount of substance adsorbed. It was clearly shown that the removal of dye or
metal is dependent on its initial concentration in solu-
193
Table 17
Adsorption parameters and economic evaluation of three adsorbents (Nawar and Doma, 1989)
Compound used
Adsorbents material,
particle size 0.30.4 mm
Adsorbent dosage (g l1 )
Comparative cost
per kg adsorbent
Comparative cost
to remove kg dye
Comparative cost to
remove kg dye in (%)
Sandocryl orange
Peat
Rice hulls
Activated carbon
Peat
Rice hulls
Activated carbon
1.8
16.3
13.6
72
77.7
204
0.04
0.01
1
0.04
0.01
1
1.46
3.3
277
58
15.8
4163
0.53
1.52
1.4
0.38
Lanasyn black
tion due to the change in equilibrium limit. This is the

aforesaid disadvantage of the stirred tank. It could be
transferred into an advantage if the adsorption would
take place in a packed bed. Possible design considerations are given in Fig. 8. Similarities are described by
Balk
ose and Baltacioglu (1992), they suggest further
experiments with controlled ow rates and tightly
packed wool beds. Kumar and Dara (1982) achieved
higher adsorption results in a column for all tested
heavy metals, also did Bankar and Dara (1982) and
Randall et al. (1975).
4.3.12. Post-treatment
Nigam et al. (2000) removed several textile dyes from
euents using the residues wheat straw, wood chips and
corncob shreds. The adsorption rate was rather good,
up to 75% of the dyes could be removed. The authors
additionally investigated the suitability of the dyeadsorbed residues for SSF by the white-rot fungi
Phanerochaete chrysosporium and Coriolus versicolor,
both possessing dye degradation capabilities. It could be
determined that both dye adsorbed residues wheat straw
and corncob shreds were heavily colonised and hence
are suitable substrates for fungal colonisation. Visual
substrate decolourisation occurred; which has to be
precisely determined in future experiments. The fermented residue is useful as a soil conditioner. Other
groups have used Pleurotus pulmonarius for the degradation of antrazine (Masaphy et al., 1996).
Depending on the recycling method for the spent
adsorbents an equal ratio between adsorption and desorption becomes an important goal. The high adsorption rate is the only point of interest if the laden
adsorbents is afterwards metabolised by micro-organisms. A regeneration/desorption has to be taken into
account, if the substances should be recycled, several
methods are described (Hamer and P
uschner, 1997;
Urano and Tachikawa, 1992; Urano et al., 1992).
4.3.13. Future considerations
Depending on the origin the residues adsorb more or
less water. Oil press cakes, like olive or sunower cake,
exhibit little water binding capacity, beverage residues

like carrot or grape pomace swell considerably in water.
Hydration properties can be reduced by establishing
cross-links between the cell wall polysaccharides using
the pre-treatment chemicals formaldehyde (Kumar
and Dara, 1982; Randall et al., 1975; Dronnet et al.,
1998a,b), epichlorohydrin, divinylsulfone, glutaric dialdehyde, or citric acid. The saponication doubled
the cation-exchange capacity, and epichlorohydrin was
most eective improving the binding properties of the
investigated beet pulp per unit of hydrated volume, i.e.,
decreased its hydration properties and increased metal
binding capacities (Dronnet et al., 1998a,b).
Laufenberg and Filipini (2002) found that their bioadsorbents carrot pomace and sugar beet pulp exhibit
some properties which are dicult to handle, these are
in particular: no stable size, the particles are brittle, the
colour leaking distorts the results, and the phase separation is dicult. Corrective actions in future experiments should include
mechanical pre-treatment to enlarge surface area and/
or stabilize the suspension,
chemical pre-treatment to prevent colour leaking,
packed bed technology to enhance eectiveness towards the equilibrium limit, enlarge contact area
and to simplify phase separation, desorption, and recycling,
SSF to change particle composition and naturally inuence pH-value,
extrusion to add promoters, concentrate existing promoters, remove disturbing components, combine two
materials with diering properties, coat or line components, and inuence the suspension behaviour,
adding fat containing residues like olive cake to reduce the brittleness.
5. Conclusions and outlook

This clean production concept shows a good utilisation potential for solid vegetable waste. It could achieve
a reduction of investment and raw material costs and
194
can contribute to a waste minimised food production.

Especially the development of bioadsorbents is a promising area to add value to vegetable residues. They will
appear as a cheap and environmentally safe alternative
to commercial ion-exchange resins.
Nawar and Doma (1989) have made economical
considerations for three bioadsorbents at equilibrium
under similar experimental conditions in 1989. They
used peat, rice hulls and activated carbon for stirred
tank and xed bed experiments to remove dyes from
wastewaters. The costs of removal of 1 kg of each of the
studied dyes via dierent adsorbents showed that for
sandocryl orange the costs of peat are 0.53% and of rice
hulls 1.52% of the costs of activated carbon. For lanosyl
black removal the values are 1.4% and 0.38%, respectively, see Table 17.
The cheapness of rice hulls in particular and vegetable residues in general means that regeneration is a
further goal in clean production but under economic
considerations not absolutely necessary.
Acknowledgements
Special thanks to Conny Schnitter, MEng, who spent
four weeks in Lappeenranta/Finland doing the adsorption experiments and setting up the analysis.
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Transformation of Vegetable Waste Into Value Added Products

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Transformation of Vegetable Waste Into Value Added Products

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Bioresource Technology 87 (2003) 167198

Transformation of vegetable waste into value added products:

, Benno Kunz a, Marianne Nystroem

Corresponding author. Tel.: +49-228-734-274; fax: +49-228-734429.

Todays society, in which there is a great demand for

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198

problems and represent a loss of valuable biomass and

Fig. 1. The holistic concept of food production.

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198

Fig. 2. Circular structure of a sustainable economy (source: adapted

Long term goals

1.2.2. Challenge for the vegetable/beverage industry

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198

1.2.3. End of pipe solution?

Closed loop of valuable constituents

3. Technical implementation by three selected examples.

2. Need statement: the vegetable waste situation

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198

Quantity and waste type

Germany, 1997 (Henn, 1998)

Belgium, 1992 (Lucas et al., 1997)

105,000 t/a biowaste (vegetable, garden and fruit waste)

Thailand, 1993 (Prasertsan and Prasertsan, 1996) palm oil

386,930 t/a empty fruit bunches

Spain, 1997 (Clemente et al., 1997)

>250,000 t/a olive pomace

EEC, 1996 (Dronnet et al., 1998a)

14,000,000 t/a sugar beet pulp (dry matter!)

Portugal, 1994 (Carvalheiro et al., 1994)

14,000 t/a tomato pomace

Jordan, 1999 (Haddadin et al., 1999)

36,000 t/a olive pomace

Malaysia, 1996 (Hussein et al., 1996) palm oil production

2,520,000 t/a palm mesocarp bre

Australia, 1995 (Tran and Mitchell, 1995)

400,000 t/a pineapple peel

300,000 t/a grape pomace in California only (1994) (Nakata, 1994)

lignocellulosic materials have been studied. Low cost

The improved utilisation of vegetable waste, outlined

3. The upgrading concept

M: grinding, C: phosphoric acid

Superior to commercial carbons in metal

Op: wastewater treatment, metal and organics adsorption

Toles et al. (2000)

Fi: pie lling, oatmeal crackers

Carson et al. (1994)

O: avours, volatile aldehydes for chemical

Almosnino and Belin (1991)

O: Fine chemicals, polyphenols

Lu and Foo (1997)

B: degradation of linoleic acid by

C: CO2 avour extraction, fractionated precipitation

Apple pomace, spent malt

M, B: SSF with Thamnidium

Banana pith waste (banana

M: grinding, B: SSF lactic acid

Highest avour production with amaranth

Carrot pomace, citrus

B: SSF A. niger mass multiplication

Citrus by products and

Fi: food supplement c-linolenic acid,

Stredansky et al. (2000)

Fi: substitute for marzipan, oil for bitter

Tuncel et al. (1998)