Bioresource Technology 87 (2003) 167198

Review paper

Transformation of vegetable waste into value added products: (A) the upgrading concept; (B) practical implementations
Gnther Laufenberg u
a b

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. PII: S 0 9 6 0 - 8 5 2 4 ( 0 2 ) 0 0 1 6 7 - 0

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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.

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

169

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.

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!).

Fig. 2. Circular structure of a sustainable economy (source: adapted from Stahel Walter R. The Product-life Institute, Geneva).

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.

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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.

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,

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

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 2 Waste quantities in dierent countries (selection) Country/state Germany, 1997 (Henn, 1998) Quantity and waste type

171

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) 105,000 t/a biowaste (vegetable, garden and fruit waste) 280,000 t/a estimations due to legislation of separate household collection 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) >250,000 t/a olive pomace 14,000,000 t/a sugar beet pulp (dry matter!) 14,000 t/a tomato pomace 36,000 t/a olive pomace 2,520,000 t/a palm mesocarp bre 1,440,000 t/a oil palm shells 4,140,000 t/a empty fruit bunches 400,000 t/a pineapple peel 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)

Belgium, 1992 (Lucas et al., 1997) Thailand, 1993 (Prasertsan and Prasertsan, 1996) palm oil production

Spain, 1997 (Clemente et al., 1997) EEC, 1996 (Dronnet et al., 1998a) Portugal, 1994 (Carvalheiro et al., 1994) Jordan, 1999 (Haddadin et al., 1999) Malaysia, 1996 (Hussein et al., 1996) palm oil production

Australia, 1995 (Tran and Mitchell, 1995) USA

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

Table 3 Current utilisation concepts for vegetable pomace (selection) Residual matter/co-product Almond shells Apple pomace Pre-treatment M: grinding, C: phosphoric acid pre-treatment, P: heat activation B: SSF Candida, Sacch., Torula spp., P: drying P: drying, M: powdering 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 M, B: SSF with Thamnidium elegans B: enzymatic degradation M, P: drying, grinding C, M, P Results 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 Application/secondary use Op: wastewater treatment, metal and organics adsorption O: ethanol, Ff Reference Toles et al. (2000) Joshi and Sandhu (1996)

172

Apple pomace Apple pomace

Fi: pie lling, oatmeal crackers O: avours, volatile aldehydes for chemical industry O: Fine chemicals, polyphenols Fi: avour extract

Carson et al. (1994) Almosnino and Belin (1991)

Apple pomace Apple pomace, Pepper peels Apple pomace, cassava bagasse Apple pomace, spent malt grain Apricot seeds Banana pith waste (banana stem marrow) Blackcurrant and apple pomace

Carrot pomace

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

Fi: food avours

Lu and Foo (1997) Bundschuh et al. (1988), Bundschuh et al. (1986) Christen et al. (2000)

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

Fi: food supplement c-linolenic acid, O: pharmaceutical application Fi: substitute for marzipan, oil for bitter almond oil, protein enhancer O: dye removal in wastewater treatment Fi: dietary bre in food, nutritional value and healthy food, binding metals, O: binding capacities for toxic metals potential for adsorption? Dietary bre enhancement in bread, sourdough substitute in rye and white bread Fi: cake, dressings, pickles, Fi: bread

Stredansky et al. (2000)

Tuncel et al. (1998) Namasivayam and Kanchana (1992) Borycka and Zuchowski (1998)

Filipini and Hogg (1997)

Carrot pomace Carrot pomace Carrot pomace, citrus and pineapple peels and pomace Carrot residue, orange waste, mango peel and stone Cauliower leaves, cabbage leaves Citrus by products and wastes M, P B: SSF A. niger mass multiplication 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 Protein content rose from 14.5% to 22.6%

Fi: multifunctional ingredient in beverages 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)

B: 1. cellulolytic degradation by A. niger, 2. Torulopsis utilis, P: 3. drying M, P

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)

Citrus peel Citrus residues, apple pomace, sugar beet pulp Cocoa pod husk, bean shells and germ Corncob shreds, wheat straw, wood chips

B: enzymatic, cellulolytic and pectinolytic hydrolysis, microbial conversion M, P M: chopping, B: SSF with Phaenerochaete chrysosporium and C. versicolor

Pectin extraction, phytochemicals

Fi: stabiliser, thickening agent, gelling agent, soluble bre, O: several applications O: Pectin, liquid biofuel, substrate for bioconversions Fi: stabiliser, thickening agent, gelling agent, soluble bre, Ff: protein rich pod husk Op: bioadsorbents for wastewater treatment, O: soil conditioner after SSF

Widmer and Montanari (1995) Grohmann and Bothast (1994)

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

Nambudiri and Shivashankar (1985) Nigam et al. (2000)

Corncobs Corncobs and onion skin

M, P: drying, pyrolysis, C: ZnCl2 as activator M, P

O: general use in wastewater treatment Cu ion adsorption is lignin and cellulose dependent, simple modications necessary, packed bed investigations Investigated new dietary bre compositions for the application in food Op: alternative bioadsorbents for wastewater treatment O: SSF, fungal inoculate production Fi: health quality improvement by adding bre product Fi: as stabilisers, thickening agent, jellies, etc. Fi: dietary bre supplement, insoluble is major fraction Fi Both bre enhancement and antioxidants in food, carrier idea

Tsai et al. (1998) G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Odozi and Emelike (1985), Hawthorne Costa et al. (1995) Zheng and Shetty (1998) Borycka (1996) Attri and Maini (1996) Valiente et al. (1995) Martin-Carron et al. (1997) Saura-Calixto (1998)

Cranberry processing waste Fruit pomace Galgal peel (citrus pseudolimon) Grape pomace Grape pomace Grape pomace

B M: powdering, C: pectin extraction M: grinding, P: drying Combination of the antioxidential potential of polyphenols in grape pomace with the dietary bre matrix M: grinding, P: drying, B: SSF, UASB reactor C, M, P

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)

Grape pomace, Carrot pomace 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 Mango kernel Mango peel

Pectin extraction Determination of nutritional value, several analyses Interactions of dietary bres with Fe and Ca High fungistatic activity towards Phoma tracheiphila, causing citrus malsecco Flour substitute with moderate sensory acceptability, higher calories and protein Pectin extraction

O: substrate in bioreactor UASB, Fi: bread improver, sourdough substitute, dietary bre and b-Carotene enhancer Fi: stabiliser, thickening agent, gelling agent, soluble bre Fi: possible application as food ingredients

Lucas et al. (1997)

Higareda et al. (1995) Haque et al. (1997)

C, P C: avonoid extraction C, M

O: possible adsorbents, Fi: importance for human nutrition O: natural fungicide in citrus fruit cultivation Fi: for biscuits Fi: stabiliser, thickening agent, gelling agent, soluble bre

Torre et al. (1995) Chkhikvishvili and Gogiya (1995) Arogba (1999) Srirangarajan and Shrikhade (1976) 173

Table 3 (continued) Residual matter/co-product Mango peel and stone Pre-treatment Results 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%). Application/secondary use Fi and O: pectin, Kernel fat: use in soap manufacturing or as cocoa butter substitute, potential for the preparation of sweetmakers 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 Reference Nanjundaswamy (1997)

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Oat, corn rice, soybean hulls; pea pods, wheat and corn bran Oil palm shells Olive cake Olive cake, sugarcane bagasse Olive oil industry waste Olive pomace

M: peeling, purifying, milling, P: drying M, P: drying, pyrolysis, C: ZnCl2 , CO2 , as activators P: drying, C: extraction with hexane B: SSF In mixtures with several chemicals Main component is fibre > 70%. C: extraction, P: drying, chemical analysis P: drying, M: grinding, B: delignication, saccharication M, C 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 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 Wastewater treatment concept for the pectin production industry. Material balance developed Dye removal with cellulosic material, parameters: initial conc. of dye important, particle sizes of adsorbent, pH-value Pb is preferably adsorbed to Zn Quantities and potential usage

Inglett (1998)

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)

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

Olive pomace

Clemente et al. (1997)

Olive pomace Onion skin

Ff: fodder enhancement Op: alternative bioadsorbents for wastewater treatment

Haddadin et al. (1999) Kumar and Dara (1981), Bankar and Dara (1982)

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

Fi: onion oil avour Fi: General application for dietary bre enhancement O: pectin wastewater treatment

Brose (1993) Larrauri et al. (1999) El-Nawawi and Heikal (1996)

Op: dye removal in wastewater treatment

Namasivayam et al. (1996)

Palm kernel husk Palm oil mill waste

M, C

Peanut and walnut shells Peanut skin

M, C

Rich in tannin, possible use in wastewater treatment Stirred tank and packed bed investigations, two types untreated and treated peanut skin

Op: alternative bioadsorbents for wastewater 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 Op: alternative bioadsorbents for wastewater treatment

Omgbu and Iweanya (1990) Prasertsan and Prasertsan (1996)

Randall et al. (1974) Randall et al. (1975)

Pear and kiwi pomace Pineapple cannery waste

C, M P: heat treatment, M: centrifugation, B: ethanol fermentation B: SSF Aspergillus foetidus ACM 3996 M, P

Major analysis of several compounds 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 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 Stirred tank and packed bed investigations, seven heavy metals tested Parameters: pH-value, ionic strength, temp. 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

Fi: sugar source, bre enhancement insoluble/soluble, pectin Op: liquid fuel production

Martin-Cabrejas et al. (1995) Nigam (1999)

Pineapple peel

Fi: citric acid, O: pharmaceuticals

Tran and Mitchell (1995)

Potato peel

Fi: bread bre improvement

Toma et al. (1979)

Potato starch waste, carrot pomace

M, P, B

Fi: multifunctional ingredient in general, focus on bread and beverages

Laufenberg et al. (1996) G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198

Spent malt

B: Ceratocystes mbriata

Fi: general application, O: pharmaceutical industry

Fischbach et al. (2000)

Sugar beet pulp, cereal bran Sugar beet pulp

M and P: free ferulic acid from pectin, B: SSF with two microorganisms P, C, B

Fi: vanillin as a food avour, O: avour compound for chemical use Fi: dietary bre, esp. soluble. Two novel food ingredients were developed, FF: enzymes for use in feeds Fi: dietary supplement in cookies

Asther et al. (1997)

Broughton et al. (1995a,b)

Sugar beet pulp

C: washing with ethanol, P: drying, M: milling

Kksel and Ozboy (1999) o

Sugar beet pulp

C, M, P: saponication or pretreatment with formaldehyde or epichlorohydrin

Op: heavy metal removal in wastewater treatment

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

Sugarcane bagasse, bark and onion skin Sugarcane bagasse Sugarcane bagasse, pecan shells Sunower heads Tomato pomace

M, C C: lignin extraction P, P, C: grinding, pyrolysis, phosphoric acid activation M: grinding, B: fungal cultures, pure and mixed P: drying, C: extraction B: mesophilic fermentation

Op: alternative bioadsorbents for wastewater 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) Wang et al. (1997) Carvalheiro et al. (1994)

Fi: stabiliser, thickening agent, gelling agent, soluble bre Ff: feed stu or fodder enhancement

Tomato skins and seeds Urban organic waste

Ff, Fi: biocolorants Fi or O: chemical industry

Al-Wandawi et al. (1985) Sans et al. (1995)

175

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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

Giovannozzi-Sermanni et al. (1995)

Schutz et al. (1982) Feil (1995) Zeller (1999)

Reference

Fi: Natural vanilla avour O: bioplastics with special properties Fi: dietary bre enhancement, avour encapsulation and application in various food Ff: for ruminants

Kumar et al. (2000)

Fi: multifunctional food ingredient with specied physicochemical and nutritional properties Op: paper and pulp bre resource (lignin)

Op: heavy metal cations removal in wastewater treatment M, P: washing, drying, C: petroleum ether degreasing

Balkse and Baltacioglu (1992) o C: chemical, M: mechanical, P: physical, B: biotechnical; Ff: fodder/feed, Op: operational supply, Fi: food ingredient, O: other and (): no data available.

Gupta et al. (1993)

Dexter and Wood (1996)

Porous carbohydrate ingredients with carrier function to encapsulate avours Analysis of the nutritive potential, cauliower leaves best nutritive score

Pre-treatment

Residual matter/co-product

Vanilla shells Vegetable raw materials Vegetable residues (not specied) Vegetable waste, 24 types

Wheat straw, corn stalks

B: biodegradation of hemicellulosic fraction by L. edodes

CO2 avour extraction M, P, B

Table 3 (continued)

Wheat straw, insoluble straw xanthane Wool bre

Wheat bran

M: grinding, C: alkali treatment

M: debranning, polishing

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

Results

Patent

Op: wastewater treatment adsorbent

Application/secondary use

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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 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

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

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

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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; Kksel o and Ozboy, 1999), orange, mango and apple peel (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, 1995; Kksel and Ozboy, 1999), beverages (Henn and o Kunz, 1996; Henn, 1998; Laufenberg et al., 1996; Sreenath et al., 1995), jam (Grigelmo-Miguel and Martin-

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; Schrder, o 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

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 Apple pomace Barley pomace Carrot pomace Cocoa pod husks/bean shells (Nambudiri and Shivashankar, 1985) Corncobs Kiwi pomace Lemon peel Lemon pulp Olive cake Pea pots Peach pomace (Pagn a and Ibarz, 1999) Pear pomace Potato peel (Toma et al., 1979) Potato pulp Soybean shells Sugar beet pulp Fibre Total 62.5 65.3 29.6 36.3 Insoluble 48.3 62.1 18.9 Soluble 14.2 3.2 10.7 15.69 2225 6 18.2 13.7 Pectin Lignin Cellulose

25.8 50.9 45.8 69.4 90.1 54.5 43.9 73 15.8 64.6 75.3

18.7 28.2 26.0 65.7 84.7 35.4 36.3

43a 7.1 22.7 19.8 3.7/15.5 (Haddadin et al., 1999)a 5.4 19.1 7.6 6.2a 6.4 7.7 25.2/22.1 (K ksel and o Ozboy, 1999)

7.25 25.23 12.02 4.10 7.05 16 $15 (Tuncel et al., 1998) 30 (Purchase, 1995)/26 (Broughton et al., 1995b) 3.9 (Torre et al., 1995)/ 5.5 (Valiente et al., 1995)

17 (Hawthorne Costa et al., 1995) 3.2 5.5 2.9 37.2/35.4 (Haddadin et al., 1999) 5.2 13.8 1.85 (K ksel and o Ozboy, 1999)/4.56 (Broughton et al., 1995b) 41.2 (Torre et al., 1995)/53.6 (Valiente et al., 1995)

32 18.4 (Haddadin et al., 1999) 16 23/27.2 (Kksel and o Ozboy, 1999)

9.4 56.9 50.1

White wine pomace

58.6

56.3

2.3

Results expressed as percentage of original dry matter, (): no data available. a As hemicellulose.

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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-

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; Kksel and o Ozboy, 1999). 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.

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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. 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-

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

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 0.724% (Lu and Foo, 1997); 350.6 mg/kg , FA 8.0 mg/kg (Lucarini et al., 1999)
a b b

Coloured

b-carotenea 3 mg/kg Anthocyanins 9.1 g/kg (Mrissyov et al., 1999b) a a a Tannins 3.1%a 2%a ; 11.7%a (Zeller, 1999) 2535%a (Anon., 1999) Naringin 0.071.7%b 10.121.6%a; c Leucoanthocyanidin (Nambudiri and Shivashankar, 1985) Anthocyanins 16.6 g/kg (Mrissyov et al., 1999b) a a a Anthocyanins Anthocyanins Carotenoids Anthocyanins 8.0 g/kg (Mrissyov et al., 1999b) a a a 5.5%a 0.3%b Hesperidin 1.32.4%b /1.72%a (Manthey and Grohmann, 1996); Nobiletind 32% (Manthey and Grohmann, 1996) 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)
a a

Carotenoids Anthocyanins Carotenoids Betanine 414.3 mg/kgb (Mrissyov et al., 1999a) a a a

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).

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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),

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. (Kster, E. International FoodTec Congress, o 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.

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G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 8 Selected avours and selling prices in US$ per kg Flavour/aroma c-Deca lactone d-Deca lactone 1-Octen-3-ol 2-Heptanone Benzaldehyde Ethyl butyrate Isoamyl acetate Isoamyl butyrate Phenethyl alcohol Raspberry ketone Vanillin Vanillic acid Description Peach, fruity Coconut, creamy Mushroom Cheesy, spicy Almond Fruity, pineapple Banana, fruity, sweet Banana, fruity, pineapple Roses Raspberries Vanilla Vanilla Synthetic 75.00 130.00 184.00 39.00 31.00 31.00 31.00 31.00 31.00 58.00 31.00 410.00 Natural 1400.00 5500.00 198.00 55.00 31.00 345.00 2050.00 3000.00 685.00

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, 1999). a 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 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). 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

Source: Flavors & Fragrances 2000, Aldrich Milwaukee WI USA, (Sigma, 2000).

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: 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 Vanillin c-Deca lactone Isoamyl acetate b-Phenethyl alcohol 2-Heptanone Ethyl butyrate Feed conc.a 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 Selling price in US$/kg Natural extract 4000 (Asther et al., 1997) Biotechnical 6000 Year 1996 1998 1992 1999 1997 1994 1991 1996

Biotechnical 2500 Synthetic 39 Biotechnical 180

() No data available. a Related to biotechnical production.

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 9 Flavours and bione chemicals produced by SSF of vegetable residues (selection) Year 1991 2000 Residual matter Apple pomace (Almosnino and Belin, 1991) Apple pomace, spent malt grains (Stredansky et al., 2000) Carrot, citrus, pineapple pomace (Mukherjee and Sen, 1998) Cassava bagasse, apple pomace (Christen et al., 2000) 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) Linseed cake, castor oil cake, olive press cake, sunower cake (Laufenberg et al., 2001) Olive cake, sugarcane bagasse (Cordova et al., 1998) Olive pomace (Haddadin et al., 1999) Description/conversion principle 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 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 Product Volatile aldehydes, alcohols

183

1998 2000

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

1997

1994 1998

2001

1998 1999

1995 1997 1997 1994

Pineapple waste (Tran and Mitchell, 1995) Potato waste (Lucas et al., 1997) Sugar beet pulp, cereal bran (Asther et al., 1997) Tomato pomace (Carvalheiro et al., 1994)

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,

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G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 10 Isoamyl acetate formation depending on the substrate used (based on (Christen et al., 1997)) Residual matter 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 Isoamyl acetate formation in lmol l1 Not detectable Not detectable 0.45 0.8 2.1 9.5 48

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

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).

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(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. 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

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 Apple pomace, spent malt, spent hops, carrot pomace Flavour Ethyl butyrate (pineapple), ethyl pentanoate (apple), isoamyl acetate (banana) Vanillin Micro-organism C. mbriata

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)

Pycnoporus cinnabarius, A. niger

c-decalactone (peach) 1-Octen-3-ol (mushroom) c-decalactone, 6-pentyl-a-pyrone (nutty) c-decalactone

Yarrovia lipolytica

P. pulmonarius M. suaveolens, T. harzianum T. harzianum

Castor oil cake (Laufenberg et al., 2001) Sunower seed cake (Laufenberg et al., 2001) Olive press cake (Laufenberg et al., 2001) Soybean coarse meal

c-decalactone, d-decalactone (coconut) Pyrazine (roast avour)

P. ovale, Ceratocystis moniliformis 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

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(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 (Balkse and o 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 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) Surface area in m2 g1 1200 1200 300 3

Fig. 7. Natural properties of vegetable waste (average) and expected product prole for carbons in wastewater treatment.

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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.

(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.

4.3.1. 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

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,

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Table 13 Surface area reduction in dependency of particle size, determined for carrot pomace Particle size (lm) 032 3263 6390 90125 125180 180250 250355 355500 500710 7101000 10001400 14002000 Mean d (lm) 16 47.5 76.5 107.5 152.5 215 302.5 427.5 605 855 1200 1700 Density (g cm3 ) 1.43 1.41 1.39 1.4 1.39 1.39 1.39 1.37 1.37 1.35 1.35 1.34 Volume (m3 ) 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 Surface (m2 ) 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 Surface (m2 kg1 ) 131.118 44.792 28.212 19.933 14.152 10.038 7.134 5.122 3.619 2.599 1.851 1.316 Surface (m2 g1 ) 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:

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 14 Physically and chemically activated carbons made from vegetable residues as a feedstock (selection) Material/ adsorbents Almond shells (Toles et al., 2000) Particle size 10 20 mesh size Adsorbent dosage (g l1 ) 1 Removed component Initial conc. Agitation type and time pH-value Temp.

189

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)

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 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

67

23 C

10

Cu2 , Cd2 , Zn2 , Ni2 , ionic strength 0.03

0.25 mmol of each metal

250 rpm, 2 h

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 10 g Cu2 l1 20 g Cu2 l1

Adsorbent dosage (g) 1 1

Bound chemical 5.0 g Cu2 7.5 g Cu2

Percentage removal 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).

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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 (Balkse and Baltacioglu, 1992), on lignin from sugaro cane 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).

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).

4.3.8. 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-

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 Material/adsorbents Particle size (lm) Adsorbent dosage (g l1 ) 10 and 20 0.56 10 and 20 2.5, 5, 6, 9 30 100 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) 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

6 180 and 7101500 531000 125180 and 7101500 531000 3, 0.3, and 0.2 mm3 <200

Cd, Pb, Ca, low 3040%

Textile dyes, up to 80% Vanillin, humic acid

20100 mg l1 10 and 20 mg l1

140 rpm/20200 min. No agitation/5, 10, 20 min, and 1, 8, 24 h Batch mode Continuous/15 min. Soaking for 48 h

2"11# 4", 7, 10#

30 2 23 2

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

Hg2 , Pb2 , Cd2 , Cu2 , Ni2 73100% Cu2 Several red, blue and black dyes; 7075% removal Ni, Mg, Zn, Pb, Cd, Ca, Hg, Mn-cations Basic blue 4195% removal, acid blue 148, reactive red 184 Hg, Cd, Ni, Zn, Cr, Pb

126, 709, 996 mg l 6 103 ; 0:5 104 mole l1 200500 mg l1

2#10" 6

35 20, 30 or 48

0.1, 0.5 and 0.9 mol l1

10

142740 mg l1

Continuous/24 h

"6 and higher, lower #

Room temp.

1801000

502000 mg l1

120 rpm/90 min.

30"50# strange! 211

10

45100 mg l1

Powdered 75500 >500 <1000 160, 300, and 1200 200500

40 210 2 10 10

Ca2 , Mg2 Dyes, 7392% Pb2 6080%, Zn2 13 24% Cu2 Sandocryl orange 98% and lanasyn black 78% Ca2 , Pb2 Cd2 , Zn2 , Ni2 , Ca2 , 72% removal, 10 min Cd2 , Pb2

0.420 103 mg l1 Ca2 , 0.21200 mg l1 Mg2 1060 mg l1 525 mg l1 10 mg l1 50 mg l1

Gently agitated/10 min. 140 rpm/2090 min Gently agitated/30 min 15"120 min

410", less # 3"12# 6 or higher Black 36, orange 2 11 3.57"

30, 50, 100 29 2 Room temp. Room temp.

1.82, 7.27, 14.55 5

0.01 M solution

Constantly stirred/2 h Shaking/8 h

25 1

16 mmol dm3

"5 or 6"

30, 40, "50

"0.5 and 1.0 mol dm3 191

192

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 16 Physicochemical mechanisms for the uptake of components from solutions Residue or main component 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) Mechanism Ion exchange

Ionic strength

pH-value

Corncobs (Hawthorne Costa et al., 1995): carboxylate groups Straw and straw xanthane (Kumar et al., 2000)

Ion exchange, chelation, and coordination, but without modication also surface precipitation Ion exchange Ion exchange

Temp. (C)

2080"

3.6

25 1

(") 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

Agitation type/time

Continuous/15 min

25 or 50, no eect

Basic red 22 and acid red 114 Cr3 , Cr6 Cr, Pb, Cu, Ni, Fe, Mn, Zn

Ni, Cu, Zn, Cd, Hg, Pb 70%

Removed component

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-

50300 mg l1

Initial concentration

37.3 mg l1 Cr 64 mg l1 others $0.5 mg l1 20 1000

0.25 1.5

Adsorbent dosage (g l1 )

Table 15 (continued)

Sugarcane bagasse pith (Ho and McKay, 1999) Wheat straw and insoluble straw xanthate (Kumar et al., 2000) Wool bres (Balkse and o Baltacioglu, 1992)

Material/adsorbents

150"1000#

17 on average

Particle size (lm)

15

50200 mg l1

G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 Table 17 Adsorption parameters and economic evaluation of three adsorbents (Nawar and Doma, 1989) Compound used Sandocryl orange Adsorbents material, particle size 0.30.4 mm Peat Rice hulls Activated carbon Peat Rice hulls Activated carbon Adsorbent dosage (g l1 ) 1.8 16.3 13.6 72 77.7 204 Comparative cost per kg adsorbent 0.04 0.01 1 0.04 0.01 1 Comparative cost to remove kg dye 1.46 3.3 277 58 15.8 4163

193

Comparative cost to remove kg dye in (%) 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 Balkse and Baltacioglu (1992), they suggest further o 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 Pschner, 1997; u 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

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G. Laufenberg et al. / Bioresource Technology 87 (2003) 167198 clays. Industrial Engineering and Chemical Research 31 (9), 2181 2189. Balkse, D., Baltacioglu, H., 1992. Adsorption of heavy metal cations o from aqueous solutions by wool bers. Journal of Chemical Technology and Biotechnology 54, 393397. Bankar, D.B., Dara, S.S., 1982. Binding of calcium and magnesium by modied onion skins. Journal of Applied Polymer Science 27, 17271733. Bonnin, E. et al., 1999. Enhanced bioconversion of vanillic acid into vanillin by the use of natural callobiose. Journal of the Science of Food and Agriculture 79, 484486. Borycka, B., 1996. Fruit pomace in new dietary ber compositions. Przemysl-Fermentacyjny-i-Owocowo-Warzywny (Poland) 40 (12), 3739. Borycka, B., Zuchowski, J., 1998. Metal sorption capacity of bre preparations from fruit pomace. Polish-Journal-of-Food-and-Nutrition-Sciences 7 (48), 6776. Bramorski, A., Soccol, C.R., Christen, P., Revah, S., 1998. Fruity aroma production by Ceratocystis mbriata in solid cultures from agro-industrial wastes. Revista de Microbiologia 28 (3), 208212. Brose, D.J., 1993. Novel process technology for utilisation of fruit and vegetable waste. SBIR Phase I project USDA ICSRS, Washington, DC. Broughton, N.W., Dalton, C.C., Jones, G.C., Williams, E.L., 1995a. Adding value to sugar beet pulp. Hoehere Erloese aus Zuckerruebenschnitzeln. Zuckerindustrie 120 (5), 411416. Broughton, N.W., Dalton, C.C., Jones, G.C., Williams, E.L., 1995b. Adding value to sugar beet pulp. International Sugar Journal 97 (1154), 5760, 9395. Bundschuh, E., Baumann, G., Gierschner, K., 1988. Untersuchungen zur CO2 -Hochdruckextraktion von Aromastoen aus Reststoen der Apfelverarbeitung. Deutsche Lebensmittelrundschau 84, 205 210. Bundschuh, E. et al., 1986. Gewinnung von nat rlichen Aromen aus u Reststoen der Lebensmittelproduktion mit Hilfe der CO2 -Hochdruckextraktion. Lebensmittelwissenschaft und Technologie 19, 493496. Carson, K.J., Collins, J.L., Peneld, M.P., 1994. Unrened, dried apple pomace as a potential food ingredient. Journal of Food Science 59 (6), 12131215. Carvalheiro, F., Roseiro, J.C., Collaco, M.T.A., 1994. Biological conversion of tomato pomace by pure and mixed fungal cultures. Process biochemistry 29 (7), 601605. Chkhikvishvili, I.D., Gogiya, N.N., 1995. Flavonoids of mandarin fruit wastes and their fungistatic eect on the fungus Phoma tracheiphila. Applied Biochemistry and Microbiology 31 (3), 292 296. Christen, P., Bramorski, A., Revah, S., Soccol, C.R., 2000. Characterization of volatile compounds produced by Rhizopus strains grown on agro-industrial solid wastes. Bioresource Technology 71, 211215. Christen, P., Meza, J.C., Revah, S., 1997. Fruity aroma production in solid state fermentation by Ceratocystis mbriata: inuence of the substrate type and the presence of precursors. Mycological Research 101 (8), 911919. Christen, P., Villegas, E., Revah, S., 1994. Growth and Aroma production by Ceratocystis mbriata in various fermentation media. Biotechnology letters 16 (11), 11831188. Chu, D.C., Juneja, L.R., 1997. General chemical composition of green tea and its infusion. In: Yamamoto, T. et al. (Eds.), Chemistry and applications of Green tea. CRC Press, New York (Chapter 2). Clarke, S., 1995. Eat bagasse. Sugar Journal 58, 12. Clemente, A., Sanchez-Vioque, R., Vioque, J., Bautista, J., Millan, F., 1997. Chemical composition of extracted dried olive pomaces containing two and three phases. Food-Biotechnology 11 (3), 273 291.

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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