A modular strategy for processing of fruit and vegetable wastes into value-added products

13 A modular strategy for processing of fruit and vegetable wastes into value-added products G. Laufenberg, Bayer BioScience GmbH, and Technical University Berlin, Germany, and N. Schulze, University of Bonn, Germany

Abstract: The large amounts of by-products and wastes from the processing of fruit and vegetables, characterised by reusable substances of high value, are investigated as potential new raw materials. The principal aim of the upgrading concept is described in terms of the reintegration of residual matter into the chain of food production and the strategy, based on the synchronisation of waste and product streams for realising an industrial implementation of plant residue recycling, is outlined. Selected examples are presented using the perspectives of the triangle ‘pre-, prime and adaptation processing’ to underline the need for sustainability Key words: solid-state fermentation, bioadsorbents, sustainability, waste management, reintegration, multifunctional food ingredients.

13.1 Introduction The food industry is one of the largest and, therefore, important economic sectors in Europe. One great challenge for this sector is its production of large amounts of by-products and wastes. The total amount of food residues generated in the EU has been estimated at approximately 222 million tonnes annually.1 As most residues are characterised by a significant content of organic matter2 and of many other reusable substances of high value,3,4 they can have great potential as new raw materials. Thus, the principal aim of the upgrading concept is the reintegration of residual matter into the chain of food production.5 The concept provides a strategy for realising an industrial implementation of plant residue recycling. This strategy, as well as its background, i.e. the synchronisation of waste and product streams, is described in detail in sections 13.2 and 13.3. To underline the advantages and the need for the concept of sustainability, sections 13.4–13.7 present

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selected examples using the perspectives of the triangle ‘pre-, prime, and adaptation processing’. First, the production of decalactones via solid-state fermentation using oil press cakes is studied highlighting necessary pre- and prime processing steps (13.5). Prime and adaptation processing steps are essential treatments, if improved particle properties are requested for bioadsorbents in waste water treatment in 13.6. Success in the production of multifunctional food ingredients is mainly achieved by profound adaptation processing governing the final food quality (13.7). Together with descriptions of the aforementioned perspectives, reviews from the relevant literature are reported. In addition to reviews already published,4,6 the material is updated, enhanced, and supported with experimental data. Section 13.8 looks at future trends and section 13.9 presents sources of further advice, such as projects and networks.

13.2 Strategy for the development of multifunctional food ingredients based on vegetable residues: the upgrading concept An important factor in the upgrading process is the development of a procedure that uses standard technical equipment. The goal of upgrading is a product with the 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 of the residues, particularly if stored in the production unit before 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 fermentation is acidification with, for example, citric, acetic or ascorbic acids. For sensorial reasons and because of its influence on colour stability, an application of ascorbic acid would be most suitable for food applications. Hence, almost any recycling process will start with pre-treatment (ensiling), drying, size reduction and fractionation. The overall recycling strategy, described in Fig. 13.1, is designed in a modular manner, and is thus subdivided into substance characterisation, definition of objectives, product and process design and application, and optimisation. The result is a final product that is optimised with regard to the desired product properties, the example shown being for a multifunctional food ingredient. The first phase comprises substance characterisation; the optimal recycling and application areas and possibilities are developed, based on these results. Particle classification, chemical analysis and physicochemical properties are the important steps in this phase.

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Residue

Particle classification Analysis

Definition of objectives

Physicochemical properties

Market perspectives

Alternative utilisation

Prototype development

Termination

Evaluation

Extension of partial qualities and sub-processes

Termination

Evaluation

Design of final product and entire process

Final product

Production of multifunctional food ingredient

Technological quality Physiological quality

Application

Sensorial quality

Fig. 13.1

Strategy for the development of multifunctional food ingredients based on vegetable residues: the upgrading concept (modified according to Henn7).

Following this, the definition of objectives will describe the desired properties of the future food ingredient as well as the food for which it is to be used. At this point, a decision has to be made about its theoretical use. Based on these ‘key properties’, its advantages will be considered for the improvement of a product or its processing quality; either as a technological improvement, or as a health or taste improvement of a product. Next, product and process design covers product and dispersion properties as well as their changes depending on the process parameters. Obvious

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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; therefore it is useful to concentrate on the valuable ingredients as well as on the desired technological, sensorial and physiological properties. Continuous control and improvement of the upgrading process and product can be gained by prototype development and definitions of partial qualities as well as the incorporation of feedback. Then, during the application phase, the food product and the newly designed food ingredient will be combined. At this point of interaction, its theoretical use and practical application in a real food system come face to face. The quality-related properties of the new product have to be assessed and compared with similar products already on the market. From this, the chances of a successful launch may be forecast. Sensorial quality is the most important criterion for a multifunctional food ingredient that is to be used in a new product. After the sensorial, technological and nutritional qualities of the new product have been compared to a so-called ‘gold standard’, the optimisation is nearly complete. Final investigations into the product’s properties will discover anything which could be to the consumers’ benefit or even its unique selling position. The latter is often science based and hence measurable. Instead of producing a multifunctional food ingredient, the goal could alternatively be the bioconversion of the residue into a food flavour or the development of an operational supply material like a bioadsorbent. Hence, differing objectives will affect the product and process conception and the application phase.

13.3 Synchronisation of all product streams for improved utilization of organic residues As shown in Table 13.1 and Table 13.2, the quantities of organic residues obtained – in most food-processing plants these are a major bulk product – are far larger than the quantities eventually being further utilised in secondary processes. Certainly, the numbers in Table 13.2 seem to be fairly out-of-date, but checking the latest literature it could be determined that there has been hardly any progress in collecting recent data.8 The synchronisation of all product streams, converting the residual stream into a coproduct stream, seems to be a prerequisite for the improved utilisation of these organic residues at a higher economic level. A wide selection of both suitable residual materials and potential final products is essential for the development of a new management concept, wherein the determination of potentially suitable residues and the final product variability are important tasks. The outlined concept will combine aspects of technological product development with residue material/product management.

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Table 13.1 tonnes9

Food and agriculture commodities world production in million

Product Apples Banana Cassava Coconut Citrus fruit Coffee Corn Grape Olives Onion Pineapple Potato Soybean Sugar beet Sugar cane Tea Tomato Wheat Total cereals Brans Total fruit Total oil crops Total vegetables 1 2

Production yield1

Waste2

Food manufacture2

Food2

61.9 71.3 202.6 54.7 108.5 7.8 721.4 66.6 16 55.1 15.3 327.6 204.26 249.2 1324 3.3 (4.0) 120.4 627.1 2264 141.1 503.3 132.7 865.8

4.9 8.4 26.8 2.5 8.6 0.1 26.1 2.2 0.2 4.7 1.6 22.4 4.2 0.5 17.5 0.075 9.7 20 78.2 0.2 42.4 10.4 70.2

4.9 1.1 1 24 0.3 0.01 65 37.7 12.5 0.0006 0.14 12.6 163.1 242 1227.2 – – 4.5 – 7.5 1.4 304.7 0.5

48.7 55.4 100.5 21.5 92.2 6.9 110 21.5 2.6 45.8 14.6 202 9.8 – – 3.8 97.4 415.6 – 1.15 378.4 45.7 708.2

2004 figures. 2002 figures.

13.3.1 The engineering view The product engineering view, using the uniformity of all product streams, is illustrated in Fig. 13.2. As part of a holistic concept, all production streams are turned into potential product streams. This synchronisation of food processing streams is called the ‘synchronisation hexagon’. The residual matter, the former by-product or waste stream, now re-enters the processing as a raw material. Converting the residues in a three-step process, employing pre-, prime and adaptation processing, that results in valueadded products with additional profit for the economy and ecological gains. 13.3.2 The new sustainability concept The synchronisation hexagon is the operational core of the new sustainability concept, which starts with the different available residues of food processing, especially from the fruit and vegetable industry. An important factor in the upgraded processing is the development of a procedure that uses standard technical equipment. The reason for this is that success in a food business, unlike for example pharmaceuticals, is not dependent on

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Table 13.2 Waste quantities in various countries Country/state

Quantity and waste type

Germany (1997)7

380 000 t a−1 organic waste only from potato, vegetable and fruit processing 1 954 000 t a−1 spent malt and hops (breweries) 1 800 000 t a−1 grape pomace (viniculture) 3 000 000 t a−1 crude fibre 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 juice10 105 000 t a−1 biowaste (vegetable, garden and fruit waste) 280 000 t a−1 estimations owing to legislation of separate household collection 386 930 t a−1 empty fruit bunches 165 830 t a−1 palm press fibre 110 550 t a−1 palm kernel shells 1 000 000 t a−1 cassava pulp (1994)13 >250 000 t a−1 olive pomace 14 000 000 t a−1 sugar beet pulp, dry matter (1996)15 450 000 t a−1 onion waste (2001)16

Belgium (1992)11

Thailand (1993)12 palm oil production Spain (1997)14 EEC Portugal (1994)17 Jordan (1999)18 Malaysia (1996)19 palm oil production Australia (1995)20 USA

World (1998)16

14 000 t a−1 tomato pomace 36 000 t a−1 olive pomace 2 520 000 t a−1 palm mesocarp fibre 1 440 000 t a−1 oil palm shells 4 140 000 t a−1 empty fruit bunches 400 000 t a−1 pineapple peel 300 000 t a−1 grape pomace in California only (1994)21 9 525 t a−1 cranberry pomace (1998)22 200 000 t a−1 almond shells (1997)23 3 300 000 t a−1 orange peel in Florida (1994)24 5 to 7 million t a−1 grape pomace

new knowledge, but rather on better, more efficient use of current knowledge and skills, enhanced by vigorous marketing. The sustainability concept, as an innovative approach to the utilisation of all vegetable waste, is not focused on the implementation of new technology but on the variation of processing based on established techniques. Thus, besides the use of environmentally benign manufacturing, economic considerations are taken into account. Waste minimisation strategy The strategy of the sustainability concept is shown in Fig. 13.3, starting with the various available residues from the fruit and vegetable industry (e.g. pomace, seeds). The technological part consists of three processing steps:

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Preprocessing

Raw material

Intermediate product Residual matter

Food Adaptation processing

Prime processing

Ingredient

Fig. 13.2 The holistic approach to food processing: the synchronisation hexagon.

• pre-treatment or pre-processing; • conversion or prime processing; • adaptation processing. In most cases, the microbiological quality of residue materials requires technological treatment for their hygienisation (pre-processing). The result of this stage is their conversion from residue materials to raw materials. Afterwards, a varying range of techniques will be applied in order to optimally exploit the valuable components of the residue materials. This stage of the upgrading concept comprises the prime processes, which can be biological, chemical, and/or physical processes. The results of this technological treatment are intermediate products. These intermediate products serve as raw materials for further processing in order to vary their properties. This stage comprises all the procedures of adaptation processing for their intended application in different fields of food processing. Depending on the application requirements, further technological procedures may be required in order to achieve new products with added values. At this stage, it is necessary to take into consideration all the quality aspects of the final food product that could be altered by the application of these new product ingredients.

A modular strategy for processing of fruit and vegetable wastes Food processing

293

Upgraded processing

Example carrot pomace

Food processing

Residual matter

Carrot pomace

Vegetable waste

Pre-processing

Hygienisation, drying

Raw material

Carrot fibre

Main product

Prime processing

Chemical treatment

Biological treatment

Intermediate product

Multifunctional fibre

Adaptation processing

Grinding Particle modification Encapsulation

Product 1

Application field 1

Physical treatment

Prime processing - Lactic acid fermentation - Enzymatic degradation - Acid /alkaline treatment - Milling - Temperature treatment

Product 2

Product n

Application field Application field .... 2 n

Fig. 13.3

1. Soft drinks, e.g. ABE drinks 2. Fibre rich dairy products, e.g. smoothies, yogurts 3. Fibre rich bread, e.g. sourdough bread 4. .......

Flow chart of the sustainability concept.

From food engineering to product development: main stages Every residue management system needs monitoring and targeting with respect to waste stream identification, quantification, and site utilities. Detailed information should be available about: • the properties of residue materials before and after processing, • the properties of the target food product that are influenced by the upgraded residue material, and • the desired nutritional and sensorial parameters of the final food product. The upgrading strategy is subdivided into modules and each is assigned specific aspects to be tackled as shown in Fig. 13.4. This process diagram

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Vegetable matter

Potential properties of raw material

Potential food properties influenced by raw material

Needed treatments for modification of raw material

-

Hydrocolloid properties Water/ oil binding capacity WBC/ OBC Swelling capacity SC Surface area / adsorption rate .....

-

Dairy products

-

Beverages Baking goods .....

-

Physically

-

Product development (final product)

-

(vitamin and dietary fibre content, texture, structure, freshness) (mouthfeel, sweetness, colour intensity, ...) (WBC, density, network structure, ...)

(particle size, ultrasound splitting, polymer ratio, high-pressure homogenisation) Chemically (surface properties, functionality, WBC, SC, hydrocolloid properties) Biologically (enzymatic degradation/modification, catalytic metabolism, acidification/ alkalisation)

Investigations into interactions with other ingredients Optimisation of rheological, sensorial, nutritional/ physiological properties

Food

Fig. 13.4

Main upgrading stages and assigned specific aspects.

serves as a basis for the investigations that follow. The results of these investigations will converge into the upgrading procedure (algorithm). Requirements for selected residue–product relationships In this sub-section, selected examples of residue–product relationships are presented. In Fig. 13.5, the relationship between residual matter and a possible bioadsorbent is shown. Considering this relationship is an essential step towards adaptation processing, since there are certain standard features for adsorbents in waste water treatment. All vegetable residues, as carbohydrate polymers, possess the ion-exchange capacities that are essential for the adsorption behaviour. The moderate surface area and chemical stability can be influenced by several pre- and prime processing operations. Since adsorption capacity is not exclusively dependent on the surface area, and bearing in mind that other ingredients may possibly improve the adsorption behaviour, it seems realistic to adapt residues to an adsorbent’s product profile.

A modular strategy for processing of fruit and vegetable wastes Adsorption rate

High

Moderate

Surface area

High

Moderate

Chemical stability

Good

Possible

Regeneration

Easy

Decent

Residual matter

Good

Macropores : micropores

50:50

Chemical inertness

High

Low Acceptable

Pore size distribution

Very cheap Bulk ware

Fig. 13.5

Adsorbent

Decent

Prize

Low

Handling

Easy

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

Nutritionally acceptable Moderate taste and odour Balanced composition (insoluble : soluble) Bioactive compounds Residual matter

Long

Life cycle

Low, easy disposal

295

Good shelf life Food processing compatible Highly concentrated Easy to handle Defined colour and texture Cheap (bulk ware)

Vitamin and dietary Fibre content Texture/ structure, Mouth feel, Freshness Density, viscosity Porosity

Food ingredient

Network structure Water binding capacity Emulsifying properties Low price

Fig. 13.6 Natural properties of vegetable waste (average) and food properties and quality being influenced by multifunctional food ingredients.

The importance of the relationship between residual matter and a possible multifunctional food ingredient in the development of adaptation processing is shown in Fig. 13.6. Vegetable residues that have been separated out during food processing can, of course, be reintegrated into the chain. Vegetable residues are nutritionally acceptable, since the majority of their constituents are dietary fibre fractions in a particular ratio of soluble and insoluble fibres. If it is technologically necessary, this ratio can be modified, together with the content of bioactive components. Several residue types can be combined to maintain particular standards or if additional

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Residual matter

Excellent

Balanced ratio of components

Possible

Free of microbicides

Moderate Good High

Fig. 13.7

Pureness/ specificity

Easy handling

Biosubstrate

Shelf life (stability) Biodegradable

Acceptable

Universally applicable

Very cheap

Low price

Bulk ware

Available

Natural properties of vegetable waste (average) and expected product profile for bioconvertable substrates in biotechnology.

technological effects need to be achieved, e.g. enhanced viscosity, or nutritional improvements for food enrichment. Residues that are used as a substrate for bioconversion via fermentation have to fulfil certain requirements, as shown in Fig. 13.7. The relationship between the residual matter and a possible biosubstrate is of major importance for the prime processing module where the actual production of valuable substances, such as flavours or enzymes, takes place. Vegetable residues as biological material are frequently used as a substrate for fermentation, but checks must be made to ensure the microorganisms’ optimum growth conditions are matched. Depending on the project task, different types of screening will be performed. If a particular product has to be synthesised, the residues need to be screened for a substrate supply and the content of microbiocidal ingredients. If a particular residue has to be used as a substrate, the micro-organisms have to be screened for their ability to metabolise the specific substrate and their ability to produce ‘biochemicals’. 13.3.3 Making decisions via matrix configuration (algorithm) The stages of the upgrading process from the residue material to the application concept can be summarised in the algorithm shown in Fig. 13.8.

13.4 Selected examples of the sustainability concept in practice In the experimentation stage, the sustainability concept will be verified by three different examples. Together, the examples exhibit all the processing

A modular strategy for processing of fruit and vegetable wastes Residue

Characteristics of residue material

Pre-processing necessary?

No

Yes Prime or pre-processing biological chemical physical Suitable raw Determination of specific application requirements

Properties to change?

No

Yes No Processing is required? Yes -

Processing biological chemical physical

Intermediate product Intermediate

Modifications are needed? Yes Deliberated processing

Application Food ingredients

Fig. 13.8

Product development

Creating a new product via matrix configuration.

No

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steps shown in the synchronisation hexagon, i.e. pre-, prime and adaptation processing. Each example focuses on one particular processing step, describing and verifying the problem in depth. First, the bioconversion of oil press cake into flavours demonstrates the pre- and prime processing stages. Second, the use of several residues as bioadsorbents for wastewater pretreatment demonstrates prime and adaptation processing, with particular focus on prime processing, where the conversion and modification of the particles to achieve maximum adsorption capacity takes place. Third, the use of multifunctional ingredients in food products demonstrates the prime and adaptation processing stages, with particular focus on the adaptation processing that governs the final food quality. The fibres’ rheological behaviour is influenced by several operational units: fibre splitting and stretching, grinding and milling. These prime processing steps will certainly modify the adsorption properties and particle structure as mentioned previously. Fibre-enriched rye–sourdough bread was chosen as an example for adaptation processing, with special focus on the bread volume. The experimental stage is purposefully structured in a modular way to prove its validity and general applicability.

13.5 Oil press cake for decalactone aroma generation 13.5.1 Pre-processing: evaluation by agar-plate test Olive press cake requires the most intensive pre-treatment. Olive cake contains up to 0.3% phenolic compounds, which are known to inhibit the growth of many bacteria, yeasts and fungi. The pre-processing stage was carried out for dried and crushed olive cake, using the methods described in Table 13.3 to degrade, destroy or extract the polyphenolic fraction, and employing several treatments. After pre-treatment, the mixtures were filtered and the residues dried at 60 °C. Evaluation of the pre-treatment methods was carried out using an agar-plate test in which agar was prepared from the aqueous extracts of the corresponding pre-treated olive cake according to the standardised procedure described.6

Table 13.3 Linear growth velocities of the fungus Ceratocystis moniliformis on various agar plates prepared with aqueous olive cake extracts No.

Pre-treatment

0 1 2 3 4 5 6

Control Untreated Boiled Enzymatically treated Alkaline hydrolysis Acid hydrolysis Boiled and enzymatically treated

Linear growth velocity (cm d−1)

R2

0.6 0.2345 0.276 0.2394 0.3265 0 0.2536

0.8444 0.9578 0.9535 0.9583 0.9969 – 0.9756

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As Ceratocystis moniliformis has been found to be very sensitive to olive cake polyphenols, it was chosen as a reference micro-organism. Agar plates of each agar were inoculated and incubated, and the diameter of the mycelium was then determined every four days as the mean value of the fungal mycelium measured at three different points. Linear regression of the mycelium diameters at four different time intervals produced the linear growth velocities described in Table 13.1. Table 13.1 shows that methods 2, 4 and 6 seem to be the most suitable for removing the phenolic fraction of olive cake, although its total removal could not be achieved. The linear growth velocity of 0.6 cm d−1 of the control was not attained by any of the methods presented. Hydrolysis of the olive cake with NaOH solution does not seem to be the most suitable pre-treatment method. During solid-state fermentation (SSF) with this pre-treated olive cake, no microbial growth could be determined, even though the alkaline medium was neutralised. Methods 2 and 6, both following the methodology of Panizzi et al.,25 also produced good microbial growth for all the selected micro-organisms in SSF. The strongest micro-organism growth was achieved by the olive cake that was boiled and enzymatically pre-treated. Hence, this method was chosen for further experiments with different oil press cakes. 13.5.2 Prime processing: aroma formation on selected oil press cakes The samples released fruity or nut-like odours after SSF as described in Table 13.4. Olive cake samples that were boiled and enzymatically pretreated released a light nut- or coconut-like odour, which led to the assumption that small amounts of δ-decalactone could have been synthesised. This odour impression was overlaid by the characteristic aroma of the olive cake itself. Linseed samples fermented with Trichoderma harzianum also contained a nut-like aroma note; these samples were chosen for gas chromatography (GC) analysis. Castor cake incubated with Trichoderma harzianum and Moniliella suaveolens released intensive nut-like and peachy fruit aroma notes, respectively, strongly indicating the presence of decalactones. All the samples described were concentrated by simultaneous steam distillation–extraction (SDE) according to the method described by Godefroot et al.26 and analysed by GC. Analysis by gas chromatography and gas chromatography– mass spectrometry All SSF samples chosen during sensory evaluation were analysed by GC. Only castor cake incubated with Moniliella suaveolens contained any amounts of γ-decalactone, which was determined by comparison of the retention times during GC analysis and then verified by GC–mass spectrometry (MS). δ-Decalactone was not synthesised by any sample at all. In

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Table 13.4

Results of the sensorial evaluation of the SSF samples

Substrate/ microorganism Olive cake (boiled + enzyme)/Ceratocystis moniliformis Linseed cake/ Trichoderma harzianum Castor cake/Moniliella suaveolens

Castor cake/ Trichoderma harzianum

Growth description

Aroma description

Good growth starting on the tenth fermentation day with formation of a white wad-like mycelium Visible growth starting on the second fermentation day with formation of a short-haired white mycelium. Production of green spores. Visible growth starting on the second day of fermentation with formation of a light green-white mycelium

Formation of a weak nut-like odour Formation of a weak nut-like odour.

Visible growth starting on the second day of fermentation with formation of a short-haired white mycelium. Production of green spores after the tenth day.

Formation of a strong fruity odour starting at the second day of fermentation Strong nut-like odour starting on the tenth day of fermentation.

9:56

γ-decalactone peak

10:00

Fig. 13.9

20:00

GC of Moniliella suaveolens grown on castor cake for four days.

addition, samples of castor cake with Trichoderma harzianum were found to produce small amounts of the decalactone 6-pentyl-α-pyrone, responsible for the intensive nut-like aroma of the sample. Castor cake, with its high content of ricinoleic acid, is known to be an excellent precursor substance for lactone production. After SSF with Moniliella suaveolens, the biosubstrate contained considerable amounts of γ-decalactone, a lactone with a peachy aroma note, as shown in Fig. 13.9.

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85 41 55

100

128

85 43 55

69

50

96

128

100

150

200

Mass spectrum of γ-decalactone produced by Moniliella suaveolens.

Fig. 13.10 250

γ-decalactone yield (mg kg–1 DM)

200 180,7

169,2 150

172,7

163,6 121,3

100 R2 = 0,935 50

46,8

0

0 0

Fig. 13.11

2

4

6 8 Fermentation time (d)

10

12

14

Lactone yield of Moniliella suaveolens inoculated on castor cake (polynomial regression).

The presence of γ-decalactone was verified by GC–MS. As shown in Fig. 13.10, the synthesised lactone contains the characteristic mass 85 m/z, which is the stable lactone-ring consisting of five carbon atoms. Verification with a standard substance clearly determined the desired γ-decalactone. GC analysis of five samples taken during the fermentation of castor cake with Moniliella suaveolens determined the lactone formation during fungal growth. The highest content of γ-decalactone was reached on the fourth fermentation day, with 180.7 mg kg−1 dry matter. After that, the γ-decalactone production slowly decreased to a level of 46.8 mg kg−1 dry matter after 12 days, as shown in Fig. 13.11. The aroma development clearly

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shows that the lactone is an intermediate product of the secondary metabolism of the fungus. The hydroxy fatty acid, ricinoleic acid, is degraded via β-oxidation. Another decalactone, 6-pentyl-α-pyrone, was synthesised by Trichoderma harzianum incubated on castor cake. The concentrations were significantly lower that the formation of γ-decalactone, therefore it was not examined further.

13.6 Adsorption of ecotoxic chemicals employing vegetable bioadsorbents 13.6.1 Prime processing: adsorption properties and particle analysis Particle structures visualised by scanning electron microscope Scanning electron microscopy (SEM XL20, Philips / NL) may be used to visualise the particle structures of the vegetable residues. The samples were fixed on double-sided adhesive carbon tabs mounted on SEM tubs, coated with gold/palladium in a sutter coater, and then examined at 5 kV. In the following figures, selected residues are shown after being magnified from 750 to 6000 times. The residues were chopped, torn, pressed, ground, heated, buffered, and fermented. Several of the processing steps, particularly the pre-processing and stabilisation, modified the particles. In many cases, a combination of unit operations was applied to modify the form, shape and surface area. Hence, shape and structure of the the particles may vary depending on: • • • •

the vegetable material being scanned, the drying method, the mechanical method being applied for size reduction, and any kind of pre-treatment being applied to change the particle structure or composition.

The native carrot pomace particles were dried and ground. The fact that parts of the cell walls remain is clearly visible in Fig. 13.12; note the bunch of vascular bundles in the centre of the image. Powdered vegetable and fruit residues possess a typical capillary system, and this special biological structure influences the functional behaviour of the macroscopic parts of the cell wall. Furthermore, carrot pomace and apple fibres exhibit a strongly folded surface as shown in Fig. 13.13. The structure of apple fibre AFE 400 is almost cubical and its water-binding capacity is three times less than that of wheat fibre (product information). It can be observed in Fig. 13.14 that the surface of the carrot pomace particles has changed owing to the alkaline pre-treatment. The particles are evenly shaped, almost rectangular, and the surface is smooth and even.

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Acc.V Magn 5.00 kV 600x

Fig. 13.12

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WD 50 μm 11.2 Food Technology Uni-Bonn

Native carrot pomace, particle size 63–90 μm.

Acc.V Spot Magn 5.00 kV 4.0 800x

WD 20 μm 13.8 Food Technology Bonn

Fig. 13.13 Apple fibre AFE 400.

Hence, the surface area is reduced, and the binding sites may also be blocked. The sunflower pellets shown in Fig. 13.15 have been treated in a hammer mill and sieved to the described mesh size. The particles are flat and rough,

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Acc.V Spot Magn 5.00 kV 4.0 150x

Fig. 13.14

WD 200 μm 13.5 Food Technology Bonn

Carrot pomace pretreated with alkaline buffer solution, particle size 125–180 μm.

Acc.V Spot Magn 5.00 kV 4.0 100x

Fig. 13.15

WD 200 μm 14.1 Food Technology Bonn

Ground sunflower pellets, 125–180 μm particle size.

A modular strategy for processing of fruit and vegetable wastes

Acc.V Spot Magn 5.00 kV 4.0 375x

Fig. 13.16

305

WD 50 μm 14.1 Food Technology Bonn

Linseed particles, 125–180 μm particle size.

similar to broken slate. No fibre structure can be recognised and the particles are compacted owing to the pelletising. The linseed particles shown in Fig. 13.16 are very different in shape. No clear structure can be identified; the shape is uneven, almost torn and shredded. The rape seed particles have been dried, ground, and sieved to certain mesh sizes. Note the characteristic, almost spherical shape of the 180 µm mesh size fraction in Fig. 13.17. A detailed picture of the rape seed particles is provided in Fig. 13.18. Owing to the cross-sectional cut, the cells can be clearly identified. Figure 13.19 shows a carrot pomace particle pre-fermented with Penicillium roquefortii. The carrot pomace vascular bundle is strongly colonised and covered with Penicillium spores. Swelling capacity kinetics The swelling behaviour over time was investigated for certain residues to determine if there is a time dependency for the uptake of water. Swelling capacity kinetics (SCK) tests were done for acidic, alkaline, and fermented carrot pomace; fermented olive press cake; and apple pomace. Carrot pomace Carrot pomace absorbs three to four times more water than apple pomace or olive press cake. It can be determined from Fig. 13.20, 13.21 and 13.22 that the various particle sizes absorb the water differently. The larger sizes beyond 500 μm form a second group which absorbs more water in a

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Acc.V Spot Magn 5.00 kV 4.0 63x

Fig. 13.17

Acc.V Spot Magn 5.00 kV 4.0 1000x

Fig. 13.18

WD 500 μm 13.6 Food Technology Bonn

Canola meal (rape seed) after extraction.

WD 20 μm 13.7 Food Technology Bonn

Canola meal (rape seed) details scan.

A modular strategy for processing of fruit and vegetable wastes

Acc.V Spot Magn 5.00 kV 4.0 750x

Fig. 13.19

307

20 μm WD 13.9 Food Technology Bonn

Carrot pomace particle pretreated by Penicillium roquefortii.

Swelling capacity (mL g–1)

28 24 20 16 12 8 4 0 0

Fig. 13.20

5

10

15

32–63

63–90

180–250 710–1000

20 Time (h)

25

30

35

90–125

125–180

250–355

355–500

500–710

1000–1400

1400–2000

Swelling capacity kinetics of acidic carrot pomace for certain particle sizes.

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Handbook of waste management and co-product recovery

Swelling capacity (mL g–1)

28 24 20 16 12 8 4 0 0

5

10

15

20 Time (h)

25

30

32–63

63–90

90–125

125–180

180–250

250–355

355–500

500–710

710–1000

1000–1400

1400–2000

Fig. 13.21

35

Swelling capacity kinetics of fermented carrot pomace for certain particle sizes.

Swelling capacity (mL g–1)

28 24 20 16 12 8 4 0 0

5

10

15

20

25

30

Time (h)

Fig. 13.22

32–63

63–90

90–125

125–180

180–250

250–355

355–500

500–710

710–1000

1000–1400

1400–2000

Swelling capacity kinetics of alkaline carrot pomace for certain particle sizes.

35

A modular strategy for processing of fruit and vegetable wastes

309

Swelling capacity (mL g–1)

28 24 20 16 12 8 4 0 0

5

10

15

20

25

30

35

Time (h) 32–63

63–90

90–125

125–180

180–250

250–355

355–500

500–710

710–1000

1000–1400

1400–2000

Fig. 13.23

Swelling capacity kinetics of fermented olive press cake for certain particle sizes.

progressive curve shape. The acidic pomace, with no difference between Lactobacillus farciminis fermentation and chemical treatment, absorbs 22 to 24 mL g−1. Owing to the alkaline pre-treatment, the water uptake is reduced to a maximum of 17 mL g−1, corresponding to the structural observations in Fig. 13.14. Olive press cake Water absorption for olive press cake (Fig. 13.23) is really low, even for the fermented cake. There is no observable difference between the particle sizes. Apple pomace Apple pomace (Fig. 13.24) behaves very similarly to olive press cake with regard to water absorption. The total water uptake is slightly higher and there is little difference in absorption between the particle sizes. It could be concluded that there is no strong correlation between water uptake and time. The particles absorb the water quickly and do not exhibit any particular change after roughly 10 h. However, there are differences between the individual residue types. It can be concluded that: • the water uptake is dependent on the residue type (different polymers), • the absorption kinetics are always similar, and • the pH value seems to influence the water uptake.

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Swelling capacity (mL g–1)

28 24 20 16 12 8 4 0 0

5

10

15

20

25

30

35

Time (h) 32–63 180–250 710–1000

Fig. 13.24

63–90 250–355 1000–1400

90–125 355–500 1400–2000

125–180 500–710

Swelling capacity kinetics of apple pomace for certain particle sizes.

Swelling capacity The swelling capacity (SC) was determined in a 24-hour test. All results shown are mean values of double determinations. Some of the results are bundled to compare the various pre-treatment methods more easily. Figure 13.25 shows the SC in relation to various pre-treatment methods for carrot pomace. The acidic and alkaline pre-treatments were done with buffer solutions (citrate buffer pH 3.8, carbonate buffer pH 9.31), and the biological pre-treatment with the micro-organisms Lactobacillus farciminis (pH drop) and Penicillium roquefortii (pH rise). The acidic treatment has a moderate influence on SC, as does the alkaline treatment. The biological pre-treatment has a far greater influence, with the greatest increase shown by the fermentation of Lactobacillus farciminis. Different behaviour can also be observed for the particle sizes. The smaller particle sizes are less sensitive to the pre-treatment; the larger the particle, the higher the SC. Figure 13.26 clearly shows the influence of the pre-treatment methods. The zero line is the swelling capacity of the native carrot pomace. The Lactobacillus farciminis fermentation displays an outstanding influence on the water uptake. The results are very different for the olive cake fractions (Fig. 13.27). Each of the olive cake residues absorbs little water compared with the carrot fraction. The average water uptake is 2 to 4 mL per g olive cake. There is also no obvious influence from the pre-treatment steps. The SC is not modified by the thermal treatments of spray drying or oven drying, or

A modular strategy for processing of fruit and vegetable wastes Native Acidic Alkaline Lactobacillus farciminis Penicillium roquefortii

20 Swelling capacity, SC (mL g–1)

311

18 16 14 12 10 8 6 4 2

14

00

–2

–1

00

40

0

0

00 00 10

0–

10

71 71

0– 50

35

5–

50

0

0

5 35

25

18

0–

0–

5–

25

18

0

0

25 12

–1 90

63 –9 0

32 –6 3

0

Corn class (μm)

10

Influence of chemical and biological treatment on swelling capacity of carrot pomace.

Acidification Alkalization Lactobacillus farciminis Penicillium roquefortii

8 6 4 2

25 0– 35 5 35 5– 50 0 50 0– 71 0 71 0– 10 00 10 00 –1 40 0 14 00 –2 00 0

18 0– 25 0

0 12

5–

18

25 –1 90

–6 32

63 –9 0

0

3

Swelling capacity, SC (mL g–1)

Fig. 13.25

Corn class (μm)

Fig. 13.26

Swelling capacity variation owing to biochemical pre-treatment (zero-line = native carrot pomace swelling capacity).

acidic or alkaline pre-fermentation. A very slight trend may be observed for the particle fractions; the smaller particle sizes adsorb a little more water compared with the larger fractions. Figure 13.28 shows the effects of the pre-treatment steps. The zero line is the native, spray-dried olive cake. With the larger particle fractions, the influence of the biochemical treatment is observable, but in different directions, either reducing or improving the SC.

Handbook of waste management and co-product recovery 20 18 16 14 12 10 8 6 4 2 0

35 5 35 5– 50 0 50 0– 71 0 71 0– 10 00 10 00 –1 40 0 14 00 –2 00 0

0– 25

18

12

0–

5–

25

18

0

0

25 –1

32

90

3 63 –9 0

Spray dried Oven dried Lactobacillus farciminis Penicillium roquefortii

–6

Swelling capacity, SC (mL g–1)

312

Corn class (μm)

Fig. 13.27

Influence of biochemical treatment and drying mode on swelling capacity of olive press cake.

Oven dried Lactobacillus farciminis Penicillium roquefortii

2

–4

0

0

00 –2 00

14

10

00

–1

10

40

00

0 0– 71

50

0– 50

5– 35

71

0

5 25

0–

35

0 18

0–

25

0 12

5–

18

25 –1

–9

0 90

–2

63

–6

3

0

32

Swelling capacity, SC (mL g–1)

4

Corn class (μm)

Fig. 13.28 Variation in swelling capacity owing to biochemical and thermal pre-treatment (zero-line = SC of spray dried olive press cake).

Figure 13.29 shows a selection of carbohydrate-rich residues and their SC in relation to all particle sizes. As expected, owing to their typical capillary system and biological structure, they adsorb 4 to 9 mL g−1 of water. Figure 13.30 compares the SC of oilseed residues. Sunflower-seed cake is outstanding in its water uptake, followed by linseed cake. In Table 13.5 the SC of all tested residues is presented. Mean values over all particle fractions for each residue were calculated and the mean values were compared with the commercial fibre products of wheat fibre WF200 and WF600, and apple fibre AFE400 (Rettenmair, Hünfeld, Germany). Wheat

20 18 16 14 12 10 8 6 4 2 0

313

00

14

14 00 –

10 00 –

20

00

00 10

10

0– 71

50 0– 7

00

5

35 5– 5

25

0–

35

0 25

0 0– 18

12

5–

–1 90

18

25

0 –9

32

–6

3

Spent malt Apple pomace Corn cob Sugar beet pulp Carrot pomace

63

Swelling capacity, SC (mL g–1)

A modular strategy for processing of fruit and vegetable wastes

Corn class (μm)

20 18 16 14 12 10 8 6 4 2 0

Swelling capacity of selected carbohydrate-rich residues.

0 00

14

00

–2

–1 00 10

0–

10

71 71

0–

40 0

00

0

0 50

35

5–

50

35 0– 25

18

0–

25

5

0

0 12

5–

18

25 –1 90

63 –9 0

Linseed Olive Sunflower Rape seed

32 –6 3

Swelling capacity, SC (mL g–1)

Fig. 13.29

Corn class (μm)

Fig. 13.30

Swelling capacity comparison of selected oilseed residues.

fibre possesses the highest SC, closely followed by the pre-treated carrot pomace (Lactobacillus farciminis), and untreated sunflower-seed cake. The biochemical pre-treatment is successful in the improvement of SC, and alternative materials, apart from apple and wheat fibre, could also be taken into consideration for improving the water uptake. Water-binding capacity The water-binding capacity (WBC) or water-holding property is defined as the ability to absorb water and to hold it even after treatment with external

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Table 13.5 Average swelling capacity for the tested residues Residues Wheat fibre WF200 Carrot Lactobacillus farciminis Sunflower Linseed Carrot Penicillium roquefortii Acidic carrot Alkaline carrot Wheat fibre WF600 Native carrot Apple pomace Apple fibre AFE400 Spent malt Sugar beet pulp Rape seed Corn cob Olive Lactobacillus farciminis Olive spray dried Olive oven dried Olive Penicillium roquefortii

Swelling capacity (mL g−1) 18.22 13.12 10.52 9.76 9.75 9.25 8.97 7.67 7.52 7.30 6.93 6.58 6.43 5.29 4.05 3.96 3.86 3.71 3.60

forces. To apply these external forces, a laboratory centrifuge was used. The particles did swell for 24 h in the same way as described for the SC. The WBC is related to the structure of the particles, therefore changing the particle structure, size or composition will result in a change in the WBC. In the following figures, the results are bundled to compare the influence of the pre-treatment methods more easily. The particle sizes are expressed as the lower class limit of the respective fraction (32–63 μm becomes 32 μm). All the results shown are mean values of double or triple determinations. Standard deviation was not included in the charts to simplify comparison of the materials. Figure 13.31 exhibits the WBC resulting from various pre-treatment steps for carrot pomace. The application of external forces, here centrifugation, does shift the results for the fermented samples. There is an influence on the WBC from the alkaline and the acidic fermentation, but it is less pronounced than for the SC results. The smaller particle sizes react differently to the pre-treatments, which sometimes even have the effect of decreasing the WBC. The larger the particles, the stronger the positive influence of the pre-fermentation. Figure 13.32 shows the changes in WBC compared with that of native carrot particles, which is represented by the zero-line. There is a clear trend for the enhancing effect of the Lactobacillus farciminis treatment. The

A modular strategy for processing of fruit and vegetable wastes Native carrot Acidic carrot Alkaline carrot Lactobacillus farciminis Penicillium roquefortii

10 Water binding capacity, (mL g–1)

315

9 8 7 6 5 4 3 2 1 0

32

Fig. 13.31

63

90

125

180 250 355 Particle diameter (μm)

500

710

1000

1400

Influence of chemical and biological treatment on water-binding capacity (WBC) of carrot pomace.

Relative WBC (mL g–1)

3 2 1 0 32

63

90

125

180

250

355

–1

500

710

1000

1400

Acidification Alkalization Lactobacillus farciminis Penicillium roquefortii

–2 –3 Particle diameter (μm)

Fig. 13.32 Variation in water-binding capacity owing to several pre-treatment steps (zero-line = native carrot pomace WBC).

results are very different for the WBC of the olive cake fractions shown in Fig. 13.33. Oven-dried, spray-dried, and Lactobacillus farciminis-fermented samples exhibit the water uptake that was determined for the SC in Fig. 13.27 as 2 to 4 mL g−1. Penicillium roquefortii pre-fermentation is outstanding in its influence on the WBC, which is enhanced for all particle fractions. This effect becomes even more obvious in Fig. 13.34, where the relative changes in WBC are plotted against the WBC of spray-dried olive cake as the zero line.

Water binding capacity (mL g–1)

316

Handbook of waste management and co-product recovery Oven dried olive Spray dried olive Olive Lactobacillus farciminis Olive Penicillium roquefortii

10 9 8 7 6 5 4 3 2 1 0

32

63

90

125

180

250

355

500

710

1000

1400

Particle diameter (μm)

Fig. 13.33

5

Relative WBC (mL g–1)

4

Influence of biochemical treatment and drying mode on water-binding capacity of olive press cake.

Olive oven dried Olive Lactobacillus farciminis Olive Penicillium roquefortii

3 2 1 0 32

63

90

125

180

250

355

500

710

1000

1400

–1 –2

Particle diameter (μm)

Fig. 13.34 Variation in water-binding capacity owing to several pretreatment steps (zero-line = spray dried olive press cake WBC).

Figure 13.35 shows a selection of carbohydrate-rich residues and their WBC for all particle sizes. The greatest amount of water is absorbed by carrot pomace, spent malt and sugar beet pulp; all three materials seem to be able to hold the water owing to their fibre composition. Corn cobs and apple pomace exhibit moderate WBC between 2 and 4 mL g−1. Figure 13.36 shows the WBC of selected oilseed residues. Again, sunflower cake is outstanding in its WBC, closely followed by linseed cake. It could be determined that there is a strong correlation between the water

A modular strategy for processing of fruit and vegetable wastes

Water binding capacity (mL g–1)

10

317

Spent malt Apple pomace Corn cob Sugar beet pulp Native carrot

9 8 7 6 5 4 3 2 1 0

32

63

90

125

180

250

355

500

710

1000

1400

Particle diameter (μm)

Fig. 13.35 Water-binding capacity of selected carbohydrate-rich residues.

Water binding capacity (mL g–1)

10

Linseed

9

Olive

8

Sunflower Rape seed

7 6 5 4 3 2 1 0

32

63

90

125

180

250

355

500

710

1000

1400

Particle diameter (μm)

Fig. 13.36 Water-binding capacity comparison of selected oil seed residues.

uptake, the water holding capacity and the pre-treatment steps. There are differences between the residue types and the pre-treatment steps. Differences between the particle sizes are not significant. It can be concluded that • the SC and WBC are affected by the pre-fermentation, • the improvement in SC and WBC is always greater for carrot pomace compared with olive cake,

318

Handbook of waste management and co-product recovery S´V (d´) =7054.75 m–1 0–32 32–63 63–90 90–125 125–180 180–250 250–355 355–500 500–710 710–1000 1000–1400 1400–2000 >2000

Fig. 13.37

S´m (d´) =0.00503 m2 g–1 1% 1% 4%

7%

30% 12%

23%

22%

Particle size distribution of native carrot pomace.

• of the carbohydrate residues, sugar beet pulp and carrot pomace have the greatest SC and WBC, and • of the oilseed residues, sunflower and linseed exhibit the greatest SC and WBC. Sieve analysis Sieving analysis was performed on selected vegetable residues to determine the particle size distribution of the dried material. For each material, 200 g were used to guarantee that even fine particles for the lower mesh sizes could be collected. The materials chosen were: native carrot pomace, alkaline carrot pomace, acidic carrot pomace, Penicillium roquefortii-fermented carrot pomace, spray-dried olive cake, Penicillium roquefortii-fermented olive cake, Lactobacillus farciminis-fermented olive cake, apple pomace, sugar beet pellets, spent malt, rape seed, and sunflower cake pellets. The results are too extensive to present here in full. Therefore full details are presented for carrot pomace. Figure 13.37 and 13.38 show the particle distributions of native carrot pomace. Figure 13.38 displays the sieve analysis for native carrot pomace, which was dried and sieved. The columns represent the mass of each fraction as a percentage of the total mass. In addition, undersize and oversize are plotted against particle size; the d0.5 can be determined at their intersection. The abscissa is not a numerical scale, therefore it is known only that the median must be in the class range 710–1000 μm and the modal value is 1400–2000 μm. If undersize and oversize are plotted against particle size on a numerical scale, the d0.5 can be determined as 890 μm, as shown in Fig. 13.39. Particle size analysis via RRSB and surface area determination Plotting the average particle diameter d¯ of each fraction against the cumulative undersize in a double logarithmic plot produces a steep straight line as

319

100.0 80.0 0.8

% Fraction Undersize (U) Oversize (O)

70.0 60.0

0.6

50.0 40.0 30.0

22.4% 23.4%

0

0

00 >2

14

00

–2

00

40

0

0

00 10

00

–1

10 0–

50

0–

71

0

0

0.4%

50

5

0.2

6.9% 12.0%

5–

35

0 25 25

0–

0 0–

18 18

5–

–1

90

12

32 32 –6 3 63 –9 0

0–

25

0.0% 0.0% 0.1% 0.3% 0.8% 1.3%

0.0

3.8%

35

10.0

71

20.0

0.4

28.8%

Particle diameter (μm)

Fig. 13.38

Sieve analysis of native carrot pomace.

1 0.8 0.6

Undersize (U) Oversize (O)

0.4 0.2

90 0 10 00 11 0 12 0 00 13 00 14 00 15 00 16 00 17 00 18 00 19 00 20 00

70 0 80 0

0 10 0 20 0 30 0 40 0 50 0 60 0

0

Particle diameter (μm)

Fig. 13.39

Native carrot sieve analysis on a numerical scale.

shown in Fig. 13.40. The regression line equation is shown in the chart, as well as R2 as a statistical parameter, representing the correlation grade. With this information, the data in Table 13.6 can be determined according to the methodology explained in Table 13.7 and Equation 13.1, respectively. 1 ⎛ ⎞ lglg ⎜ = n lg d − n lg d ′ + lglg e ⎝ 1 − D(d) ⎟⎠ y = mx + y0

[13.1]

Undersize and oversize

1

90.0

Undersize and oversize

Cumulative distribution, Qr(d) (relative %)

A modular strategy for processing of fruit and vegetable wastes

Qr (d)

320

Handbook of waste management and co-product recovery 2 1 0 –11 –2 –3 –4 –5 –6

1.5 y = 2.7649x – 8.4626

2

2.5

3

3.5

lg lg 1/1–U Linear (lg lg 1/1–U)

R2 = 0.973

Particle diameter (μm)

Fig. 13.40

RRSB plot for the sieve analysis of native carrot pomace (calculated via MS Excel).

Table 13.6 Diameters and surface areas calculated for carrot pomace

Table 13.7

Quantity

Values for native carrot

d0.5 d0.632 S′V (d′) S′V (d¯ ) Sm (d′)

744.99 μm 850.48 μm 7054.75 m−1 7590.61 m−1 0.00503 m2 g−1

Determination of d and surface area S′V (d′) from Equation 13.1 y = 2.7649x − 8.4626

Regression line equation

A

B = 1/(1 − A)

C = lg B

D = lg C

E=D+ 8.4626/2.7649

10(E) = diameter (μm)

Median at d0.5 Statistic d′

0.5 0.632

2 2.7173913

0.30 0.43

−0.52 −0.36

2.87 2.93

744.99 850.48

S′V (d′) Sm (d′)

7054.75 m−1 0.00503 m2 g−1

If the density of carrot pomace is known, the mass-related surface area Sm can be determined according to Equation 13.1 as 0.00503 m2 g−1. Thus, a determination of the surface area of each residue is feasible and the results can be compared. Table 13.8 is a list of the relevant data resulting from the particle size analysis and surface area determination. The numerous calculations for these determinations are shown elsewhere.5 It seems that the calculated surface area for the residues is not directly connected to their WBC and SC data. The mass-related surface Sm(d′)

A modular strategy for processing of fruit and vegetable wastes Table 13.8 and mass

321

Surface area determination for selected residues, related to volume S′v (d′)

Sm(d′) / (m2 g−1)

Sm(d′) / cm2 g−1

Carrot pomace Native Penicillium roquefortii Alkaline Acidic

7054.76 4773.39 4216.36 3878.57

0.005039114 0.003409563 0.003011687 0.002770408

50.39 34.10 30.12 27.70

Olive cake Native Penicillium roquefortii Acidic

2524.42 2992.73 2838.58

0.00180316 0.00213766 0.00202756

18.03 21.38 20.28

Residue Spent malt Apple pomace Sugar beet pellets Sunflower cake Rape seeds

2430.12 3162.56 7827.23 6946.79 7306.05

0.0017358 0.00225897 0.00559088 0.00496199 0.00521861

17.36 22.59 55.91 49.62 52.19

shows the highest values for native pomace, which is in contrast to the respective SC and WBC results. It can be concluded, that • for carrot pomace, all pre-treatment steps decrease the surface area, • olive cake exhibits a reduced surface area for all pre-treatment methods compared with the other residues, and • native sugar beet pellets, sunflower cake, rape seeds, and carrot pomace possess the highest surface areas determined. 13.6.2

Adaptation processing: adsorption using carrot pomace and sugar beet pulp

Objective: Wastewater pre-treatment containing aromatic components An initial series of experiments was performed with three different residues, examining their ability to adsorb aromatic wastewater components. Vanillin, as an example of a substance of ecotoxic relevance, was tested in aqueous solution, together with benzaldehyde, phenol and humic acid. The adsorbing conditions were determined for changes in the process parameters that could affect them. The residues carrot pomace, corn cob, and sugar beet pulp, dried and ground to particle sizes of 125–180 μm and 710– 1500 μm, were used as bioadsorbents. In a second series of tests, carrot pomace and sugar beet pulp were inoculated with Lactobacillus farciminis and fermented for 20 h. This pretreatment step was supposed to enhance the shelf life of the fresh pomace and partly degrade the components. The tests should reveal if there is any

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Handbook of waste management and co-product recovery

correlation between the targeted metabolism of lactic acid fermentation and the adsorbent capacity. pH With regard to pH, it was determined that the order of the adsorption rates of the materials was carrot pomace > corn cob > sugar beet pulp. Carrot pomace adsorbed vanillin best at pH 4, corn cob at pH 7 and sugar beet pulp at pH 10. A clear pH dependency was identified, which changed with the chemical adsorbed. Best adsorption results were achieved for vanillin at an acidic pH, the sequence being pH 4 > pH 7 > pH 10. A clear tendency was noted for the pH-adjusted carrot pomace and sugar beet pulp to return to their initial pH after a certain time owing to the ion-exchange mechanism. Adsorption time and dosage In the experiments, the adsorption time and adsorbents dosage were simultaneously varied. The optimum adsorbent dosage was determined as 20 g L−1 with a contact time of 5 min. A contact time of 5 min is sufficient to adsorb 75–85% of the chemical. Targeted metabolism The adsorption rate is decisively influenced by the method of acidification, as mentioned previously. Hydrochloric acid enhances the capacity owing to the change in pH, but the metabolism of certain micro-organisms also influences the particle character (e.g. different configuration of carbohydrates and lignin fraction and/or degradation in total). This targeted use of metabolism produced superior results. The fermented samples did not need any pH adjustment, were stable in shape and initial pH, and tended to adsorb more substance than the HCl-adjusted samples.

13.7 Multifunctional food ingredients in novel products 13.7.1 Asparagus residues as a potential sauce binder Initial investigations into the usability of asparagus wastes as a sauce thickener were conducted. The product should serve as an alternative for the usual sauce thickener made of modified starches. Previous suggestions, such as its utilisation in paper production,27 were not successful owing to its high lignin content. The development of the process took place as shown in the decision matrix in Fig. 13.8; this section focuses on the prime and adaptation processing steps. After several steps of pre-treatment (physical, chemical, biotechnological), a dried and brownish raw material was produced, which had the characteristic aroma of pyrazine and pyrrol. Owing to this aromatic flavour and its colour, dried asparagus peel (DAP) was considered to be a promising

A modular strategy for processing of fruit and vegetable wastes

323

raw material for a brown sauce thickener. The main objectives of the next step, namely prime processing, were an increase in viscosity (if DAP was mixed with water) and the ratio of dietary fibres, while maintaining the sensorial quality. For the following adaptation steps, the example used was a sample of asparagus waste that was first frozen, then dried at 100 °C for 3 h without extracting any water, and ground with a centrifugal mill (mesh size 80 μm). The dried raw material amounted to 7.7% of the peels. The viscosity of DAP in water (100 g L−1) was too low to measure. Therefore, a model sauce was used consisting of sunflower oil in water (10% v/v). A determination of rheological properties (CR rotating cylinder viscosimeter) was performed for boiled-up samples of the model sauce with 100 g L−1 of commercial sauce thickener (Maggi), DAP or DAP plus xanthan gum (2.5 g L−1), respectively. The results for shear stress and viscosity, at given shear rates, are shown in Table 13.9. It can be seen that the rheological properties of the model sauce with commercial sauce thickener and DAP + xanthan gum are similar, while the viscosity and shear stress with DAP are much lower, even not detectable in a range of 23.5–74.8 s−1. The DAP behaved like a Newtonian fluid, as can be seen in Fig. 13.41, where the data for DAP follow a linear regression. The model sauce containing DAP is thus of ideal viscosity and DAP is not suitable for use as a thickener. The results for DAP + xanthan gum and

Table 13.9 Results of rheological measurements of model sauce with DAP, DAP + xanthan gum, and commercial sauce binder Shear stress (Pa) Shear rate (s−1) 23.5 42.0 74.8 125.5 223.4 386.7 683.5 1200.0 683.4 386.8 223.3 125.4 74.7 42.0 23.5

Viscosity (Pa·s)

Sauce thickener

DAP

DAP + xanthan gum

Sauce binder

DAP

DAP + xanthan gum

4.0 5.3 7.4 9.9 12.8 15.8 22.2 31.3 20.9 14.6 12.1 8.9 6.8 4.8 3.8

* * * 1.9 3.3 5.3 9.5 19.7 10.4 4.8 3.0 1.9 * * *

4.9 5.5 6.6 7.8 9.7 12.0 16.9 23.3 15.8 11.3 9.0 7.4 6.1 5.1 4.4

0.171 0.126 0.099 0.079 0.057 0.041 0.033 0.026 0.031 0.038 0.054 0.071 0.091 0.115 0.162

* * * 0.015 0.015 0.014 0.014 0.016 0.015 0.012 0.013 0.015 * * *

0.209 0.131 0.088 0.062 0.043 0.031 0.025 0.019 0.023 0.029 0.040 0.059 0.082 0.121 0.187

* Not detectable.

324

Handbook of waste management and co-product recovery Commercial sauce thickener increase DAP DAP + xanthan gum decrease DAP + xanthan gum increase Commercial sauce thickener decrease Linear (DAP)

30 Shear stress (Pa)

25 20 15 10 5 0 0

200

400 Shear rate

Fig. 13.41

600

800

1000

(s–1)

Comparison of shear stress of DAP, DAP + xanthan gum and commercial sauce thickener.

commercial sauce thickener show that they possess similar shear thinning properties. They form non-Newtonian liquids, so the relation between shear rate and shear stress is not linear, but can be described by the power law. The increase and decrease of shear rate are both shown; they have corresponding flow curves, thus their behaviour is thixotropic. Further treatments of adaptation processing were conducted, including extraction with 2.5 m NaOH and 0.1 m HCl. Greenshields et al.28,29 found that an alkaline extraction of plant fibres and cereals, with subsequent enzymatic linking of polysaccharides via ferulic acid, results in a gel with specific flexibility and cohesiveness. DAP was suspended in water (50 g L−1), 5% (v/v) NaOH was added and the suspension was stirred at 70 °C for 50 min. The suspension was centrifuged and HCl was added to the supernatant solution stepwise until the pH was <7. The results for shear stress are presented in Table 13.10. Pentosanes and hemicelluloses are soluble in aqueous NaOH, thus the xylans contained in DAP can be dissolved. The non-soluble residue is discarded after centrifugation. After pH neutralisation by HCl, the dissolved xylans precipitated. It is not clear if ferulic acids can lead to the connections as described by Greenshields et al., but the formation of a gel could be observed. The viscosity increased through neutralisation by HCl (seen in Fig. 13.42, where the black column represents the total viscosity at a shear rate of 60 s−1 in the increasing shear rate cycle, and the white one the viscosity at 60 s−1 in the decreasing cycle). This shear rate was chosen because Wood (1969)

A modular strategy for processing of fruit and vegetable wastes Table 13.10 extraction

325

Shear stress of DAP after alkaline

Shear rate [s−1]

Shear stress

23.5 42.0 74.8 125.5 223.4 386.7 683.5 1200.0 683.4 386.8 223.3 125.4 74.7 42.0 23.5

* 1.8 2.3 3.1 4.3 5.5 8.5 16.9 8.0 4.7 3.5 2.7 2.2 * *

* Not detectable.

Total viscosity at increasing shear rate cycle Viscosity at decreasing shear rate 0.12

Viscosity (Pa s)

0.1 0.08 0.06 0.04 0.02 0 DAP + alkaline extraction

Sauce thickener

Fig. 13.42 Viscosity of sauce thickener after alkaline extraction.

has shown that a shear rate of about 60 s−1 is produced during the tasting and spreading of sauce in the mouth by the tongue.30 As well as the raised viscosity, an increased aromatic flavour was observed. This is produced by the hydrolysis of proteins by HCl, which is traditionally used for the production of aromatic compounds such as amino acids and peptides. It can be concluded that DAP + xanthan gum looks like a promising intermediate product for use as a sauce thickener, as well as the DAP treated with NaOH and HCl. The latter intermediate is a brown liquid with

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Table 13.11 Glutamic acid production by fermentation of DAP with Corynebacterium glutamicum Sample1 A B C

Concentration of glutamic acid before fermentation (g L−1)

Concentration of glutamic acid after fermentation (g L−1)

Increase

0.018 0.014 0.015

0.016 0.030 0.024

−0.003 0.016 0.009

1 Sample A: dried (100 °C, 3 h) and ground (centrifugal mill, 80 µm); sample B: boiled (40 min), water pressed out, dried (100 °C, 3 h), ground (centrifugal mill, 80 µm); sample C: autoclaved, fermented with Lactobacillus reuteri (37 °C, 48 h), water pressed out, dried (100 °C, 3 h).

an increased viscosity; it coagulates easily and offers an aromatic and salty flavour. The following phase of adaptation processing aimed to increase the content of glutamic acid, since its flavour characteristic may improve the quality of a sauce thickener. As the intention was to use a biotechnological process, there would be no need for this treatment to be declared, as would be the case with the addition of chemical glutamic acid and its salts (E620– 625). Hence, fermentation with Corynebacterium glutamicum was performed. Different samples (differing in the kind of pre-treatment) of DAP were dissolved in water (50 g L−1), the pH was adjusted to 7.2–7.4 and the sample were autoclaved. After inoculation with C. glutamicum, the sample was incubated at 30 °C for 48 h. Results of the fermentation are presented in Table 13.11. Samples B and C showed an increase in glutamic acid, while sample A showed an even lower content after the fermentation with C. glutamicum. Surprisingly, sample B, where the highest increase in glutamic acid production was observed, had the lowest content of phenols and no high intensity of browning. Thus, accumulated Maillard reaction products may be responsible for the inhibition of glutamic acid production and C. glutamicum growth, respectively. Based on the low production rate of glutamic acid, the process is not feasible and is thus excluded as an adaptation process. Hence, the extract obtained from drying and alkaline extraction was dried again and used directly as a sauce thickener in the following sensorial tests.

13.7.2 Fibre enrichment with carrot and asparagus residues Fibre enrichment of bread has a direct influence on the bread’s quality. Therefore, research in this area mostly covers, besides the nutritional aspects, the effects on bread volume. Owing to the enhanced water binding of the dough, its freshness will be improved, but, on the other hand, the

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1400

Bread volume (mL)

1300

Carrot R2 = 0.4434

Asparagus R2 = 0.0241

1200 1100

Asparagus Carrot Linear (asparagus) Linear (carrot)

1000 900 800 0

2

4

6 8 Added fibre (%)

10

12

Fig. 13.43 The influence of fibre supplements on the volume of sourdough bread.

dough becomes heavy and sticky, reducing crumb quality, crumb elasticity and crust formation. A series of tests was performed with two selected fibre products: carrot pomace and asparagus residues. Carrot pomace is rich in carbohydrates; asparagus residues contain reasonable amounts of protein (lysine!), sugars, and folic acid. Proteins and sugars contribute to the formation of Maillard products, giving colour and flavour to the bread. The residues were tested for their ability to act as a sourdough supplement in rye bread. Mixed rye bread (3 : 2) was produced according to the following basic recipe: 600 g rye flour, 400 g wheat flour, 30 g salt, 7 g dry yeast, 770 mL drinking water, 40 g sourdough (dried). The kneading time was 3 min slow, and 5 min fast. Various percentages of asparagus and carrot fibre were added, related to the total input weight of flour. All volume determinations were done three times; in the following figures the mean volume values are plotted against the percentage of fibre added. As seen in Fig. 13.43, the added residue has almost no influence on the baked bread volume. The addition of asparagus fibre does not correlate with the bread volume. A slight trend is visible for the carrot pomace supplement, but with an R2 of 0.44, this dependency definitely needs more series of tests. In connection with this, it is very interesting that the volume of the bread normally decreases with increasing fibre content. But even after triple checking, no decrease in volume was found. Both fibres seem to be well suited for the fibre enrichment of rye bread. If warm water is added during the dough kneading, the increased fibre content does not affect the dough volume. The results are different with the addition of cold water, as is clearly shown in Fig. 13.44. The bread volume is quite high with no asparagus fibre addition, but there is an obvious decrease with the 3 and 5% fibre addition.

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Handbook of waste management and co-product recovery 1400

Asparagus, warm Asparagus, cold Linear (asparagus, warm) Linear (asparagus, cold)

Bread volume (mL)

1300 1200 1100

Warm R2 = 0.0241

1000

Cold R2 = 0.4434

900 800 0

Fig. 13.44

1

2

3 4 Added fibre (%)

5

6

Dependency of cold and warm water addition on bread volume of asparagus fibre bread.

13.8 Future trends Future-orientated added value should consist of both a substantial and an energetic utilisation of bioresources. This chapter refers solely to substantial utilisation and thus shows the great quantity of research results discussing the bioconversion of food processing residues into value-added products. The presented information reflects the great importance and the significance of recycling and upgrading of vegetable by-products and residues. Biotechnological processes in particular show an immense potential for value-addition to residual matter, which otherwise may cause environmental impact and economical disadvantages. The upgrading concept exhibits a promising utilisation for solid vegetable and fruit wastes and can achieve a reduction of investment and raw material costs and contributes to a waste minimised food production. Although nowadays the food processing industry may be regarded as very efficient, each processing step creates waste or by-products and they can only partially be avoided. This chapter has summarised the most promising approaches towards recycling of food processing residues, thus contributing to a sustainable development. The application examples underline the great potential, but much further research is necessary for a successful industrial implementation. For instance, for the utilisation of food residues as multifunctional food ingredients, the most important step to be optimised is the adaptation process. Often promising research results are not implemented owing to problems during the food application. Mostly, the sensorial aspects are limiting, e.g. dietary fibres lead to an unacceptable mouth feeling or to sedimentation. Another important example is the use of polyphenols recovered by upgrading processes. The obtained extracts are often perceived bitter or adstringent and thus rejected by consumers. For a

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successful industrial implementation such products have to be optimised, e.g. by microencapsulation techniques applied for taste masking. Furthermore, the use of vegetable residues as a substrate for production of flavours, enzymes or polyphenols, is a very interesting approach. The interest in biotechnological production of fine chemicals will even increase in the near future. In particular, the substitution of high-price fermentation substrates is very promising. The main difficulty that has to be overcome is dealing with the downstream processing. Hence, the emphasis of future research has to be put on efficient isolation and purification of biotechnically produced substances. Additionally, it was shown that there is not only a great potential in utilising vegetable residues within the food chain, but also in converting them into bioadsorbents. The latter utilisation seem to be a promising approach in waste management as well as in the treatment of (waste) waters, e.g. by adsorption of compounds such as vanillin or benzaldehyde. For a broad application, research has to be expanded to a variety of residues and an optimisation in all three steps of upgrading will be necessary. Conclusively, it can be said that the described ways of value-addition to vegetable residues are very promising and offer a great potential owing to a sustainable development. Before wide industrial implementation is possible, there are still some difficulties to be overcome within the next few years. Considering the considerable research effort that has already been carried out, good progress is expected within the coming decade.

13.9 Sources of further information and advice Beside the cited publications found in the reference list a few books of general information should be mentioned explicitly. Certainly, the Handbook of waste management and co-product recovery in food processing Volume 1, edited by Keith Waldron (2007) is leading in the field of recycling and upgrading of vegetable matters. Another key book is Olive processing waste management – literature review and patent survey from M. Niaounakis and C. P. Halvadakis (2005). Very helpful information is also given by AWARENET (2001–2004), a thematic network established to examine agro-food waste prevention, minimisation and recovery in terms of the regulatory, technology and market issues. Useful information including statistical data is found in their released Handbook for the prevention and minimisation of waste and valorisation of by-products in European agrofood industries. Further important networks and projects to be mentioned are RAMIRAN (http://www.ramiran.net, ongoing), GRUB’S UP (http:// www.grubs-up.eu, 2005–2009), BIOACTIVE-NET (http://bioactive-net. com, 2006–2008), REPRO-FOOD (2005–2008), and AIR2-CT93-1023 – Fermentative Utilization of Fruit and Vegetable Pomace and Biowaste for Production of Novel Types of Products (1994–1997). Research groups

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focusing on strategies for value-adding utilisation of food processing residues are, amongst others, the TTZ, Bremerhaven, Germany (participant/ coordinator of a series of projects, e.g. BIOACTIVE-NET and GRUB’S UP), the Institute of Food Research, Norwich, UK (Sustainable Food Chain Exploitation Platform and participant/coordinator of a series of projects, e.g. REPRO-FOOD), the Institute of Food Science and Biotechnology – Plant Foodstuff Technology, University Hohenheim, Germany, the Department of Nutrition and Food Science – Food Technology and Biotechnology, University Bonn, Germany, and the Institute of Food Technology and Food Chemistry – Food Process Engineering, Technical University Berlin, Germany (http://www.tu-berlin.de/lvt).

13.10 Further reading abu-qudais, m. (1996) Fluidized-bed combustion for energy production from olive cake. Energy 21(3), 173–178. aguilera, j.m. (2000) Microstructure and Food Product Engineering. Food Technology 54(11), 56–65. aguilera, j.m.; baffico, p. (1997) Structure-mechanical properties of heat-induced whey protein/starch gels. Journal of Food Science 62, 1048–1053, 1066. aguilera, j.m.; stanley, d.w.; baker, k.w. (2000) New dimensions in microstructure of food products. Trends in Food Science & Technology 11, 3–9. ahmenda, m.; marshall, w.e.; rao, r.m. (2000) Production of granular activated carbons from select agricultural by-products and evaluation of their physical, chemical and adsorption properties. Bioresource Technology 71, 113–123. ahmenda, m.; marshall, w.e.; rao, r.m. (2000) Surface properties of granular activated carbons from agricultural by-products and their effects on raw sugar decolorization. Bioresource Technology 71, 103–112. albrecht, w.; heidlas, j.; schwarz, m.; tressl, r. (1992) Biosynthesis and biotechnological production of aliphatic γ- and δ-lactones, in: Takeoka, G., Güntert, M., Teranishi, R. (eds.) Flavor precursors – thermal and enzymatic conversions. ACS symposium series chapter 5, 46–58. alcaide, e.m.; nafzaoui, a. (1996) Recycling of olive oil by-products: possibilities of utilization in animal nutrition. International Biodeterioration and Biodegradation 38(3–4), 227–235. alldrick, a. (2000) Fitting In. International Food Ingredients 2, 6–8. allen, d.m. (1994) Waste minimisation and treatment: an overview of technologies. GMI 5, 22–28. almosnino, a.m.; belin, j.m. (1991) Apple pomace: an enzyme system for producing aroma compounds from polyunsaturated fatty acids. Biotechnology Letters 13(12), 893–898. alonso, m.i.; valdes, a.f.; martinez-tarazona, r.m.; garcia, a.b. (1999) Coal recovery from coal fines cleaning wastes by agglomeration with vegetable oils: effects of oil type and concentration. Fuel 78(7), 753–759. al-wandawi, h. et al. (1985) Tomato processing wastes as essential raw material source. Journal of Agriculture and Food Chemistry 33, 804–807. anagnostopoulou, m.a.; kefalas, p.; papageorgiou, v.p.; assimopoulou, a.n.; boskou, d. (2006) Radical scavenging activity of various extracts and fractions of sweet orange-peel (Citrus sinensis). Food Chemistry 94(1), 19–25. anon. (1992) Meeting the challenge. Prepared foods 7, 70.

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anon. (1999) Gesunde Rottöne. Lebensmitteltechnik 7–8, 38. anon. (2000) Design and engineering of carbohydrate functionality in foods. http:// www.ifrn.bbsrc.ac.uk/vacancies/carbeng.html. anon. (2000) Natural Coloring Agent in Cheese. Food Technology 54(7), 78. anon. (2000) Süßstoffe: mit Sicherheit von Nutzen. Lebensmittel- und Verpackungstechnik LVT 45(4), 239–241. anon. (2000) Zusatzstoffe und Aromen. Lebensmitteltechnik 10, 28. anon. (2001) Sunflower. Tropical-seeds.com: Flowers and ornamentals: articles. http://www.tropical-seeds.com/tech_forum/flowers_orns/sunflower.html, 30.07.01. arlorio, m.; coisson, j.d.; restani, p.; martelli, a. (2001) Characterisation of pectins and some secondary compounds from theobroma cacao hulls. Journal of Food Science 66(5), 653–656. arogba, s.s. (2001) Effect of temperature on the moisture sorption isotherm of a biscuit containing processed mango (Mangifera indica) kernel flour. Journal of Food Engineering 48(2), 121–125. arogba, s.s. (1999) The performance of processed mango (Mangifera indica) kernel flour in a model food system. Bioresource Technology 70, 277–281. arora, a.; camire, m.e. (1994) Performance of potato peels in muffins and cookies. Food Research International 27(1), 15–22. arslan, n.; kar, f. (1998) Filtration of sugar-beet pulp extract and flow properties of pectin solutions. Journal of Food Engineering 36, 113–122. associated press (2000) More than 1,000 protest biotechnology at Boston conference. Startribune 27.03.00, A9. asther, m et al. (1997) Fungal biotransformation of European agricultural byproducts to natural vanillin: a two-step process. Food Ingredients Porte de Versailles, Paris, France, 12–14 November 1996, 123–125. attom, m.f.; al-sharif, m.m. (1998) Soil stabilization with burned olive waste. Applied Clay Science 13, 219–230. attri, b.l.; maini, s.b. (1996) Pectin from galgal (Citrus pseudolimon Tan.) peel. Bioresource Technology 55(1), 89–91. austin, l.g.; trass, o. (1997) Size reduction of solids crushing and grinding equipment, in: Fayed, M.E., Otten, L. Handbook of Powder Science and Technology. New York a.o.: Chapman & Hall, 586–634. axelrod, b.; cheesbrough, t.; laasko, s. (1981) Fatty acid activation and oxidation: Lipoxygenase from soybeans. Methods in Enzymology 71, 441–445. baek, s.c.; kwon, y.j. (2007) Optimization of the pretreatment of rice straw hemicellulosic hydrolyzates for microbial production of xylitol. Biotechnology and Bioprocess Engineering 12(4), 404–409. bailey, j.e. (1998) Mathematical modeling and analysis in biochemical engineering: past accomplishments and future opportunities. Biotechnology Progress 14, 8–20. bakir, u.; yavascaoglu, s.; guvenc, f.; ersayin, a. (2001) An endo-beta-1,4-xylanase from Rhizopus oryzae: production, partial purification and biochemical characterization. Enzyme and Microbial Technology 29(6–7), 328–334. baksh, m.s.; kikkinides, e.s.; yang, r.t. (1992) Characterization by physisorption of a new class of microporous adsorbents: Pillared Clays. Industrial Engineering and Chemistry Research 31(9), 2181–2189. balatsouras, g.; komaitis, m.; aggelis, g.; anagnostopoulou, g.; tsalkakis, g. (1991) Contribution á la valorisation des grignons d´olive. Enrichissement en matiére protéique d´un grignón d´olive dénoyauté par voie microbiologique (1) Oléagineux 46(8–9), 333–335. balköse, d.; baltacioglu, h. (1992) Adsorption of heavy metal cations from aqueous solutions by wool fibers. Journal of Chemical Technology and Biotechnology 54, 393–397.

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balzert, h. (1999) Lehrbuch Grundlagen der Informatik. Spektrum Akademie Verlag. banerjee, r.; mukherjee, g.; patra, k.c. (2005) Microbial transformation of tanninrich substrate to gallic acid through co-culture method. Bioresource Technology 96(8), 949–953. bankar, d.b.; dara, s.s. (1982) Binding of calcium and magnesium by modified onion skins. Journal of Applied Polymer Science 27, 1727–1733. bart, h.-j.; traving, m. (1998) Reaktivsorption – Rückgewinnung von organischen Wertstoffen aus verdünnten Lösungen. Chemie Ingenieur Technik 70, 1152– 1153. bartnick, j. (2001) Skript zur EDV I (Elektronische Datenverarbeitung I). Hessische Verwaltungs- und Wirtschaftsakademie VWA, University Frankfurt/G. bartolome, b.; gomez-cordoves, c.; sancho, a.i.; diez, n.; ferreira, p.; soliveri, j.; copa-patino, j.l. (2003) Growth and release of hydroxycinnamic acids from Brewers’ spent grain by Streptomyces avermitilis CECT 3339. Enzyme and Microbial Technology 32(1), 140–144. batchelor, s.e.; knight, b.e.a.; wilkinson, a.; booth, e.j.; walker, k.c. (1996) Industrial markets for oilseed rapemeal, Research Review No. OS11. bates, m.p.; philips, p.s. (1999) Sustainable waste management in the food and drink industry. British Food Journal 101(8), 580–589. bechtold, t.; mahmud-ali, a.; mussak, r. (2007) Anthocyanin dyes extracted from grape pomace for the purpose of textile dyeing. Journal of the Science of Food and Agriculture 87(14), 2589–2595. beradini, n.; knödler, m.; schieber, a.; carle, r. (2005) Utilisation of mango peels as a source of pectin and polyphenolics. Innovative Food Science and Emerging Technologies 6(4), 442–452. berghofer, e. (1982) Das Ordnungsprinzip der Grundoperationen und Grundprozesse in der Lebensmitteltechnologie. (The principle of classification of unit operations and unit processes in food technology). Zeitschrift für Lebensmitteltechnologie und Verfahrenstechnik 33, 156–172. bergstedt, u.; körner, h.-j.; kabasci, s.; deerberg, g. (2000) Simulation von Produktionsprozessen in der Biotechnologie. Chemie Ingenieur Technik 72, 1094. boger, t.; fritz, m.; ascher, r.; ernst, s.; weitkamp, j.; eigenberger, g. (1997) Selektive Trennung von p- und m-Xylol an zeolithischen Adsorbentien in der Gasphase, Chemie Ingenieur Technik 69, 475–480. bollinger, h.; noll, b. (2001) Innovation Haferfaser. Lebensmitteltechnik 4, 47–49. 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, 484–486. bonnin, e.; saulnier, l.; brunel, m.; marot, c.; lesage-meessen, l.; asther, m.; thibault, j.f. (2002) Release of ferulic acid from agroindustrial by-products by the cell wall-degrading enzymes produced by Aspergillus niger I-1472. Enzyme and Microbial Technology 31(7), 1000–1005. borrelli, r.c.; esposito, f.; napolitano, a.; ritieni, a.; fogliano, v. (2004) Characterization of a new potential functional ingredient: coffee silverskin. Journal of Agricultural and Food Chemistry 52(5), 1338–1343. borycka, b. (1996) Fruit pomace in new dietary fiber compositions. PrzemyslFermentacyjny-i-Owocowo-Warzywny (Poland) 40(12), 37–39. borycka, b.; zuchowski, j. (1998) Metal sorption capacity of fiber preparations from fruit pomace. Polish Journal of Food and Nutrition Sciences 7(48), 67–76. botella, c.; diaz, a.; de ory, i.; webb, c.; blandino, a. (2007) Xylanase and pectinase production by Aspergillus awamori on grape pomace in solid state fermentation. Process Biochemistry 42(1), 98–101.

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botella, c.; de ory, i.; webb, c.; cantero, d.; blandino, a. (2005) Hydrolytic enzyme production by Aspergillus awamori on grape pomace. Biochemical Engineering Journal 26(2–3), 100–106. braddock, r.j. (1999) Handbook of citrus by-products and processing technology. New York, Chichester, Weinheim: Wiley–VCH. bramorski, a.; soccol, c.r.; christen, p.; revah, s. (1998) Fruity aroma production by Ceratocystis fimbriata in solid cultures from agro-industrial wastes. Revista de Microbiologia 28(3), 208–212. bravo, l.; saura-calixto, f. (1998) Characterization of dietary fiber and the in vitro indigestible fraction of grape pomace. American Journal of Enology and Viticulture 49(2), 135–141. bröckl, u. (2001) Vorlesungsskript Informatik 2. Published on the wordwide web, http://www.it.fkt-esslingen.de/~broeckl/inf2/inf2dausmann.pdf. Esslingen/D. 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. (1995) Adding value to sugar beet pulp. Hoehere Erloese aus Zuckerruebenschnitzeln. Zuckerindustrie 120(5), 411–416. broughton, n.w.; dalton, c.c.; jones, g.c.; williams, e.l. (1995) Adding value to sugar beet pulp. International Sugar Journal 97(1154), 57–60, 93–95. brümmer, j.m. (1989) Eigenschaften verschiedener Ballaststoffquellen für die Brotund Kleingebäckherstellung. Ernährung 13(4), 222–229. buchenau, a. (1919) Rene Descartes: Abhandlungen über die Methode. Übersetzung mit Anmerkungen. Leipzig: Felix Meiner Verlag. budde, p. (2001) Programmierlogik. Published on the wordwide web, http://www. petra-budde.de/fachinformatikerDW/sites/programmierlogik.htm. bundesministerium für umwelt und naturschutz (1997) Kreislaufwirtschaftsund Abfallgesetz. Informationsschrift. bundschuh, e.; baumann, g.; gierschner, k. (1988) Untersuchungen zur CO2 Hochdruckextraktion von Aromastoffen aus Reststoffen der Apfelverarbeitung. Deutsche Lebensmittelrundschau 84, 205–210. bundschuh, e. et al. (1986) Gewinnung von natürlichen Aromen aus Reststoffen der Lebensmittelproduktion mit Hilfe der CO2 Hochdruckextraktion. Lebensmittelwissenschaft und Technologie 19, 493–496. campbell, g.m.; mougeot, e. (1999) Creation and characterization of aerated food products. Trends in Food Science and Technology 10, 283–296. cardillo, r.; fronza, g.; fuganti, c.; grasselli, p. et al. (1991) Stereochemistry of the microbial generation of δ-decanolide, γ-decanolide, and γ-nonanolide from C18 13-hydroxy, C18 10-hydroxy, and C19 14-hydroxy unsaturated fatty acids. Journal of Organic Chemistry 56(18), 5237–5239. cardoso, c.; mendes, r.; nunes, m.l. (2008) Development of a healthy low-fat fish sausage containing dietary fibre. International Journal of Food Science and Technology 43(2), 276–283. carle, r.; scheiber, a. (2001) Verbundprojekt: Gewinnung von Wertstoffen aus Trestern der Obst- und Gemüseverarbeitung. Teilprojekt: Isolierung von Wertstoffen aus Apfel- und Möhrentrestern. http://www.uni-hohenheim.de/ i3v/00217110/02043041.htm. carson, k.j.; collins, j.l.; penfield, m.p. (1994) Unrefined, dried apple pomace as a potential food ingredient. J Food Sci 59(6), 1213–1215. carvalho, w.; santos, j.c.; canilha, l.; silva, s.s.; perego, p.; converti, a. (2005) Xylitol production from sugarcane bagasse hydrolysate – metabolic behaviour of Candida guilliermondii cells entrapped in Ca-alginate. Biochemical Engineering Journal 25(1), 25–31.

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