15 Smoke flavourings in processed meats'1

J. ROZUM

15.1 Introduction For centuries, people have been searching for ways to preserve their hunt to ensure a food supply that would last them through the leaner times of the year. Possibly the first method used to preserve foodstuffs was smoking. Not only did it provide a cooked product with a different aroma, flavour and colour, it also prevented the product from spoiling as fast. Whether this was an accidental discovery or a thought-out process will never be known, but it changed the way people lived and ate. Wood smoke is composed of numerous chemical compounds and the possibilities of their reactions with food components are almost infinite. Over the course of the past 30 years or so, a great deal of research has been done to divide the components of smoke into major classes. Each class is considered the primary source for given functions in the smoking of foods. The major classes include acidic compounds which contribute to flavour and skin formation, phenolic compounds which provide flavour and preservation capabilities, and the carbonyls which react with proteins and other nitrogenous sources to give food a smoke colour. A fourth group, the poly cyclic aromatic hydrocarbons (PAH), are undesirable fraction of smoke as they are known to be carcinogenic. The differences in natural vaporous and liquid smoke PAH content will be discussed later. In early modern times researchers (Ostertag and Young, 1934) believed that the preservation of food by smoking was caused by the shrinkage of the muscle fibres and widening of the interstitial spaces. Other early investigators believed that the glossy appearance of meats after smoking meant that the proper resins, phenols and aldehydes were deposited onto the meat surface. The deposition of these compounds was termed the residual antiseptic effect in smoked meats. During the pyrolysis of wood to produce smoke, there are many variables which complicate any generalization as to the source of the important components of wood smoke. However, it is generally assumed that cellulose and hemicellulose form the carbonyl and acid fractions and lignin forms the phenolic fractions. It is then the make-up and amount of these components in wood which lead to the various flavours from different
*This chapter is dedicated to the memory of Dr C.M. Hollenbeck.

wood species. Knowledge of the wood and smoke chemistry allows researchers to take the smoking process a step further than the ancient caveman. They are now able to control the pyrolysis and products of the pyrolysis of wood to provide a broad spectrum of flavours and colours to the food industry. A look at the structure of these wood components, and some of the research that has been done on their breakdown products, seems to verify these generalizations (Maga, 1988). The chemical structures of the three major components of wood are shown in Figure 15.1. Some of the products and their possible pathways for formation during pyrolysis are discussed in the following sections. 15.2 Pyrolysis of cellulose

Cellulose is the major component of most wood species. The number of products produced by the pyrolysis of the cellulose component is large and

(a)

(b)

(C)

Figure 15.1 Structural inter-relationships of the three major components of wood: (a) cellulose; (b) hemicellulose; (c) lignin.

Table 15.1 Pyrolysis products of cellulose at 60O0C Compound Acetaldehyde Furan Acetone/propionaldehyde Propanal Methanol 2,3-Butanedione 1 -Hydroxy-2-propanone Glyoxal Acetic acid 2-Furaldehyde Formic acid 5-Methyl-2-furaldehyde 2-Furfuryl alcohol Carbon dioxide Water Char Tar Relative %
2.3 1.6 1.5 3.2 2.1 2.0 2.1 2.2 6.7 1.1 0.9 0.7 0.5 12.0 18.0 15.0 28.0

variable. The type and quantity of products are determined by the type of cellulose source and conditions of the pyrolysis performed. Shafizadeh (1984) has provided a list of some of the major products of cellulose pyrolysis at 60O0C (Table 15.1). The aliphatic acids and the aldehydes are the important compounds contained in smoke flavourings produced by the breakdown of cellulose. A series of pathways were proposed by Byrne et al. (1966) for the breakdown of cellulose to lower molecular weight aldehydes (Figure 15.2). It is these aldehydes which are responsible for the smoke colour formation in processed meats, including fish meat, and other foods. 15.3 Pyrolysis of hemicellulose Hemicellulose does not represent only one compound but encompasses a mixture of various polysaccharides. It represents about 20-35% of the mass of wood. It is the first component to undergo thermal decomposition in pyrolysis. Fengel and Wegener (1984) proposed some pathways for the decomposition of hemicellulose (Figure 15.3). The major degradation products are furan and its derivatives and a series of aliphatic carboxylic acids. These compounds contribute to the overall flavour and chemical properties of smoke but the exact reactions involved cannot be easily identified.

Glycollaldehyde

Furan

Glyoxal

Acrolein

Hydroxypyruvaldehyde

Figure 15.2 Mechanisms of the formation of carbonyl compounds. Acetyl groups O-Methyl groups

Furfural and Hydroxymethylfurfural

Mucic acid

Levulinic acid

1 /
i

Pyromucic acid

\ /

.1

V-Hydroxyvaleric acid

Furan

K -Valerolactone Figure 15.3 Thermal degradation products from hemicellulose.

15.4 Pyrolysis of lignin Mature hardwoods contain 20-25% lignin. The pyrolysis of lignin produces mainly phenolic compounds. A pathway for the production of phenolics from lignin has been proposed by Gilbert and Knowles (1975) as depicted in Figure 15.4. Syringol, 2,6-dimethoxyphenol, is the phenol that is produced in the greatest quantity. Syringol, and other phenolics, play the greatest role in providing the 'smoked' flavour to smoked foods. Other phenols, contributing to the flavour of foods, found in large quantities in liquid smoke are eugenol, isoeugenol, guaiacol, phenol and cresols. 15.5 Formation of colour in smoked foods The main colour-forming reaction in foods caused by smoke is the reaction of aldehydes with amino groups. This reaction, known as the Maillard reaction, and pathways involved have been described by Namiki and Hayashi (1983) as shown in Figure 15.5. Their pathway depicts the formation of a pyrazine polymer in the sugar-amino acid compound by way of a hydroxyacetaldehyde intermediate. Hydroxyacetaldehyde is the most active browning agent found in smoke. In the production of liquid smoke flavourings, every effort is made to maintain conditions for optimal aldehyde formation. This usually requires rapid quenching of the pyrolysis products to prevent their reaction with other smoke components. A recent trend in
Lignin

Ferulic acid

4-Methylguaiacol - 4-Ethylguaiacol '^"""^

4-Vinylguaiacol

I 1
r

> Acetovanillone

Vanillin

Vanillic acid

Guaiacol Figure 15.4 Thermal degradation products of ferulic acid.

Schiff base

Amadori product

Dialkylpyrazine cation radical

Figure 15.5 Two possible pathways for radical formation in the reaction of sugars with amino compounds.

liquid smoke production is in the development of a very rapid pyrolysis process to reduce the amount of time the smoke stays in the pyrolysis zone (Underwood and Graham, 1989). Current technology allows pyrolysis to occur in milliseconds instead of several seconds in older processes. Figure 15.6 shows how a reduced pyrolysis time affects the yield of hydroxyacetaldehyde. Table 15.2 shows the relative colour-forming potential of selected pure carbonyls when measured in three different ways. The browning index is a procedure used by Red Arrow Products Co. (Manitowoc, WI) in determining the amount of brown colour formation potential that is contained in their products. A glycine paper spot test involves coating a filter paper with a 1% glycine solution and allowing it to dry. A drop of the test solution is then dropped onto the glycine-coated filter paper. The filter paper is placed in an oven set at 200-30O0F (93-1490C) for approximately 1.5 min or until dry. This will give a colour which is subjectively compared to other tests. Weiner dip tests are done to determine the carbonyls' reaction potential on a meat system. Normal weiners are stuffed and dipped for a certain time in a carbonyl solution, and then processed. Colour formation on the weiners is then compared. Rozum (1994) has indicated that various individual carbonyls provide colour to slow-cooked pork fat even though the nitrogen level is fairly low in fat cells. The study

HYDROXACETALDEHYDE YIELD (*)

TIME (ms)

Figure 15.6 Fast pyrolysis of wood (hydroxyacetaldehyde versus residence time).

Table 15.2 Colour forming potential of selected carbonyls Colour intensity Darkest Browning index (pure carbonyls)3 Glycoaldehyde (18.9) Pyruvaldehyde (14.8) Glyoxal (6.4) Diacetyl (5.3) Furfural (4.9) Acetol (O) Formaldehyde (O) Glycine paper (pure carbonyls)b Glyoxal Pyruvaldehyde Glycoaldehyde Diacetyl Acetol Furfural 3-Hydroxy-2-butanone Wiener dips (pure carbonyls)b Glycoaldehyde Glyoxal Formaldehyde Pyruvaldehyde Acetol 3-Hydroxy-2-butanone Furfural

Lightest
a b

!0% solutions. Glycoaldehyde 0-3% solution; all others 5%.

also found that none of the major phenolic compounds found in smoke coloured the pork fat. In general, the reactions that occur to give the brown colour in smoked foods are time and temperature dependent. At higher temperatures the reactions tend to be fast, whereas at low temperatures the reactions tend to take longer. As an example, the glycine paper test takes about 1 min at 30O0F (1490C) in the oven to form complete colour, but takes over a year at O0F (-180C) to form any colour.

15.6 Smoke flavour in processed meats The flavour produced by smoking foods is a combination of unreacted smoke components and reacted smoke-protein components. The phenolic compounds are the major unreacted smoke components that contribute smokiness to the flavour. The unreacted and reacted acids, esters, lactones and carbonyls also contribute to the flavour. The flavour of the carbonyls comes from the Maillard reaction products. The flavour of individual smoke phenolics have been described by Kim (1974), as shown in Table 15.3. The profile of the phenolic components in a smoke can vary from one type of wood to another. The major independent wood sources are hickory and mesquite. To obtain a non-specific flavour a combination of hardwoods can be utilized. 15.7 Natural vaporous versus liquid smoke The origin of smoke flavouring can be from two sources, the burning of wood in a smokehouse or from liquid smoke flavourings. Both provide all the necessary compounds needed to flavour and colour meats and other foods. In natural vaporous smokehouses, all compounds formed from the
Table 15.3 Flavour descriptions of various phenols isolated from wood smoke Compound Phenol o-Cresol m- and /?-Cresol 2,3-Xylenol 2,4-Xylenol 2,6-Xylenol 3,4-Xylenol 3,5-Xylenol 2-Ethyl-5-methylphenol 3-Ethyl-5-methylphenol 2,3,5 -Trime thy !phenol Guaiacol 3-Methylguaiacol 4-Methylguaiacol 4-Ethylguaiacol 4-Allyguaiacol 2,6-Dimethoxyphenol 2,6-Dimethoxy-4-methylphenol 2,6-Dimethoxy-4-ethylphenol 2,6-Dimethoxy-4-propylphenol 2,6-Dimethoxy-4-propenylphenol Pyrocatechol 3-Methylpyrocatechol 4-Methylpyrocatecol 4-Ethylpyrocatechol Description Pungent Pungent Pungent Pungent Pungent Cresolic Cresolic Cresolic Cresolic Cresolic Cresolic Sweet, smoky, somewhat pungent Weak, phenolic Sweet, smoky Sweet, smoky Woody Smoky Mild, heavy, burnt Mild, heavy, burnt Mild, heavy, burnt Mild, heavy, burnt Heavy, sweet, burnt Heavy, sweet, burnt Heavy, sweet, burnt Heavy, sweet, burnt

burning of wood are deposited on the surface of the meat and the interior of the smokehouse. This includes all the wanted flavour and colouring components as well as the tars, volatile light organics and the carcinogenic PAH. It is these last three components that have caused many processors to go from the traditional natural vaporous smokehouse to liquid smoke. In the production of liquid smoke, the water insolubles (tars), light organics and PAHs are significantly reduced. This reduces the amount of time needed for clean-up (limited tar deposits), lowers light organic emissions, and lowers PAH levels in the final meat and fish products. The PAH levels may even be further reduced in some smokes by using resins to remove the PAH. Table 15.4 shows the reduction of PAH level in smoke over a period of time (Underwood and Rozum, 1995). 15.8 Evolution of smoke flavourings

The evolution of liquid smoke products has also allowed processors to obtain various flavours and colours that were not available to them before through natural vaporous smoking. They also allow the processor to add smoke flavourings to various recipes at a variety of steps in the processing. Most liquid smoke flavourings originate from one main starting ingredient, a 10% acid liquid smoke produced by a smoke generator. From this product a wide variety of acid levels, additions and deletions can be made to the smoke to produce several products. One of the first derived flavours was an oil-based smoke flavouring developed by Hpllenbeck (1969). This product is produced by extracting aqueous smoke flavouring with a vegetable oil. The oil extracts mainly phenols from the liquid to provide a flavouring agent with no colour forming properties. This product
Table 15.4 The removal of phenols from a 10% acid liquid smoke (Charsol C-10a) by adsorption on a resin column Treated volume (gal) Starting feed 10 20 30 40 50 65 75 85 95 105 Phenols (mg/ml) Carbonyls (%) Browning index
9.9 9.6 10.1 10.6 10.4 10.3 9.5 na 9.5 na 9.3

Brix

17.0 1.3 2.4 4.8 6.3 7.9 12.5 14.3 15.3 17.0 16.8

12.4 11.3 11.1 11.5 11.5 12.2 11.8 na 11.3 na 12.6

25.9 19.2 21.0 22.6 23.2 23.4 24.4 24.6 24.6 25.4 26.0

na = not analysed. a Red Arrow Products Co., Maintowoc, WI.

is widely used in processed meats and is added into the emulsion prior to stuffing. The next major development came 12 years later in the development of a brine-soluble flavouring. Underwood and Wendorff (1981) found that when a smoked oil was extracted with polysorbate 80, the phenolic compounds transferred into the polysorbate and became water soluble. This product is used as a smoke flavouring agent in almost all of the bacon currently produced in the USA, is used in other smoked meats, and is being added as a component of the pumping pickle. When the polysorbate 80 product is used internally, processors would sometimes still smoke the outside of the bacon to provide the brown colour. Seeing the need for a smoke that colours but provides low flavour, Underwood (1990) developed an aqueous product that produced colour but possessed very little flavour. This was accomplished by treating the aqueous smoke flavour with a non-ionic resin adsorption Column which removes a large portion of the phenolics from the smoke. Table 15.5 shows the removal of phenols by the resin without affecting the level of colourforming carbonyls in a 10% acid liquid smoke solution (Underwood, 1990). The low-flavour browning agent was then taken a step further to produce a product with no flavour with a high level of browning potential. This product developed by Underwood (1991) is used on a variety of products where only a minimum amount of smoke flavour is desired but a dark brown colour is wanted. The production of liquid smoke produces two main by-products, both of which can be used in other applications. One, the ash, can be used as a fuel source or can be further processed to produce briquets. The other is tar, which is the insoluble fraction that remains after the liquid smoke production. Tar is a good fuel source and can be utilized as such. It can also be processed into food additives itself. The first use of tar as a food ingredient was proposed by Miler (1969) who used various extractions to produce a product for flavouring sausages. Another important discovery
Table 15.5 Antibacterial properties of smoke flavourings in culture media Smoke flavouring E. coli Charsol C-6 (0.25% v/v, pH 2.4) Charsol C-6a (0.25% v/v, pH5.0) Charsol C-6a (0.25% v/v, pH 7.0) Acetic acid, 6.5% (0.25% v/v) Chardex3 (0.1% w/v) Aro-Smoke P-50* (0.25% w/v) CharoiP (0.25% v/v)
a a

% inhibition S. aureus
72 31 25 52 77 60 55

P. aeruginosa
52 51 54 29 46 62 52

L. viridescens
99 97 15 99 21 10 85

33 11 3 25 O 20 O

Red Arrow Products Co., Manitowoc, WI.

was by Dainius el al (1979) who used a distillation process to produce a low carcinogenic product for use in meats and pet food applications. 15.9 Food preservation with smoke Not only does smoking provide flavour, colour and other sensory effects to foods, it also affects preservation of foods. Smoke flavourings are potential effective antibacterial and antifungal agents. Varying degrees of inhibition by different smoke types against several organism types have been found (Sofos et al., 1988). The study showed that certain smoke varieties worked better than others against the same organisms. Wendorff (1981) measured the bacteriostatic and fungistatic activities of some smoke flavourings against some of the common food bacteria and fungi. Data from these tests are shown in Tables 15.6 and 15.7. It is believed that the acids and phenolics of smoke contribute to the inhibition of growth of both bacteria and fungi. However, Rozum (1995) found that when a polysorbate 80 smoke flavouring was used in cooked chicken, the phenolics were not able to control bacterial growth. It was hypothesized that
Table 15.6 Antifungal properties of smoke flavourings Smoke flavouring
a

Zones of inhibition (mm2) Penicillium sp. A. niger

18 16 12 12 9 9
A. flavus

Charsol C-6 (0.25% v/v, pH 2.5) Charsol C-6a (0.25% v/v, pH 5.0) Charsol C-6a (0.25% v/v, pH 7.0) Acetic acid, 6.5% (0.25% v/v) Chardex3 (0.1% w/v) Aro-Smoke P-50a (0.25% w/v)
a

21 19 17 16 12 9

14 13 11 13 8 8

Red Arrow Products Co., Manitowoc, WI.

Table 15.7 Antioxidant properties of natural smoke flavourings Antioxidant Initial Untreated control Charoil3 (0.4%) Charoil3 (0.2%) Aro-Smoke P-50a (0.04%) Aro-Smoke P-50a (0.02%) BHA (0.02%) BHT (0.02%) Propyl gallate (0.02%)
a

Peroxide value (meq/kg fat) Week 1

3.5 1.2 1.3 1.2 1.4 1.4 1.3 1.4

Week 2
8.5 2.0 2.1 2.0 2.1 2.1 1.9 2.1

Week 4

Week 26

0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8

18.4 2.4 3.0 2.2 2.9 3.3 2.8 3.0

43.1 3.7 4.6 3.4 4.9 12.5 4.8 5.8

BHA = butylated hydroxyanisole; BHT = butylated hydroxytoluene. Red Arrow Products Co., Manitowoc, WI.

when confronted with multiple organisms, the effectiveness of the antibacterial benefits is reduced. The phenolics in oil and polysorbate 80 smoke flavourings tend to behave as strong antioxidants as shown by Wendorff (1981) with pork fat. Previous research and casual observations show that smoke-processed meats do not develop rancidity as rapidly as cured, unsmoked meats.

15.10 Summary The pyrolysis of cellulose, hemicellulose and lignin is known to provide flavour and colour to smoked meats. The aldehydes produce the colour by reacting with nitrogenous compounds in meat, while flavour is mainly provided by the phenolics that are deposited on the meat surface. Through years of research, several new and innovative ways have been developed to provide a wider range of smoke flavours to the meat and food industry. The flavours range from a basic liquid smoke to smoked oils to smoked emulsifiers plus a wide variety of liquids that have been treated to remove or add certain properties. What has already been developed will definitely not be the end of new smoke flavourings, but only a step towards future flavour development.

References
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