Alternatives to phosphates are constantly being sought. Consumers are all too aware of clean-label food products and the demand is ever increasing. For many years, meat and poultry producers and processors have relied on that staple additive of phosphates.
For many product developers, the current marketing trend is to find ingredients which create that sought after clean-label. Any ingredient which satisfies consumer demand but offers a functional alternative which is as good if not better and is not too expensive is very much sought after. So it is with finding an alternative that standard of the meat processing world, sodium phosphate and its derivatives.
A number of articles have dealt with the issue in recent times (Jeong, 2016). Here we look at three classes of alternative ingredient solutions based on an understanding of their properties. These will include carbohydrates, proteins and surfactant molecules. We’ll also cover off the chemical structure of such ingredients and the impact they have on the biological, physiological and physical properties of meat muscle.
A Brief Look at Classification of Meat and Poultry Products
To understand how alternatives to phosphates might work requires an understanding of basic meat products.
Four categories exist:
Whole muscle – where intact muscle cells form a sophisticated 3D structure with water entrapped in the cellular and extracellular spaces. A pork or beef loin which is injected with phosphates would be such a product.
The Formed and Restructured meat product – chunks and pieces of meat are bound and ‘glued’ together. A good example would be restructured chicken nuggets.
Coarse Ground – minced and milled meat known as ground meat that destroys much of the 3D structure but still leaves the fibres intact. Think of burgers and patties!
Emulsified meats – a case of complex structural systems that would make a meat batter. These are mainly protein mixes containing solubilized muscle proteins, muscle fibres, fat, fragmented myofibrils and fat and water droplets. Meat sausages such as Bologna and other salamis or pates would be good examples here.
Each of these particular categories of meat product requires particular functional ingredients either alone or in combination. These improve certain functional attributes and targetted qualities in each of these classes (categories).
What Are The Main Goals To be Achieved In Each Category?
For a whole muscle or formed/restructured meat food, a primary objective of a functional ingredient(s) is to improve brine retention during marination and injection and to increase cooking yield. That pork loin mentioned earlier needs to retain moisture before and after it is cooked if it is to have the desired succulence.
For formed and restructured meat foods such as a deli chicken food, an additional benefit is to increase binding between meat pieces in the formulation. That same benefit is also conferred on coarse ground and minced meat foods too. The final category, emulsified meat foods rely on functional ingredients to stabilize the water and fat components in the meat emuslion especially when being processed.
Last but not least, functional ingredients are added to each of these meat foods whatever their classification to modify and improve texture. In virtually all the systems it is about moisture retention because meat quality depends so heavily on a juicy mouthfeel rather than one which is dry and difficult to chew on.
What Functional Ingredients Are Available To Us?
Three classes of functional ingredients are allowed to be used in meat products. The main synthetic ingredient is the group of alkaline phosphates and much of our discussion centres on their properties.
The alternatives are all clean-label based. Firstly, carbohydrates from plant sources such as flours and starches, natural plant fibers and hydrocolloids.
The other major group are proteins. There are a large selection of plant proteins to choose from. There are also animal proteins which may be derived from blood and from muscle meat itself, collagen, dairy proteins such as casein and whey, and egg proteins such as albumen from egg white.
Each functional ingredient has its own molecular mechanism of action.
Why Does Sodium Phosphate Work In Meat Products ?
Sodium phosphate is only permitted at a usage level of 0.5%w/w in processed meats. This is the final level in cooked processed meats like ham and sausages. Normally sodium phosphate is injected into muscle or into meats which have been minced, ground up or emulsified. It functions by retaining moisture in muscle fibres especially during cooking. Phosphate is also used to reduce rancidity, retain colour, improve elements of texture and is part of the curing process for producing high quality ham and sausage. It produces a better quality food because it is more moist, is bulkier and generally appears and tastes better (Tan et al., 2018).
At the chemical level, fresh meat ages which is characterized by a change in pH which becomes more acidic because lactic acid increases in the meat. There is a loss of calcium as it leaches from muscle and with it a loss of moisture. The fibres start to degrade and their structure collapse. This gives the impression that the meat is becoming tougher to eat and becomes dry. Using sodium phosphate is said to overcome these changes, not necessarily reversing it but by artificially maintaining a more alkaline pH. The increase in pH helps to increase the electrostatic repulsive forces between the myofibrillar proteins as the pH moves away from the isoelectric point.
It also retains calcium and magnesium by chelating these ions which under normal circumstances would leach away. By doing this, it also reverses rigor by splitting the actomyosin complex and adds to the increase in the electrostatic repulsive forces between myosin and actin.
A third mechanism of action is to increase ionic strength which leads to solubilization of a significant portion of the myofibrils.
In so doing this, the muscle fibres are allowed to swell as they would in a fresh piece of meat. So, the meat tissues retain their structure and increase their water holding capacity implying they do not allow water to migrate away especially during cooking or storage.
Phosphate solutions are usually injected as a brine. It is a common method of preparation and has been used along with lactate, salt, natural flavours, water etc. The meat processor is often looking to increase the meat’s weight by up to 10%. Addition of brine solutions helps to counter losses during storage (purge) or during cooking.
The performance of commercial phosphate blends is affected by the use of hard water, inadequate brine temperature, improper blend of phosphates (diphosphates, triphosphates, sodium tri-polyphosphate, hexametaphosphate, and pyrophosphate), and incorrect formulations of the marinade or injecting solution (Baluyot and Clark, 1996).
Other approaches to replacing phosphate will come with the use of marinades. For example marinades are regularly used with raw poultry meat to generate a flavour at the surface (Saha et al., 2009). A typical marinade will be an aqueous solution of salt, phosphate and flavouring. It is applied to the meat with soaking, injection and vacuum tumbling depending on the type of meat product. Here, the water holding capacity of the meat is improved and with it the phosphate alters pH and there is extraction of myofibrillar proteins so that phosphate can bind.
Alternatives to phosphates have been difficult to source because they cannot find the functional replacement that does everything that a phosphate can when it comes to meat (Sindelar, 2015). Phosphates as we have already mentioned also serve as antimicrobial agents in many respects.
The Nutritional Reason To Replace Phosphates
The main functional reason for replacing phosphates is to avoid using too much salt because of its links to cardiovascular disease and high blood pressure (hypertension) in particular. Having said that, many consumers are not only looking for foods generally with reduced salt but also lower in fat and sugar content. Another reason for replacement is the issue that synthetic phosphate could inhibit calcium absorption and disrupt bone formation (Virpi et al., 2006). Meat, especially processed meats are a classic example of the drive to manage consumer expectations. The use of alternative ingredients however will only be possible if they supplant phosphate because of a particular function that they can substitute for.
One of the reasons phosphates (and polyphosphates for that matter) are used in meat products is to improve water-holding capacity which in turn improves cook yield as well as increasing the weight and improving succulence. One of the other main reasons phosphates are successful is they sequester divalent metal ions like calcium. These bind to meat proteins and to then reduce dissociation of actomyosin (Trout, 1984).
When added to meat, phosphates attach to positively charged groups of proteins but the rest of the molecule attracts water molecules hence the increase in their water-holding capacity. The phosphate behaves as a polyanion and is the reason such an alternative is added. For maximum water binding and cook yield, a pH of 6-7 and an ionic strength of 0.6 are usually required.
What alternatives to phosphates are there?
Simple and direct replacement of tripolyphosphate for example is feasible. Some researchers have added 0.1% ammonium hydroxide (Cerruto-Noya et al., 2009) because it is alkaline. A trial was conducted into paired USDA Select beef strip loins. They were injected with either an alkaline‐based (3.6% sodium chloride, 1% Herbalox seasoning, adjusted to pH 10 with ammonium hydroxide [0.1%] or a phosphate‐based (3.6% sodium chloride, 1% Herbalox seasoning, 4.5% sodium tripolyphosphate) brine.
Mushrooms As Alternatives To Phosphates
One potentially valuable alternative is mushroom. In many ways mushrooms have even become an important alternative to meat but they have also been incorporated into meat foods to help reduce sodium content (Mattar et al., 2018). These researchers used a shiitake (Lentinus edodes) mushroom extract in some low-sodium burgers as a means of improving their taste and so creating a healthier meat food.
Many mushrooms are used in sauces primarily as flavour enhancers. Whilst they might not function like a phosphate where water holding capacity is concerned, they can be used to improve the taste of meat foods like burgers. It also means the ingredient list can be made to look more attractive by removing chemical sounding names and replacing them with ingredients like mushroom extract.
Not only is sodium content reduced, but mushroom extracts can also reduce lipid oxidation (Tom et al., 2018) and also replace fat (Wong, 2017).
People have tried winter mushroom powder (WMP) in emulsion-type sausages (Choe et al., 2018). Winter mushroom is also known as enoki or enokitaki. The powder also inhibited lipid oxidation and reduced fat separation. The WMP was added to a sausage emulsion at levels between 0.05 and 2% w/w with phosphate as a control at 0.3%. Here the winter mushroom powder increased the pH of the meat batter when the level was above 1.0%. If the level was 2% w/w then there was a noticeable change in the colour and sensory properties.
The same mushroom composition has been tried with low-salt chicken sausage (Jo et al., 2018). Likewise, the mushroom Flammulina velutipes works well at levels up to 5% in Cantonese sausages (Wang et al., 2019).
Amino-Acids As Alternatives To Phosphates
Various amino acids have zwitterionic properties which may behave like polyphosphates. Four amino acids were added to white shrimps – these were glycine, proline, lysine and arginine. Two amino-acids, lysine and arginine were highly effective. The arginine treated shrimps had a higher sensory acceptance than those treated with phosphates (Wachirasiri et al., 2016).
The Use Of Protein Solutions
At the other scale, protein hydrolysates are effective such as seal meat (Shahidi & Synowieki,1997).
Vann and DeWitt (2007) replaced phosphates in strips of beef loin which were made into an example of a steak. The control was a typical phosphate solution versus the experimental solution of an acid solubilized protein solution. The protein solution was chopped up beef which had its pH lowered to 2.5. using 50% phosphoric acid. The solution was filtered.
The phosphate injection was 4.5% phosphate, 3.6% sodium chloride, 91% water and a 1% Herbalox seasoning (Kalsec). The protein solutions injected were 1:9 protein to water and the other was an aqueous solution containing 1% Herbalox seasoning and 3.6% sodium chloride. In that study the protein-enhanced steaks were comparable to the phosphate-enhanced steaks in terms of their degree of discolouration and overall acceptability.
Just worth stating some of the terms used. The cook yield refers to the percentage of liquid lost during the cooking of a meat. Purge analysis is measure of the amount of water lost during storage.
Shear force is an analytical measure of the sensory aspect of ‘bite’. These are usually based on Research Guidelines for Cookery, Sensory Evaluation, and Instrumental Tenderness Measurements of Fresh Meat (AMSA, 1995).
The phosphate-treated steaks though performed better in terms of their fat and leanness colour, level of aerobic bacteria resistance, degree of lipid oxidation, percent purge, cook yield and a measure of shear force called the Warner-Bratzler shear force.
Other Protein Sources
Dehydrated beef protein appears to be effective when injected into beef strip loins (Lowder et al., 2011; 2013).
Other meat sources are also very good such as seal meat and dry collagen. Soy proteins and isolated soy proteins appear to work well. High-protein additives can be effective. Sodium caseinate, skim milk powder and whey have also been tested out (Ellekjaer et al., 1996; Yetim et al., 2006).
In nearly all countries, milk proteins are legally allowed in meat products. In the USA, skim milk powder and whey protein are allowed, but caseinate is not approved for use in sausages. In Norway, sausages can be made with the addition of non-meat proteins, including whey protein, skim milk powder and caseinate, as long as there is 80% water in the fat-free phase, up to 15% fat in the batter and 60% fat in the dry matter (Norwegian Food Regulation, 1983).
In various foods, milk proteins such as casein and whey are used as emulsifiers and as fat and water binders. Skim milk powder (35% w/w/ protein) is often used as filler in comminuted meat products because it has such as good binding effects. If lactose or indeed any reducing sugar is present, then browning is possible because of Maillard browning reactions with proteins (Mortensen, 1986).
Use Of Prune And Dried Plum
Dried plum and prune have also been assessed (Hooshmand and Arjmandi, 2009; Jarvis et al., 2012). The basis behind the use of dried plum and indeed any other fruit material is due to the action of pectin which is a fibre especially for moisture retention, the use of malic acid to enhance and improve flavour (Decker, 1999).
Dried plum also contains sorbitol – up to 17% which is humectant in its own right (Stacewics-Sapuntzakis et al., 2001). It attracts water molecules to its hydroxyl groups through hydrogen bonding.
Not everyone likes the addition of fruit to a meat product because of the flavour. Children for example did not rate breakfast sausage patties that had been prepared with blueberry puree or dried plum puree. They preferred the control sausages because they had a better mouthfeel, taste and overall liking (Leheska et al., 2006).
In another example, a trained sensory panel found the addition of dried plum to sausage a little better (de Gonzales et al., 2008a). The dried plum addition enhanced sweet taste, decreased salt and bitter tastes, and masked cooked pork/brothy, cooked pork fat, spicy/peppery, and sage flavors. They found that overall, pork sausage with 3% dried plum was as acceptable to consumers as the control, but patties with 6% dried plum were less desirable.
Addition of fresh plum juice concentrate, dried plum juice concentrate, or dried plum powder to beef roasts also altered flavours.
Use of Carbohydrates
Polysaccharides have been used as thickeners because they bind water and that property has been put to some use in meat products. Unfortunately, the role has been limited to comminuted foods where meat is concerned or as a coating. The inclusion of 5% plum ingredients (fresh plum juice concentrate, dried plum juice concentrate, or dried plum powder) in hams was shown to increase the fresh/dried plum aromatic note and sweet taste slightly, but decreased saltiness, resulting in a few sensory attributes of ham being affected only minimally (de Gonzalez et al., 2009).
Pectin as a single ingredient has been used in marinades for improving water holding capacity but could not alter the pH of chicken breast meat like sodium tripolyphosphate could (Zheng et al., 1999). Here they injected the fresh split chicken breasts with either 5% sodium acid pyrophosphate (SAPP), 5% sodium tripolyphosphate (STPP), 2.5% Genu pectin (GENU), or the combination of 5% SAPP with 2.5% GENU and 5% STPP with 2.5% GENU. The breasts were stored for 7 days at chill temperature to check for both quality and numbers of psychtropic bacteria. neither phosphate or pectin had any significant effect on the microbial activity associated with the marinated chicken which suggests there was no improvement of one over the other. A mixture of tripolyphosphate with some pectin had a lower pickup but the lowest water retention in the muscle of all the treatments.
Like phosphate, pectin has a large array of carboxylate groups on its backbone. This means it can hold water very effectively which may in part explain its properties in meat.
On a more parochial level, starches from rice and wheat make good replacers in improving water capacity. Citrus pectins and vegetable fibre appear to be very good. Unlike phosphate, fibres do not work at a molecular level with the actin-myosin complex but they have a high capability for binding water and improving texture. A partial phosphate replacement is possible.
Citrus fibre which includes plenty of pectin as well as non-soluble fibres like cellulose and hemicellulose, was used in an all-pork Bologna sausage (Powell et al., 2019). The cellulose has a particularly high water holding capacity as well as swelling capacity in water, so it can absorb more moisture. The hemicellulose has a good water-binding ability because of its branched, generally amorphous, and non-crystalline structure (Wen et al., 1998). The citrus-fiber is marketed as Citri-Fi is marketed as a natural alternative to phosphate. These sausages were stored for 98 days at close to freezing to just above freezing. It was used as a replacement for sodium tripolyphosphate (Powell et al., 2019).
Frankfurters, and hot dogs, especially low-fat versions also seem to benefit from addition of citrus fibre (Song et al., 2016). Low-fat (10% fat) frankfurters with different contents (0, 1, 2, and 3%) of citrus fiber were prepared. The cooking loss, water distribution, microstructure, and protein structure were assessed and compared to those of normal-fat (20% fat) frankfurters. Whilst phosphate was not necessarily replaced it made for a better low-fat sausage.
Citrus fiber treatments resulted in Bologna sausage with acceptable technological parameters, as indicated by similar cook/chill yields and emulsion stability compared to the sodium tripolyphosphate control. The results showed the replacement of sodium tripolyphosphate with citrus fiber did not significantly alter most physical, chemical or sensory characteristics of the Bologna sausage during refrigerated storage.
Inner pea fibre was added at different amounts to low-fat ground beef and improved tenderness and cooking yields with no detrimental effects on juiciness or flavor (Anderson & Berry, 2000).
Oat bran was added to fat-free frankfurters and low-fat bologna and resulted in products with greater yields, reduced red color, and decreased purge (Steenblock et al., 2001). In another study, oat bran and oat fiber were reported to provide the mouthfeel of fat in reduced-fat dry fermented sausages (Garcia et al., 2002).
Inulin coupled with sodium carbonate has also been touted as a suitable replacement.
Generally speaking, the addition of fibre as a replacement ingredient appears to produce a harder and firmer product (Chang & Carpenter, 1997; Cofrades et al., 2000).
Calcium Binders
A number of calcium powders have been tried (Bae et al., 2017; Cho et al., 2017) based on egg shell and oyster shell powder (Lee et al., 2011). These are byproducts of their respective processing industries and a good example of finding novel applications for what is usually waste material. These materials are effectively chalk which is calcium carbonate with differing levels of other minerals.
In the work by Cho et al., (2017), minced pork products were treated with between either 0.2% and 0.5% oyster shell calcium powder and/or egg shell calcium powder. They found that using egg shell calcium on its own or in combination with oyster shell calcium powder rather than oyster shell calcium on its own in these ground meat products was enough to increase water holding properties during cooking. Unfortunately, whilst they had analytical measures from a Texture analyser, there were no sensory studies conducted to back up any findings.
In a study by Lee et al., (2011), they prepared pork sausage with 0.5% whey protein and 0.3% oyster shell calcium to show significantly better water holding capacity and lower cooking loss. The Bae et al., (2017) study though showed cooking loss in their pork products using egg shell calcium was the worst of all the natural calcium-treated additives.
In terms of texture, Cho et al., (2017) showed increased tenderness of pork products which equates with lower cooking loss. The springiness and cohesiveness of the pork product using added egg shell calcium was improved but there are still doubts about the sensory effects of adding these small amounts of additives.
In earlier times, fermented pork sausage has been fortified with commercial or hen eggshell calcium lactate (Daengprok et al., 2002).
Turkey meat products have been manufactured using various combinations of brine containing curing ingredients, gums such as carrageenan, locust bean gum, starch and nonfat dry milk with KCl (Bater et al., 1992).
Restructured meats have been constructed using alginate and calcium gels.
One of the best phosphate replaces for a marinade was a 5% carrageenan solution. A combination of carrageenan with 2% non fat-dairy milk or starch also produced acceptable benefits. Locust bean gum or KCl were not as effective when used with carrageenan.
Ensor et al. (1989) reported that an alginate and calcium binder increased cook yield of restructured turkey products. Alginate restructuring produces adequate binding of meat chunks in both raw and cooked states and does not significantly affect aroma and flavor of the cooked product (Ensor et al., 1989). Levels of sodium alginate and calcium lactate or NaCl and phosphate may be adjusted to correspond to the relative properties of the meat block. In this instance, phosphate was part of the solution but there were examples where phosphate was needed .
Sausages were prepared with different mixtures of skim milk powder, sodium caseinate and whey protein (1.5, 3, 5%). Using Principal Component Analysis (PCA), the sausages with 1.5% milk protein were most similar in sensory quality to the control and showed minimal cooking loss. A mixture of 1:1 blend of skim milk powder and whey protein produced a sausage with the lowest cooking loss.
Frankfurters are good vehicles for testing our alternatives to phosphates. A variant prepared with oat bran and added water appeared to work within reason (Chang & Carpenter, 1997). In this instance, chicken frankfurters had their fat content reduced using oat bran with added water. The level of addition was less than 2% w/w.
One piece of research looked at incorporation of 1%w/w spent yeast extract into a cooked ham. At 12 and 90 days of storage, the claim was made that there were no observable differences in physical or sensorial properties. They did notice an increase in the levels of histamine, aldehydes and esters which have a flavour impact at the end of storage. They also noticed the ham had a ‘harder’ texture which they think was due to a gel forming during cooking. The yeast extract acted as a stabilizer (Pancrazio et al., 2016).
A nonphosphate blend called SavorPhos-200 has been used in both water- and oil-based marinades for both rotisserie chickens and breast meat (Casco et al., 2013). SavorPhos (Formtech Solutions Inc., College Station, TX) is a proprietary blend labeled as citrus flour, all natural flavorings, and less than 2% of sodium carbonate as a processing aid. According to the manufacturer, it is currently approved for sale as an all-natural ingredient for chicken marinades. Citrus flour is believed to be the functional fraction of the phosphate replacer that serves as a water binder, whereas the other ingredients also help with water holding capacity.
Lactates have been tested. Sodium bicarbonate and potassium lactate used in a poultry marinade resulted in higher marinade pick-up, lower purge loss, and higher cook yield than no-phosphate added chicken products (Lee et al., 2015).
How About Starches?
We have often discussed the functional properties of starches in a number of contexts and this is one good example.
Starches have been used for over 20 years in processed meats for adding texture in terms of binding water and controlling it especially during temperature conditioning. Added starch gelatinizes during any cooking process with water present which leads to it swelling and holding water. The next example illustrates the benefits of this aspect of starch chemistry.
Native starch from tapioca for example will improve the texture of sausages following cooking (Pereira et al., 2019). If this starch is added at a 2.5%w/w level into a sausage the emulsion stability increases because fat loss as a percentage loss for example is only 0.37% compared to an untreated sausage which loses 1.1% of its fat. Similarly, in terms of cooking quality which is monitored by assessing the cook yield and level of moisture retention, the cook yield of a starch-treated sausage is 98.6% compared to 83.7% for an untreated sausage. The moisture retention is also improved; 64.5% retention (tapioca starch treated sausage) versus 53.9% retention (control/untreated sausage).
Another aspect which is more relevant to emulsified meats is that gelatinization of the starch raises the viscosity of the emulsion during cooking and that helps to retain fats and lipids in their globules which also contributes to texture and flavour. This is demonstrated using scanning electronmicroscopy which shows that larger fat globules are entrapped in the protein+starch matrix compared to a sausage without added starch.
Starch has been used in combination with kappa-carrageenan (0.15% w/w) at levels between 2 and 5%w/w in ham. The hams were examined for cooking yields, purge texture and sensory acceptance. No synergistic effects were noticed especially on moisture retention (Prabhu & Sebranek, 1997).
Generally, starches which have a higher ratio of amylopectin are better for tumbling meat. The higher ratio of amylopectin results in a lower rate of retrogradation which in turn means that the meat retains more moisture and there is little or no syneresis (water loss). This results in a better quality and more succulent product for the duration of the product’s shelf-life.
Ruusunen with others (2003) used various types of modified tapioca starch, sodium citrate and wheat bran in low-salt frankfurters. Modified tapioca starch worked in this example by decreasing frying loss and improving upon the firmness of the frankfurter given it was so low salt. It compared more favourably to the replacement with sodium citrate which also decreased frying loss but the starch performed better.
Businesses such as Advanced Food Systems offer the branded Actobind® range of modified food starch for creating specific texture effects. The ingredients are designed for foods that need full retorting. They are mainly used to totally or partially replace phosphate.
Manufactures of clean label phosphate replacers include ezimoist™ from Ulrick & Short which is claimed to be suitable for tumbling, emulsification and injection. The product is starch based. Their starch sources are tapioca, rice, wheat, pea, waxy maize and sweet potato.
The Use Of Algae
Adding edible seaweeds appears to help with phosphate replacement in low salt gel/emulsion meat products (Cofrades et al., 2008). In their study, three seaweeds collected from the Northern coast of Spain were tried. They were Sea Spaghetti (Himanthalia elongata), Wakame (Undaria pinnatifida), and Nori (Porphyra umbilicalis) which were added at two concentrations (2.5% and 5% dry matter). They concluded that adding seaweed improved the water- and fat-binding properties except in Nori’s case when added at 2.5%. The hardness and chewiness of these low salt products was higher but cohesiveness and springiness were lower. There were also differences in colour being marginally darker.
The Hofmeister series
The Hofmeister series or lyotropic series is a classification of ions based on their ability to salt out or salt in proteins. Franz Hofmeister who investigated the effects of cations and anions on the solubility of proteins developed a series. Hofmeister discovered a series of salts that have consistent effects on the solubility of proteins and (it was discovered later) on the stability of their secondary and tertiary structure. Anions appear to have a larger effect than cations, and are usually ordered:-
The order of cations is usually given as:-
The anions with the greatest stabilization ability are phosphate anions.
Alternatives which mimic it in this series are highly desirable.
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