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Although wheat (Triticum aestivum) and related cereals [Barley (Hordeum vulgare), Rye (Secale cereale) are primarily used for producing baked goods and beverages, cereal crops can be used to create many value-added goods beyond these traditional products. Fractionation of cereal grains and extraction of valuable phytochemicals allows greater access to materials for use in food additives and nutritional supplements. Fermentation for beverage and fuel bioethanol production results in not only renewable fuel, but also a range of other coproducts, including nootropics. In addition to traditional grain fermentation, straw fermentation is also discussed, which further utilizes the whole plant. The main by-product of cereal grain fermentation, wheat stillage, can undergo a range of processes to enhance its value as a animal feeds, as well as extraction of useful compounds. These methods provide a glimpse of the many sequential and divergent processes that may bring us closer to realizing the full potential of wheat and related cereal grains.
*Address all correspondence to: timothy.tse@usask.ca and martin.reaney@usask.ca
1. Introduction
Wheat is the world’s second most produced grain [1], with global production forecasted to reach a new record of 780 million tonnes for 2021–2022 [2]. Wheat end-uses include food products (e.g., bread, pasta) [1], other consumer goods (e.g., hair products, skin care, cleaning agents) [1], and industrial applications (e.g., renewable fuels) [3]. In Canada, wheat varieties are often grouped by their functional properties and are categorized as Western Canadian or Eastern Canadian varieties, depending on the regions where they are grown [4]. These varieties are often used for the food and feed industry, although those with high starch and lower protein content are typically used as animal feed or for biofuel production [4, 5].
Opportunities to increase the value of wheat start while it is still growing, as limited grazing can allow the wheat to serve as both fresh feed for cattle and produce a harvestable crop at the end of the season [6]. Under suitable climatic conditions (i.e., low early-season rainfall) grazing by domestic animals can even improve crop yields by reducing lodging and improving the crops’ response to late-season rain [7]. After harvest, the most common processes for adding value to wheat are food related. In areas with high wheat production, flour mills can use the largest portion of available wheat by far, with most of the remaining wheat going towards production of breakfast food, pet food, and feed for livestock [8, 9].
In addition to traditional uses of wheat, fractionation of whole wheat grains can add considerable value. It is predicted that by 2024 the wheat starch market will exceed $4 Billion (USD) owing to significant use of wheat in agriculture-based industries [10]. The extraction of starch from wheat is an involved process requiring steeping and degermination [10]. After fractionation, bioactive compounds can be extracted and concentrated from individual wheat fractions, such as vitamin E from the germ and bran layers [11].
In North America, wheat is one of the predominant feedstocks for starch-based bioethanol production, especially where this cereal crop is locally available and abundant [12]. Wheat bioethanol is a renewable source of fuel, and its use can reduce greenhouse gas emissions when used to displace petroleum-based gasoline. Several valuable co-products can also arise from ethanol fermentation, including nootropic compounds, organic acids, glycerol, and a variety of fusel alcohols [13].
The recovery of grain by-products also holds crucial opportunities for wheat valorization, as waste products such as wheat straw also have value. Historically, wheat straw is incorporated into soil after harvest to improve soil quality, or removed and used as a component of animal feed or building material [14, 15]. Straw has also been investigated as a resource for liquid biofuel production (e.g., ethanol, butanol) [16, 17].
After alcoholic fermentation, additional processing can increase the total added value by utilizing the leftover stillage. Although fermentation consumes most available starches and sugars, proteins from both the wheat and yeast are left in the stillage after the ethanol is evaporated from the mash [18]. This protein-rich mixture can be integrated in animal feeds, as well as have valuable components removed to produce industrial chemicals [19].
In this chapter, we review value-added processes and products that go beyond the use of wheat for flours and beverages. These processes include fractionating whole wheat grain, extracting bioactive phytochemicals, fermenting both milled wheat and wheat straw for biofuel production, as well as the use of the resulting byproducts from wheat fermentation. Together, these processes provide a multitude of paths towards enhancing the total value of wheat.
Mature cereal grain like those from wheat, rye, and barley are primarily composed of starch, protein, and cell wall polysaccharide (Figure 1). Typically, these materials account for 90% of grain dry weight [20]. Many bioactive components of wheat grains (e.g., polyphenols, phytic acid, phenolics, and minerals) are concentrated in the bran [21, 22, 23], specifically the aleurone layer [24]. The aleurone layer contains the highest amounts of bioactive compounds with antioxidant activity [25, 26, 27, 28]. Additionally, wheat germ is also a source of value-added compounds including vitamin E (e.g., tocopherols) and oil.
Figure 1.
Anatomy of wheat grain.
Wheat bran obtained by milling constitutes about 15% of the mass of milled grain, and is composed primarily of the outer pericarp, inner pericarp, testa, hyaline layer, embryo, aleurone layer, and residual starchy endosperm (Figure 1) [20, 21, 22].
Starch accounts for ~60–70% of the mass of wheat grain [29] and is primarily composed of amylose and amylopectin [30], making it suitable for a wide variety of industrial applications, food products, and other consumer goods.
After milling, the endosperm is the primary product that makes up white flour (refined flour), while whole wheat flour (whole-grain flour) consists of the bran, germ, and endosperm [31]. Compared to white flour, whole wheat flour is richer in vitamins, phenolic acids, and minerals, as the whole kernel is included [31]. Meanwhile, due to the absence of bran, germ, and the aleurone components, white flour is more suited for use in baked food products that require leavening [31]. Further fractionation and milling processes can be used to isolate valuable bioactive phytochemicals.
Protein fractionation and extraction is another method of wheat valorization. Protein content can be influenced by the application of nitrogen fertilizer, which can result in an increased proportion of gliadin proteins, thus affording wheat that produces dough with increased extensibility [32]. Proteins make up to 7–22% of wheat grain dry weight [33], although it is unevenly distributed in the grain. For example, 5.1% of protein has been reported for the pericarp, 5.7% for the testa, 22.8% for the aleurone, and 34.1% for the germ [34].
Solvent fractionation can produce several protein concentrates with unique properties. Wheat protein fractions, like all proteins, are classified based on differences in their solubility: albumins are water soluble, globulins are soluble in dilute salt solutions, prolamins are soluble in 70% aqueous ethanol, and glutenin is soluble in dilute acids/bases [11]. Each protein fraction imparts different functionality to wheat products and when isolated can be used in specific applications. For example, wheat albumin can be used as a nutraceutical that controls blood sugar [35]. Wheat globulin has been found to increase dough stiffness and can be used in noodle products to improve both extensibility and hardness [36].
The other two fractions of wheat protein, gliadin and glutenin, are together know as gluten. Gluten is commonly marketed in two forms; vital wheat gluten, which can be hydrated using water to recover its elastic properties, and nonvital wheat gluten, which is irreversibly denatured [37]. Although nonvital wheat gluten is typically used as an ingredient for protein enrichment, vital wheat gluten can also be used for its structural properties [38]. Vital wheat gluten can be used to fortify flour and increase the elastic properties required for bread-making or can be used to produce textured protein products used to imitate or extend meat. Wheat gluten can also be used as a stabilizing agent for foods, particularly, commercially produced sauces. Vital wheat gluten has recently been gaining attention for its use as a biodegradable polymer suited for the manufacture of packaging materials.
Natural antimicrobials are more readily incorporated into wheat bioplastics than traditional plastics. Protein-based plastics are prepared at lower temperatures using conditions that are less likely to volatilize and/or degrade antimicrobials [39]. Additionally, wheat gluten has been proposed as a sensing material to monitor carbon dioxide accumulation within food packaging [40]. In the future, gluten-based foods might be available in biodegradable gluten-based packaging that acts as a matrix for antimicrobials such as essential oils, and provides feedback on whether the food inside is spoiling!
Whole wheat is a rich source of bioactive phytochemicals including, flavonoids, phytic acid, phenolic acids, carotenoids, tocopherols, alkylresorcinols, benzoxazinoids, phytosterols, γ-oryzanol, β-glucan, and lignans (Table 1) [41, 42]. Methods for extraction of these phytochemicals (Table 1) are further detailed in Luthria et al., [42]. Most of the phenolic acids (e.g., ferulic acid) exist in the form of bound insoluble complexes and are primarily aggregated in the cell wall matrix of whole grain [43]. These compounds have anti-inflammatory properties that promote gastrointestinal health [23]. They can also act as antioxidants to prevent heart disease and lower the incidence of colon cancer [23]. Consequently, wheat phenolic acids can have great value when formulating functional food products. Destruction of the cell wall matrix is necessary to increase the accessibility of these bioactive compounds. This can be accomplished using a variety of processes including the use of enzymes, fermentation [44], steam explosion, and ultra-fine grinding [45].
Other antioxidant compounds include pigments (e.g., carotenoids). These are typically found in the germ, aleurone, and endosperm fractions [46], although the distribution of these compounds can vary depending on the type of wheat (e.g., einkorn, durum, and common wheat) [47, 48, 49]. Carotenoid content in wheat grain can range between 1.8 and 5.8 mg/g [50]. These pigments (e.g., lutein, zeaxanthin, β-carotene) can have provitamin A activity and provide protection against cardiovascular disease and UV-inducing skin damage, as well as yielding products that impart improved antioxidant capacity and can mitigate oxidative stress [11, 46].
Wheat is also a moderate source for vitamin E (e.g., α-tocopherol) [11], providing approximately 5-17 mg of α-tocopherol equivalent per 100 g [51, 52]. The sum of all tocopherols and tocotrienols (a.k.a. tocols) in wheat is in the range of 49–58 mg/g [53, 54, 55]. Wheat germ tocols are primarily α- and β-tocopherols, whereas tocols of the pericarp, testa, and aleurone are enriched in tocotrienols [11]. α-Tocopherol is a fat-soluble antioxidant that protects cell membranes with high contents of polyunsaturated fatty acids against oxidative damage [56, 57]. When consumed, these tocols mitigate the production of reactive oxygen/nitrogen species and modulating signal transduction [56] thereby boosting immune response [57].
Wheat β-glucans, lignans, and phytosterols have been investigated as treatments for hypercholesterolemia and cardiovascular disease [58, 59, 60]. Importantly, a major lignan in wheat bran was identified to be secoisolariciresinol diglucoside (SDG), which is known to be converted into the mammalian lignans enterodiol and enterolactone by intestinal microflora [61, 62]. Wheat also contains lariciresinol diglucoside. These lignan metabolites function as antioxidants and free radical scavengers, leading to decreased risk of cancer development [61, 63] and hypocholesterolemic properties [64]. These compounds are predominantly concentrated in the outer layers of the grain (e.g., seed coat and pericarp), and in the aleurone layer; however, small concentrations can be found in the inner endosperm [65]. Compared to other cereal grains, wheat is not rich in lignans [66], although they can be a source of SDG. Approximately, 2 mg/g of secoisolariciresinol can be found in the common wheat germ, refined flour, and whole grain flour [65]. Overall, total lignan content in common wheat can range from 2 to 52 mg/g in the germ, refined flour, or whole grain flour [65].
Other value-added components include oil content in wheat bran (3–4%) and germ (7–9%) [67]. Due to the presence of antioxidant bioactive phytochemicals the health benefits of these oils have been investigated [67]. For example, wheat germ oil and wheat bran oil were found to contain high amounts of polyunsaturated fatty acids, as well as bioactive compounds tocopherols, carotenoids, and oryzanol like compounds (e.g., steryl ferulates) [67]. Wheat germ oil can be obtained via mechanical pressing of separated wheat germ, whereas supercritical CO2 extraction [68, 69], or solvent extraction [70] can be used to recover oil from both wheat germ and wheat bran. The content of bioactive compounds in these oils could be of sufficient quantity to mitigate cardiovascular disease, diabetes, cancer, and other diseases [67]. They have also been utilized in a range of medicinal (e.g., fish oil production), cosmetic (e.g., shampoo), insect control, vitamin, feed, and food products [70]. More recently, the utilization of wheat germ oil and wheat bran fiber have successfully been applied as a fat replacer in developing low-fat beef patties, resulting in better quality, stability, and reduced cholesterol content [71]. Since wheat germ is a by-product of wheat milling and contains extractable oil, isolation and purification of these oils can add significant value as a source of bioactive phytochemicals.
In general, the stability of wheat bioactive phytochemicals can be influenced by processing (milling, fermentative proofing, baking, enzymatic hydrolysis, extrusion, cooking, steaming, malting, etc.) [72] and storage conditions (temperature, light, pressure, time, etc.) [73]. For example, cooking of wheat grain can result in a 55% loss of tocopherol content [74], and increased temperatures and pressures can result the degradation of antioxidant pigments [75]. Therefore, depending on the wheat variety, food processing and milling methods can greatly affect the concentration and activity of wheat bioactive compounds [42, 76].
Bioethanol can be produced using any sugar or starch-rich crop, and is an increasingly attractive fuel type as it reduces reliance on the limited supply of fossil fuels. Biofuels generated from renewable feedstocks can contribute to the reduction of greenhouse gases when compared to crude oil. Globally, the total production of ethanol is over 26 billion gallons in 2020 [111]. In Canada, wheat is the second most common feedstock used for bioethanol, and wheat fermentation is of interest for developing local and renewable energy supplies across many parts of Asia, Europe, and North America.
Ethanol production for biofuels is typically accomplished with a simplified process. Wheat entering the process is typically coarsely milled then rapidly heated with steam to destroy any microbial contamination and produce a thick mash. Sugars are released from the starch by an enzymatic process called saccharification. Initially, starch is treated with heat tolerant alpha-amylase that can function at temperatures as high as 95°C. Subsequently, glucoamylase is added to release more sugars. Other enzymes are optionally added to decompose pectins and hemicellulose. After saccharification, nutrients are added to accelerate the fermentation [112]. Fermentation using yeast (typically Saccharomyces cerevisiae) converts the sugar to ethanol, with many factors affecting the final ethanol yield [113]. After fermentation, the mixture, called beer, is transferred to a distillation system where ethanol is distilled from the beer [13]. Finally, the ethanol mixture is further purified through rectification and dehydration, resulting in a final ethanol concentration of 95% or higher [114].
A relatively recent improvement to the fermentation process, referred to as very high gravity (VHG) fermentation, involves the use of the highest possible concentration of sugar in the mash. Select yeasts strains have been identified that can tolerate both the high initial sugar concentration and high ethanol concentrations (>15%) [114, 115]. By fermenting high concentration solutions, considerable amounts of water can be saved, allowing plants to operate at higher capacity without the need for additional space and equipment [116]. The yield of ethanol from wheat can be improved through selection of high starch and low protein cultivars [117].
During fermentation of wheat grain, additional value-added compounds are also produced including glycerol, succinic acid, acetic acid, lactic acid, and α-glycerylphosphorylcholine (e.g., a nootropic compound) [13, 118]. The nootropic compound α-GPC has been investigated as a treatment for Alzheimer’s disease and strokes [119]. Production of α-GPC varies significantly with cultivar, and several cultivars have produced promising amounts of this substance when fermented [118, 120].
Despite the potential positives of bioethanol as a replacement for fossil fuels, there have been many criticisms of the use of food sources for bioethanol production. A major concern is that using crops in large-scale production of bioethanol will divert food to the energy sector. It is feared that this competition will increase food prices and contribute to the scarcity of available products as the world population grows [121, 122]. As production of biofuel expands, the materials used must be based on non-food sources such as byproducts, waste, or agricultural losses to remain economically viable and sustainable. Most wheat produced is used for human consumption; it is grown in over 120 countries, and accounts for approximately 1/5 the world’s caloric needs [123]. To avoid competing with food crops for agricultural land, bioethanol can instead be produced using less nutrient-rich parts of the crop, such as the straw.
Wheat straw is one of the most abundant agricultural byproducts and is of low commercial value. Straw is primarily used for cattle feed, disposed of, or even burned as waste. On average, 1 kg of straw is collected for every 1.3 kg of grain [124], and this straw can be used as a feedstock for producing bioethanol. Pre-treatment of lignocellulosic products such as wheat straw is required prior to fermentation and is performed using hydrolysis to make cellulose more conducive to enzyme action [125]. Commonly, steam explosion is used as a pre-treatment method and combined with an acid catalyst in wheat straw bioethanol production [124, 126, 127, 128]. Other studies have demonstrated success in using H2SO4 prior to steam treatment to improve sugar, and therefore ethanol, yields [129]. Production of biofuels from cellulose-rich materials is generally more complex and requires new technologies, but the prices of raw materials such as wheat straw are significantly less and act as an incentive for the biofuel industry to pursue lignocellulosic resources. Currently, the overall production of bioethanol from grain is less costly than from wheat straw [130], however, as the technology develops and government restrictions on greenhouse emissions increase, the use of cellulose-rich materials in bioethanol production is likely to grow significantly.
Biofuel production also provides an opportunity to reclaim damaged and spoiled crops [131]. Damaged grains (e.g., discoloration, breakage, cracking, fungi infection, insect damage, chalky grain) used for ethanol production can reduce feedstock costs by a factor of 10 when compared to grains of higher quality [131]. Alcoholic fermentations of wheat damaged from some of these materials, such as Fusariumfungal infections, can produce stillage/wet grains that are unsuitable to use as feed for cattle due to the presence of mycotoxins [132], however, these byproducts need not go to waste. Fermented Fusariuminfected wheat can be fed to black soldier fly larvae which are able to degrade the toxins, allowing the wheat’s nutrients to be recovered [133, 134]. The larvae can then be dried and sold as a highly nutritional and protein-rich feed ingredient.
Alcoholic fermentation of wheat depletes available simple sugars and starches, as these are used for the yeast to grow and produce ethanol. However, after the ethanol is distilled from the beer, the remaining stillage contains protein, oils, fiber, and non-starch carbohydrates. These residual nutrients can also add significant value to fermented wheat through a variety of different processing options. Most commonly, whole stillage is separated into thin stillage (liquid containing suspended solids) and distillers’ wet grains (wet solid portions) using physical processing techniques such as screening and centrifugation [135]. The thin stillage can then be dewatered and heated, resulting in a condensed syrup known as distillers’ soluble. By mixing the syrup with wet grains as they dry, a nutritional cattle feed referred to as distillers’ dry grains with soluble (DDGS) is produced [136].
Compared to unprocessed stillage/wet grains, DDGS has a much greater shelf life and is more readily transported [137]. The DDGS also contains a higher concentration of protein (~38%) than unfermented wheat [19], and the sale of cattle feed typically provides 10–20% of an ethanol producer’s revenue [137]. Fermented wheat can also be further enhanced as a feed product through various protein concentration methods [18], including secondary fermentation using lactic acid bacteria. Secondary fermentation can result in an increase in higher value compounds such as 1,3-propandiol, and a feed with up to 60% protein [138] and greater probiotic content [139].
Alternatively, protein from DDGS can be solubilized and extracted to allow amino acids to be removed individually [19]. By leaving essential amino acids in the DDGS, the product can retain value as an animal feed, while allowing valuable non-essential amino acids to be extracted. The extracted amino acids can include aspartic acid, glutamine, glycine, l-arginine, l-lysine, l-phenylalanine, proline, and serine [19]. These non-essential amino acids can have further value added through various chemical transformations, such as aspartic acid into acrylamide [140].
Protein can also be concentrated by the removal of other substances, such as fiber, from the fermented wheat products. Fiber can be removed via aspiration of DDGS coming from dry-grind ethanol facilities [141]. This can allow the fiber-rich fraction to be valorized through the extraction of phytosterols, which are concentrated in the fraction. The reduced fiber content of the remaining fraction results in higher protein and fat content, improving its value as a feed [142]. DDGS can also be fractionated into high protein and high fiber fractions through sieving [143]. By using a combination of both air classification (winnowing) and sieving, a fiber fraction of around 50% reduced protein, and a fraction with an additional 30% protein can be produced, compared to the whole DDGS [117]. Oil is another component of wheat that is still present after fermentation. Although there are patented techniques for extracting oil from corn DDGS and thin stillage [144, 145], the lower oil content of wheat and other grains has resulted in oil extraction techniques remaining largely undeveloped for fermented wheat products.
Wheat is one of the largest grain crops produced in the world, second only to corn, with United States and Canada being the two largest exporters of wheat globally. Typically, the end products of wheat are used as food sources for either human or animal consumption, however, the production of biofuel using feedstocks such as wheat is steadily expanding. The fractionation and appropriate selection of harvested wheat crops is crucial to increase economic value; wheat varieties can be tailored for specific applications, such as biofuel production, or the extraction of bio-active phytochemicals. Furthermore, the stability, quality, and concentration of bioactive compounds can be affected by the processing and storage conditions of wheat, which contribute to the value of these products in cosmetics or antioxidant and anti-inflammatory supplements. Typically, biofuel production uses wheat grain with high starch content to create efficient and productive fermentations. This type of biofuel production is under increasing criticism for the diversion valuable food sources and agriculturally productive land. By using grain production by-products such as wheat straw, or damaged grained crops, ethanol production can be accomplished with reduced greenhouse gas emissions and less expensive, renewable feedstocks. Lignocellulosic by-products can add significant value to wheat through fermentation and will be of growing interest with increasing societal and economic pressures to reduce dependency on petroleum. Even after fermentation, the remaining stillage can be used as high protein feed, and have valuable products diverted to industrial streams. Overall, these processes can substantially enhance the value of wheat and reduce agricultural waste. The future will likely lead to new techniques and further improvements in wheat processing.
This work was supported by the Saskatchewan Agricultural Development Fund (20190155, 20190154, 20180281, 20180248, 20180255, 20170133); National Sciences and Engineering Research Council of Canada Discovery Grant (RGPIN-2018-06631); and Mitacs (IT19122, IT16156).
Dr. Martin J.T. Reaney is the founder of, and has an equity interest in, Prairie Tide Diversified Inc. (PTD, Saskatoon, SK, Canada: previous company name is Prairie Tide Chemicals Inc.).
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Written By
Timothy J. Tse, Farley Chicilo, Daniel J. Wiens and Martin J.T. Reaney
Submitted: December 21st, 2021Reviewed: January 11th, 2022Published: February 26th, 2022
Open access peer-reviewed chapter - ONLINE FIRST
