MXPA06008761A - Calcium fortification of bread dough - Google Patents

Abstract

Calcium additives useful for fortifying baked goods, such as bread products, with calcium are disclosed. The calcium additives are particularly useful for fortifying leavened baked goods with calcium. Methods for preparing the calcium additives and using the calcium additives to fortify baked goods are also disclosed. Generally, the calcium additives comprise suspensions of calcium carbonate in acidic aqueous solutions such as citric acid solutions.

Description

FORTIFICATION OF BREAD CALCIUM Field of the Invention The present invention relates generally to compositions and methods of enrichment of foods with calcium. More specifically, the present invention relates to calcium carbonate suspensions in aqueous acid solutions which are useful for enriching the calcium content of baked products, particularly, fermented bread products. Background of the Invention Calcium is an essential nutrient and the most abundant mineral in the human body. Calcium plays a vital role in the construction of healthy teeth and bones, blood coagulation, muscle contraction, nerve function and heart function. In addition to these benefits, it has recently been suggested that calcium reduces the risk of recurrence of colon polyps. See the Publication of Baron J. A. et al. , New England Journal of Medicine 1999; 340: page 1 01 to 1 07. More importantly, calcium reduces the risk of bone loss caused by osteoporosis, both in men and in women, a condition that afflicts more than 44 million individuals only in The United States of America. With a population that is aging in the United States of America, it is estimated that the figure will rise to more than 61 million per year in 2020. This growing health crisis is largely a result of calcium deficiency in the diet. In recognition of the benefits of calcium, doctors recommend high daily calcium assimilations for people of all age groups. For example, the National Academy of Sciences ("ÑAS") of the Istituto de Medicina recommends the daily assimilations of calcium shown below.

National Institute of Sciences, Institute of Dietetic Medicine Calcium Reference Assimilation (DIR) for Men and Women Age ARD 1-3 years 500 mg 4-8 years 800 mg 9-18 years 1, 300 mg 19-50 years 1, 000 mg 51 years in 1, 200 mg forward Similarly, the Daily Tolerance Recommended by the United States ("USRDA") of calcium for adults is 800 to 1, 400 mg. However, it has been estimated that half of all Americans do not consume sufficient amounts of calcium. What is more problematic, 80% of the women in the group with the highest risk of developing osteoporosis, do not consume enough calcium. In addition, the estimates reveal that only 20% of girls and 50% of boys between the ages of 9 and 9 years get a recommended daily assimilation of calcium. This is particularly problematic because 90% of the human bone mass is developed by the age of 17 years. Therefore, a correct intake of calcium during these years is critical to avoid the presentation of osteoporosis in later life. For many individuals, it is difficult to comply with the daily assimilation of calcium suggested by doctors only from dietary resources. This calcium deficiency is due in part to the low calcium content of the foods that comprise the typical diet. Calcium supplement tablets and multiple vitamins represent an important alternative for dietary calcium. However, most commercially available multi-vitamin tablets provide only 10% to 20% of the recommended dose of calcium. Supplemental calcium tablets provide more calcium, generally 500 to 600 mg. To comply with the recommendations, two tablets should be consumed daily. Unfortunately, very few people adhere to the calcium supplement regimens, due in part to the fact that the calcium tablets that are currently available are very large and difficult and uncomfortable to swallow. Milk is widely recognized as a good source of calcium. You should consume several glasses of milk every day in order to get enough calcium. For example, children 9 to 18 years of age should consume at least four glasses of milk daily in order to receive the correct amount of calcium. Nevertheless, the popularity of carbonated drinks has resulted in a decline in milk consumption among children. In addition, many individuals suffering from lactose intolerance can not drink milk. Other individuals choose not to drink milk because of its high content of saturated fats. Consumers' health awareness is increasingly demanding alternative sources of calcium from dietary products. This is evident from a recent study by International Mintel that shows an increase in food products and beverages sold in North America which advertise the calcium content. According to the study, 32% of dairy products, including milk and cheese, 27% of beverages and 18% of fast food advertise the calcium content. In contrast, only 5% of the baked goods have adopted the calcium content. This is unfortunate because bread and cereal products are the most ubiquitous food sources worldwide. For example, the Department of Agriculture of the States of America estimates that approximately 90.71 8 kg (200 pounds) of flour and cereal products per capita were consumed in the United States in 2001. A figure which has been constantly growing during the last three decades. In contrast, only 1 02.206 L (22 gallons) of milk per capita was consumed in the United States during the same period. Clearly, bread products would provide an ideal vehicle to supplement the dietary assimilation of calcium. Unfortunately, conventional breads represent a deficient source of calcium. The total mineral content of wheat is generally in a range of 1% to 2% by weight. The minerals present in wheat are mainly distributed in the shell and are present in the endosperm, the fraction of wheat from which most of the commercial flours are produced, to a smaller degree. For example, wheat generally contains about 0.45% by weight of elemental calcium. The shell fraction contains approximately 0.128% or by weight of elemental calcium, while the flour fractions, such as farina, patent flour and clear flour contain less than 0.03% by weight of calcium. Breads made from these conventional flours will obviously contain only a small fraction of the recommended daily calcium intake. It is conventional in the baking industry to add calcium sources to bread products, such as "mass conditioners". Generally, calcium sulfate or calcium carbonate is added to the dough, in order to regulate the pH and increase the electrolytic resistance of the soft water to avoid a soft or sticky dough. Said calcium conditioners for the doughs are generally added to the dough in amounts of about 0.1% to 0.6% by weight. These calcium conditioners of the masses are not present in sufficient amounts to contribute in an important way to the calcium value of the resulting bread products. Calcium sulfate and calcium carbonate can not be added directly to the dough in large enough quantities to contribute to the calcium content of the bread, due to inherent limitations imposed by the chemistry of the dough. In the fermentation process that occurs in fermented breads, pH plays a critical role in controlling yeast activity, amylolytic activity and gluten behavior. The pH of the bread is generally in a range of about 5.1 to about 5.4. To reach these final pH levels, the dough must have a final pH level as low as 4.5 to 5.2, however the pH must drop even lower during the fermentation process. For example, the typical commercial production of bread fermented by the process of dough-biscuit, the pH of the ingredients initially mixed in the biscuits is approximately 5.3. As the fermentation process proceeds, the pH will fall rapidly during the first two hours of incubation. The fall in pH is mainly the result of lactic, succinic and acetic acids produced by fermentation. During the next two hours of fermentation, the pH will stabilize at a final value of about 4.7. When the remaining ingredients of the dough are added to the sponge cake, the pH will quickly rise again to its initial value of approximately 5.3 due to the effects of dilution and regulation of the added flour. The subsequent fermentation again results in the pH falling to a final value of about 5.0. As the dough is baked, the volatilization of the fermentation acids causes the pH to rise to a final value of about 5.4 in the finished bread product. Some specialty breads, such as French bread can have a pH as low as about 3.8 to 4.0, still requiring lower pH drops during the fermentation process. Calcium salts, such as calcium carbonate, calcium sulfate and calcium citrate exert a regulatory effect on the chemistry of the dough by reacting with organic acids produced during fermentation. Even relatively low levels of these calcium salts will prevent the pH from lowering during fermentation, interfering with the functioning of the yeast and altering the taste and texture of the resulting bread product. At higher levels, these salts can result in a dough with a basic pH. Despite its low solubility in water, a saturated aqueous solution of calcium carbonate has a pH between 9 and 10 at room temperatures. Therefore, calcium carbonate can not be added directly to the dough without presenting the acidic pH characteristic of most of the bread dough. In addition, a very low solubility in water of calcium carbonate can result in granular precipitates when it is added in large amounts to the mass. For these reasons, it is not appropriate to fortify bread products by adding traditional calcium salts directly to the dough. To date, efforts to increase the calcium content of bread by other methods have met only with limited success. US Pat. No. 5, 108,764 issued to Craig describes the step of raising the mass of the addition of calcium carbonate for its nutritional value in the production of reduced fats or without added fats. The amount of calcium carbonate added is described as "minor". US Patent No. 6,126,982 issued to Malmasado discloses bread products having increased calcium contents produced from flours having large amounts of added quality products. This patent proposes to produce bread products that have up to 200% USRDA calcium dose per serving. However, the utility of the method described by Malmasado is limited by the requirement of the addition of medium quality products, since many commercial breads require highly purified flours. U.S. Patent No. 5,514,387 issued to Zimmerman et al. , describes biscuits and other baked goods that provide more than 10% of the USRDA calcium dose. The process described uses emulsifying compositions, such as combinations of polysorbate 60 and sodium stearoyl lactylate to reduce hardness and dry mouth sensation caused by the addition of insoluble calcium salts, such as calcium carbonate. The fermented biscuits produced by the method described in this patent report that they have pH values between 6.6 and 8.2, much higher than the tolerable pH of a typical commercial baked bread product. US Pat. Nos. 4, 859,473 and 5,066,499 granted to Arciszewski et al. , describe the addition of calcium carbonate to the step of raising the dough in a process to prepare biscuits and biscuits with low sodium content. Calcium carbonate is added for its nutritional value in amounts of up to approximately 10% by total weight. The resulting pH of the baked products described, between 6.5 and 8 is higher than the tolerable pH of most commercial baked goods. US Patent No. 6,210,720 issued to Leusner et al., Describes a lightly cooked cereal dough that is a fortified product with at least 0.3% calcium. The process described comprises the addition of calcium carbonate having a small average particle size and a calcium sequestering agent, such as phosphate salts or citric acid to a traditional cereal dough. The calcium carbonate and the calcium sequestering agent are added to the mass together with a wet mixture. Calcium fortification of fermented bread products is not described. U.S. Patent No. 5,945, 144 issued to Hahn, et al. , discloses a paste fortified with calcium produced by adding calcium salts, such as calcium strata to the bread dough before extrusion. The methods described would not be applicable for preparing fermented bread products fortified with calcium. U.S. Patent No. 5,260,082 issued to del Valle, et al., Describes a calcium citrate additive for baked goods. Calcium citrate is prepared by reacting the citric acid with calcium hydroxide or calcium carbonate in an aqueous solution followed by dry spraying to produce fine crystals of calcium citrate. The calcium citrate crystals are added directly to the dough to produce the mentioned bread products so that they have an improved volume, shelf life and microwave baking capacity compared to both the control loaves that do not have the additives and the Bread products prepared from commercially available calcium citrate. U.S. Patent No. 5,260,082 does not disclose the addition of calcium citrate to bread products because of its nutritional value. It would be desirable to enrich a variety of bread products with sufficient amounts of calcium to supply the recommended daily dose of calcium. To this end, it would be desirable to enrich bread with calcium carbonate because calcium carbonate is the most abundant and least expensive source of elemental calcium. Therefore, it is an object of the present invention to produce bread products fortified with calcium, particularly in the form of calcium carbonate. It is a further object of the present invention to produce bread products fortified with calcium having organoleptic properties, crumb structure, volume and mouthfeel comparable with conventional breads. It is a further object of the present invention to produce calcium additives and methods for fortifying bread products with calcium additives. Brief Description of the Invention In accordance with the above objectives, the present invention provides baked goods, such as bread products, which are highly fortified with calcium. Calcium additives and methods for preparing such calcium fortified bread products are also provided. It was surprisingly discovered that calcium carbonate suspensions in aqueous acidic solutions prepared under the conditions described herein can be added to the dough to increase the calcium content without adversely affecting the properties of the dough. Without wishing to be bound by any theory, it is considered that the additives of the present invention exist in the form of a fine suspension of calcium carbonate powder in an acidic environment provided by soluble inorganic or organic acids. It is not expected as is known that a calcium carbonate solubilized completely in water reacts with acids to form calcium salts, carbon dioxide and water.

Said reaction is evidenced by the evolution of the carbon dioxide bubbles in appropriately prepared solutions of these ingredients. The removal of carbon dioxide in this way would be expected to lead to the reaction to completion. That is, the calcium carbonate which is in equilibrium with the soluble calcium carbonate would eventually be consumed in the presence of a stoichiometric amount of acid. The resulting solution of calcium salts would only be slightly less basic than calcium carbonate, but still has the pH of most of the masses. When the calcium additives are prepared according to the present invention, however, at ambient temperatures, there is only an initial vigorous evolution of the gas, which dissipates after several minutes. The evolution of the initial vigorous gas is generally characterized by the formation of foam above the surface of the aqueous solution indicating that some amount of calcium carbonate has reacted with the acid. After the initial reaction, generally after about 30 seconds to about 5 minutes, only a small amount of the gas emitted is observed and most of the calcium carbonate remains as a suspension in the water. At the time of dissipation of the initial foaming, the pH of the solution begins to stabilize. The evolution of the waste gas is characterized by the formation of visible bubbles on the surface of the aqueous solution and generally decreases in intensity during the next 5 to 10 minutes. After the dissipation of the foaming, the pH of the solution remains relatively stable for several minutes and possibly 1 hour or more. The relative stability of the pH and the dissipation of the foaming after the initial reaction indicate that the compositions of the present invention comprise relatively stable suspensions of calcium carbonate which pass through the reaction with the acid in only a slow amount. However, as will be seen the formation of calcium salts in low to moderate amounts, it is not harmful to the practice of the present invention as long as the pH of the solution remains sufficiently acidic, so that the properties of the dough they will not be adversely affected at the time of the addition of the calcium additive. The calcium additives of the present invention can be highly handled on an industrial scale and can conveniently be transferred to the dough mixer, by tubing or the like. By the methods of the present invention, those skilled in the art can select the proportions of the reactants and reaction times to produce a calcium carbonate suspension having a pH corresponding to the pH of any desired bread dough. One aspect of the present invention provides calcium additives for bread dough comprising an aqueous solution of an inorganic acid or organic acid and a calcium carbonate powder suspended in the aqueous solution in the organic or inorganic acid. The weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 1: 1. . The pH of the aqueous solution is from about 3 to about 6.5. The preferred acid according to this aspect of the present invention is citric acid. Another aspect of the present invention provides a method for the preparation of a calcium additive for dough comprising the steps of: (a) providing an aqueous solution of an organic or inorganic acid; (b) providing the calcium carbonate powder suspended in an aqueous solution of an organic or inorganic acid; (c) mixing the resulting suspension of calcium carbonate in an aqueous solution of an organic or inorganic acid at a sufficiently high mixer speed to maintain a substantially homogeneous suspension of the calcium carbonate powder in the aqueous acid solution; and (d) allowing the aqueous solution to reach a pH of from about 3 to about 6.5. The weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 1: 1. . In the preferred practice of this aspect of the present invention, the acid is an organic acid and more preferably the acid is citric acid. Calcium carbonate is preferably provided in the form of a powder having a small average particle diameter. Yet another aspect of the present invention provides a method for fortifying the dough with calcium. The method according to this aspect of the present invention comprises the steps of: (a) providing a calcium additive comprising (i) an aqueous solution of an organic acid or an inorganic acid and (il) the calcium carbonate powder suspended in the aqueous solution of an organic acid or inorganic acid; wherein the weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1 and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 10: 1.; and wherein the pH of the aqueous solution is from about 3 to about 6.5; and (b) incorporating the calcium additive into the bread dough. In the preferred practice of this aspect of the present invention, the acid is an organic acid and more preferably, the acid is citric acid. The methods according to this aspect of the present invention also produce a prepared bread dough fortified with calcium. Another aspect of the present invention provides a method for fortifying a burger bun with calcium which comprises the steps of: (a) providing a calcium additive comprising (i) an aqueous solution of citric acid and (il) carbonate powder of calcium suspended in the aqueous solution of citric acid; wherein the weight ratio of calcium carbonate to citric acid is from about 4: 1 to about 7: 2, and the weight ratio of water to the combined weight of calcium carbonate and citric acid is from about 1: 1 to about 10: 1; and wherein the pH of the aqueous solution is from about 3 to about 6.5; and (b) producing the dough of a hamburger bun comprising wheat flour, preferably patent flour; and (c) incorporating the calcium additive into the hamburger bun dough in an amount sufficient to produce a hamburger bun at the time of baking having an elemental calcium content of from about 0.1% to about 2.2% by weight of the bun. Burger. A further aspect of the present invention provides calcium fortified bread products comprising calcium in an amount of about 0.1% to about 2.2% by weight. The bread products according to this aspect of the present invention preferably comprise flour that is substantially free of rind and / or medium quality products of wheat. The pH of the bread is preferably from about 3.0 to about 6.5. These and other aspects of the present invention can be understood more clearly by reference to the following detailed description of the invention and the appended claims. Detailed Description of the Invention In the following description of the invention, it should be understood that the terms used have their customary and normal meanings in the art, unless otherwise specified. All weights to which we refer in this description are provided in terms of "% by weight" of the total composition, unless otherwise indicated. The term "% by weight of flour" indicates that the ingredient is measured as a percentage of the total weight of the flour alone. The term "elemental calcium" refers to elemental calcium in an oxidation state, including Ca2 +. Accordingly, when we refer to the "weight" of elemental calcium in this description, that phrase refers to the weight of elemental calcium, whether the calcium is in the form of a salt or in another form. The calcium additives for the bread dough according to one embodiment of the present invention comprise an aqueous solution of an inorganic acid or an organic acid and a calcium carbonate powder suspended in the aqueous solution of an organic or inorganic acid. The weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 10: 1. The pH of the aqueous solution is from about 3 to about 6.5. The calcium additive according to this aspect of the present invention comprises water in a weight ratio of about 1: 1 to about 5: 1 in one embodiment and from about 1: 1 to about 3: 1 in another embodiment. The most preferred calcium additives comprise water in a weight ratio of about 1.8: 1 based on the combined weight of the calcium carbonate and the acid. In a preferred embodiment, the ratio of calcium carbonate to acid in the calcium additive is in a range of about 5: 1 to about 6: 1 by weight. Preferred calcium additives have a pH of from about 4.0 to about 6.5 and preferably from about 4.5 to about 5.6. Any acid compatible with food products can be used in the practice of the present invention. The acid can be either an inorganic acid or an organic acid. Useful Inorganic acids include, but are not limited to, phosphoric acid and sulfuric acid. The most preferred acids according to the present invention are organic acids and more preferably, organic carboxylic acids. Suitable organic acids include but are not limited to formic acid, acetic acid, ethanolic acid, adipic acid, citric acid, tartaric acid, glutaric acid, lactic acid, oxalic acid, ascorbic acid, glycolic acid, mevalonic acid, malic acid, acid tartronic, maleic acid, fumaric acid, malonic acid, and succinic acid. The most preferred carboxylic salts currently for use in the present disclosure include citric acid, fumaric acid, lactic acid and malic acid. A particularly preferred acid is citric acid. In the preferred practice of the present invention, calcium carbonate is provided as a powder having a small average particle size. In another embodiment, calcium carbonate is provided as a powder having an average particle diameter of from about 0.05 μm to about 30 μm. Preferably, the average particle diameter of the calcium carbonate powder is from about 1 μm to about 25 μm, preferably from about 5 μm to about 20 μm, and more preferably from about 10 μm to about 15 μm. As used in the present description, the symbol "μm" refers to micrometers. It is well known in the art that calcium carbonate powders have a variety of average particle diameters, which are commercially available. For example, food grade and USP grade calcium carbonate powders having average particle sizes in a range of 0.7 to 20 μm are available from suppliers, such as OMYA, Inc. (Alpharetta, Georgia), JM Huber Corp. (Atlanta, Ga), and Minerals Technologies Inc. (New York, NY). Suitable calcium carbonate powders include, but are not limited to, those available from OMYA, Inc. under the trademarks OMYA-Cal FG 15, OMYA-Cal USP 15, OMYA-Cal LL OC FG 15 BTH, OMYA- Cal LL USP 15, OMYA-Cal LL USP 15 BTH, OMYA-Cal FG-10AZ, OMYA-Cal FG-6AZ, and OMYA-Cal USP-4AZ. Although calcium additives according to this embodiment of the present invention are preferably used to enrich the calcium content of baked goods, particularly fermented breads, it is contemplated that these additives will also be useful for enriching the calcium content of a variety of foods. food products. In another embodiment of the present invention, there is provided a method for preparing a calcium additive for bread dough. This method comprises the steps of: (a) providing an aqueous solution of an inorganic acid or an organic acid; (b) providing a calcium carbonate powder suspended in the aqueous solution of an organic or inorganic acid; wherein the weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 10: 1; (c) mixing the resulting calcium carbonate suspension in an aqueous solution of an organic or inorganic acid with a sufficiently high mixer speed to maintain the calcium carbonate powder as a substantially homogeneous suspension in the aqueous solution; and (d) allowing the aqueous solution to reach a pH of from about 3 to about 6.5. The calcium carbonate is preferably provided in the form of a powder having a small average particle diameter as described above. In the preferred embodiment, the ratio of calcium carbonate to acid, preferably citric acid, in the calcium additive is in a range of about 5: 1 to about 6: 1 by weight. In one embodiment, the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 5: 1. In another embodiment, the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 3: 1. Preferred calcium additives comprise water in a weight ratio of about 1.8: 1 based on the combined weight of calcium carbonate and acid. Preferred calcium additives have a pH of from about 4.0 to about 6.5 and more preferably from about 4.5 to about 5.6. Any mixing vessel can be used to combine water, calcium carbonate and citric acid. Preferably, the mixing vessel is the mixing bowl of a mechanical mixer such as a Hobart mixer. However, it is contemplated that water, calcium carbonate and citric acid may be first combined in a vessel and subsequently transferred to the mixing bowl of a suitable mixer. Calcium carbonate, citric acid and water can be added in any order or added simultaneously to the mixing vessel. Preferably, the mixing vessel is charged first with water. It has also been desirably discovered to employ a mixing vessel having approximately twice the volume of water added or more, since the initial vigorous reaction can result in foaming or formation of vigorous bubbles, which increases the total volume of the material in the mixing bowl to approximately 100%. It is contemplated that different antifoam agents such as sllicone may be useful in the practice of the present invention to mitigate the effects of foaming. Any mixer that provides sufficient agitation to maintain the calcium carbonate as a substantially homogeneous suspension in the aqueous solution can be used in the practice of the present invention. Preferably, the mixer is a high speed mixer. As used in the present description, the phrase "high speed mixer" refers to mixing speeds capable of creating a deep vortex. At low rates of agitation, calcium carbonate may precipitate or settle out of the aqueous solution, resulting in a substantially non-homogeneous suspension. It is within the knowledge of one skilled in the art to select an appropriate mixer and mixing conditions. At the time of the addition of the ingredients and the start of the high-speed mixing, an evolution of initial vigorous gas is observed. In the absence of anti-foam agents, the initial reaction generally produces a foam, which increases the volume of the mixture from about 10% to about 100%. Depending on the acid selection, the foam generally dissipates after approximately 1 or 2 minutes and a moderate to vigorous bubble formation occurs. The formation of moderate to vigorous bubbles subsists after several minutes, generally from about 4 to about 10 minutes. After about 4 to about 10 minutes, only a small amount of emitted gas is observed, and most of the calcium carbonate remains in the form of a suspension in the water. The duration of the initial vigorous production of carbon dioxide bubbles will depend on a variety of factors such as, for example, temperature, mixing speed, average particle diameter of calcium carbonate, volume of water used, acid selection and the proportion of calcium carbonate to acid. It is within the skills of the technique to modify these and other parameters to control the duration of the evolution of initial vigorous gas. Generally, after about 4 to 10 minutes, the speed of the mixer is preferably lowered. The speed of the mixer is preferably adjusted to maintain the mixture as a substantially homogeneous suspension. It should be understood that reducing the speed of the mixer is only a matter of convenience, since it has been found easier to handle the suspension at lower mixing speeds. That is, it has been found that it is advantageous to transfer the calcium additive through a tubing and the like at lower agitation rates. The pH of the solution remains relatively stable for several minutes, generally 10 minutes and possible one or more. A person skilled in the art can adjust the reaction time and the mixing speed to achieve a mixture having the desired pH. In another embodiment of the present invention, there is provided a method for fortifying a bread dough with calcium. The method according to this embodiment of the present invention comprises the steps of: (a) providing a calcium additive comprising (i) an aqueous solution of an organic acid or an inorganic acid and (ii) calcium carbonate powder suspended in the aqueous suspension of an organic or inorganic acid; wherein the weight ratio of calcium carbonate to acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 10: 1; and wherein the pH of the aqueous solution is from about 3 to about 6.5; and (b) incorporating the calcium additive into the bread dough. In a preferred embodiment, the ratio of calcium carbonate to acid, preferably citric acid, in the calcium additive is in a range of about 5: 1 to about 6: 1 by weight. In one embodiment, the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 5: 1. In another embodiment, the weight ratio of water to the combined weight of calcium carbonate and acid is from about 1: 1 to about 3: 1. Preferred calcium additives comprise water in a weight of about 1.8: 1 based on the combined weight of calcium carbonate and the acid. Preferred calcium additives have a pH of from about 4.0 to about 6.5 and more preferably from about 4.5 to about 5.6. In the preferred practice of this aspect of the present invention, calcium carbonate, citric acid and water are mixed for about 5 to about 10 minutes before addition to the bread dough. The exact mixing time may vary depending on factors, such as the amount of materials and the mixing speed. Preferably the solution must be mixed sufficiently so that the evolution of the gas subsists substantially, but not so much that the solution develops a basic pH. The calcium additives can be added to the ingredients of the bread dough in any way. For example, calcium additives can be poured directly into the mixing bowl that contains the ingredients of the bread dough. Alternatively, the calcium additives can be pumped into the mixing bowl with the contents of the ingredients of the dough through a tubing and the like. It is anticipated that the calcium additives of the present invention are well suited for large scale industrial applications, such as those used by commercial bread producers. Calcium additives can be added to any type of bread dough. Preferably, the bread dough comprises a fermentation agent. It is contemplated that the dough may comprise any fermentation agent known in the art, including but not limited to, chemical fermentation agents and bacterial fermentation agents. In the preferred practice of the present invention, the fermentation agent is yeast.

The calcium additives are preferably added to the bread dough in an amount of about 2% to about 10% by weight based on the total weight of the dough. Preferably, the calcium additives are added in amounts of about 4% to about 6% by weight based on the weight of the dough. In the most preferred practice of the present invention, the calcium additives are added in amounts of about 5% to about 6% by weight based on the total weight of the dough. The calcium additives can be employed by any known method for preparing bread doughs, including but not limited to, the "direct bread" method, the "biscuit bread" method, the "continuous mixing" method, the of "liquid cake", the method of "liquid ferment" and the method of "mass without time". The biscuit dough method is the preferred method used in commercial bakeries. In the sponge cake method, a quantity of the dough, called "a sponge cake" is prepared which serves as a prior ferment. The sponge cake is combined with the rest of the bread ingredients at a later stage. In a typical process, the cake is formed by mixing more than half the flour, most without all the yeast and a sufficient amount of water to thicken the dough, for about 4 minutes in a conventional dough mixer. Then the cake is adjusted to ferment for about 3 to 5 hours depending on the amount of flour incorporated in the cake. The fermented cake is mixed with the rest of the ingredients in a dough mixer. The resulting dough is then placed for fermentation for an additional period of about 15 minutes to 1 hour before baking. It should be understood that this procedure is only representative and that any variations or modifications to this method are contemplated as being within the abilities of a normal craftsman. In a biscuit dough method, as with any method comprising a previous fermentation step, the calcium additive is preferably added to the dough rather than added to the cake. However, it is contemplated that the calcium additive may be added to the sponge cake before the remaining flour is combined with the sponge cake. In addition, portions of the calcium additive can be added to both of the sponge cake and the final dough. If the liquid fermentation method is used, it is preferred to add the calcium additive during the mixing step of the dough after the fermentor is added. In one embodiment, the final pH of the dough is from about 3.0 to about 6.0. In another embodiment, the final pH of the dough is from about 4.0 to about 5.8. In yet another embodiment, the final pH of the dough is from about 5.0 to about 5.4. The dough can contain any type of flour. Preferred flours are those traditionally used to produce bread products. The most preferred flours according to the present invention are those used to prepare white breads, rolls and rolls, such as patent flour and clear patent flour. The term "flour" as used in the present description, includes but is not limited to, patent flour, all-purpose flour, bleached flour, bread flour, cake flour, biscuit flour, biscuit flour, durum flour , enriched flour, farina, graham flour, confectionery flour, rice flour, rye flour, self-raising flour, semolina, unbleached flour, wheat flour, whole wheat flour, wheat feed, corn feed, flour corn, durum flour, rye feed, rye flour, oatmeal meal, oatmeal, soybean meal, soybean meal, sorghum feed, sorghum meal, potato feed and potato flour. Preferred flours for use in the present invention are patent flour, clear patent flour, general purpose flour, farina flour and bleached flour. The most preferred flours are those conventionally used to prepare white bread, rolls and rolls. Most preferred flours according to the present invention have gluten contents of about 6% to about 14% by weight. In one embodiment of the present invention, these preferred flours comprise 100% by weight of the total flour content of the dough. In other embodiments, the preferred flours comprise 99%, 98%, 97%, 96%, 95%, 94%, 93%, 92%, 91% or 90% by weight of the total flour content of the dough. In one embodiment of the present invention, the dough comprises flour that is substantially free of wheat quality products. As used in the present invention, the flour that is "substantially free of medium quality wheat products" contains less than about 5% by weight of medium quality wheat products. In another embodiment of the present invention, the dough comprises flour that is substantially free of rind. As used in the present description, flour that is "substantially shell free" contains less than about 5% by weight shell. Although the above description refers to a dough made from flour, the invention is not limited in this way. It should be understood that the dough of the present invention can be prepared from alternative flours. The "bread type" products that do not comprise flour and are substantially free of flour can be prepared in accordance with the present invention. Said bread-type products can be prepared from a flour-free dough comprising, for example, gluten and grains. The bread-type products that are "substantially free" from flour will have a flour content of less than about 10% by weight based on the weight of the dry ingredients and preferably will have a flour content of less than about 5% by weight based on the total weight of the dry ingredients. In addition to the flour, the dough may contain any ingredients known in the art for use in bread products including, but not limited to, salt, fat and oil, sugar, butter, milk, dry milk, yeast foods, eggs, and gums vegetables. The bread dough fortified with calcium and prepared according to the methods of this aspect of the present invention are also provided. The dough can be any type of dough known in the art, including but not limited to bread dough, bagel dough, pasta dough, cereal dough, biscuit dough, cookie dough, cake dough, dessert dough and pizza dough. A further aspect of the present invention provides calcium fortified baked products comprising calcium from about 0.1% to about 2.2% by weight.

In one embodiment, the calcium fortified baked products comprise calcium from about 0.5% to about 1.8% by weight. In another embodiment, the calcium fortified baked products comprise calcium of about 0.8% to about 1.2% by weight. In yet another embodiment, the calcium fortified baked products comprise calcium from about 0.9% to about 1.2% by weight.

Still another embodiment, baked products fortified with calcium comprise calcium of about 1.0% to about 1.2% by weight. It should be understood that the phrase "comprising calcium from about 0.2% to about 1.2% by weight" refers to the weight of the elemental calcium instead of the calcium of the calcium salt. The baked products according to this aspect of the present invention preferably comprise flour that is substantially free of rind and / or medium quality products of wheat. Preferably, the baked products comprise patent flour. In one embodiment, the pH of the baked product fortified with calcium is from about 3.0 to about 6.0. In another embodiment, the pH of the baked product fortified with calcium is from about 4.0 to about 5.8. In yet another embodiment, the pH of the baked product fortified with calcium is from about 5.0 to about 5.4. The baked goods according to this aspect of the present invention are preferably bread products. The baked products according to this aspect of the present invention may be fermented or unfermented bread products. The additives and methods described herein are particularly useful in the preparation of fermented bread products. Baked goods in accordance with the present invention include, but are not limited to, white bread, wheat bread, tortillas, rolls and rolls, craft / specialty breads, rye bread, whole grain varieties, bagels, pasta, products fast foods based on grains, cereals, biscuits, biscuits, cakes, muffins, cakes, pancakes, pizza shells, doughs, danish, grain-based nutritional supplements and salty fast food foods, such as pretzels, tortilla chips, flakes of corn and french fries. The baked products provided by the present invention have a texture, crumb structure, taste and "mouthfeel" substantially identical to baked products that do not have added calcium. Baked products do not have a "grainy" texture that is characteristic of high levels of insoluble calcium carbonate. The preferred bread products according to the present invention are hamburger buns. Accordingly, a preferred embodiment of the present invention is a method for fortifying a burger bun with calcium. The method comprises the steps of: (a) providing a calcium additive comprising (i) an aqueous solution of citric acid and (ii) calcium carbonate powder suspended in the aqueous citric acid solution; wherein the weight ratio of calcium carbonate to citric acid is from about 4: 1 to about 7: 1 and the weight ratio of water to the combined weight of calcium carbonate and citric acid is from about 1: 1 to about 10 : 1; and wherein the pH of the aqueous solution is from about 3 to about 6.5; (b) providing a hamburger bun dough containing wheat flour, preferably patent flour, and (c) incorporating the calcium additive into the hamburger bun dough. In one embodiment, the weight ratio of water to the combined weight of calcium carbonate and citric acid in the calcium additive is from about 1: 1 to about 5: 1. In another embodiment, the weight ratio of water to the combined weight of calcium carbonate and citric acid is from about 1: 1 to about 3: 1. Preferably the preferred calcium additives according to this embodiment comprise water in a weight ratio of about 1.8: 1 based on the combined weight of calcium carbonate and citric acid. The hamburger bun dough prepared according to the present invention will preferably comprise wheat flour. In a preferred embodiment, wheat flour is patent flour. The wheat flour preferably will comprise approximately 99%, 98% or, 97%, 96% >;, 95%, 94%, 93%, 92%, 91%, or 90% by weight of the total flour content of the hamburger bun dough. Although the patent flour is the preferred flour according to this aspect of the present invention, it can be replaced by other highly purified flours, such as clear patent flour replaced by the patent flour. The calcium additive is incorporated into the mass of the hamburger bun in an amount sufficient to produce a hamburger bun at the time of baking which has elemental calcium content of about 0.1% to about 2.2% by weight of the hamburger bun. In another embodiment, the hamburger bun at the time of baking has an elemental calcium content of about 0.8% to about 1.8% by weight of the hamburger bun. In yet another embodiment, the hamburger bun at the time of baking has an elemental calcium content of about 0.9% to about 1.2% of the hamburger bun. In a further embodiment, the hamburger bun at the time of baking has an elemental calcium content of about 1.0% to about 1.2% by weight of the hamburger bun. The calcium carbonate powder is preferably one having a small average particle diameter. Preferred calcium carbonate powders have average particle diameters of from about 0.05 μm to about 30 μm, more preferably from about 1 μm to about 25 μm and even more preferably from about 5 μm to about 20 μm. The most preferred calcium carbonate powders according to this embodiment have average particle diameters of about 1.0 μm to about 1 μm. It should be understood that the mention in this description of certain ranges should not be construed as limiting the description to the described endpoints. For example, the range of "3.0 to 6.0" will be understood as describing each value between and is equivalent to the description "3.0, 4.0, 5.0, and 6.0" or "3.0, 3.1, 3.2, 3.3 ... 5.7, 5.8 , 5.9, and 6.0". The intermediate values within each range mentioned are explicitly or inherently described by the description of the wider range. Similarly, the description of the range will be understood as inherently describing the narrower ranges in it. The phrase "approximately" intends to modify each value within the range. EXAMPLE 1 This example illustrates the use of various organic and inorganic acids in the practice of the present invention. In each of the following experiments, 25 g of calcium carbonate powder (OMYA Cal Carb LL FG 15 PDR) in 60 ml of deionized water was suspended in a 150 ml graduated glass beaker equipped with a stir bar Magnetic coated with Teflon. The agitation speed was adjusted to produce a deep vortex. Then 5 g of acid was added to the suspension and the pH of the aqueous phase was measured every minute using the Orion 420A + pH meter. Table 1 provides the pH of each solution for a period of 10 minutes after the addition of the acid to the solution.

Table I The pH of Calcium Carbonate Suspensions in Various Acids DS Citrus Fumeric Lactic Phosphoric Melic Time (minutes) pH pH PH PH pH 0 3.32 5.10 2.82 3.28 3.11 1 4.00 5.32 5.32 4.08 4.36 2 4.29 5.21 5.30 4.44 5.42 3 4.45 5.25 5.31 4.65 5.54 4 4.58 5.31 5.35 4.82 5.58 5 4.68 5.32 5.39 4.92 5.59 6 4.76 5.41 5.42 5.00 5.59 7 4.82 5.48 5.43 5.07 5.61 8 4.88 5.47 5.44 5.12 5.62 9 4.92 5.47 5.44 5.16 5.63 10 4.95 5.47 5.44 5.20 5.65 In each case, it can be seen that after an initially rapid increase in pH after the addition of each acid, the pH becomes relatively stable under these conditions. For example, the pH increase from the second to the tenth minute is in a range of 0.14 for lactic acid to 0.76 for malic acid. It is clear from the data in Table I that calcium carbonate initially reacts with each acid to form some amount of calcium salt as evidenced by rapid rise in pH. However, after about 1 or 2 minutes, the reaction decreases and the pH of the aqueous calcium carbonate suspensions becomes relatively stable under these conditions. In each case, the solution remains acidic after 10 minutes and is therefore suitable for addition to a bread dough, particularly a bread dough comprising a fermentation agent. In each case, the formation of vigorous bubbles was observed after the addition of the acid. The formation of vigorous bubbles was evidenced by the formation of foam, which resulted in an increase in the total volume of the material in the beaker. That is, the surface of the solution was no longer visible due to the presence of foam above the surface. In the case of citric acid, foaming lasted for about 1 minute after the addition of the acid. The total volume in the beaker increased approximately 12% during this time. After about 2 minutes, the foam had dissipated and the volume in the beaker returned to the initial value. After 5 minutes, there was almost no bubble formation and the surface of the liquid was completely visible. When fumaric acid was added to the aqueous suspension of calcium carbonate, the results were similar to those seen with citric acid. The initial foam formation that was the result of a total volume increase in the beaker of approximately 12% subsisted after approximately 4 minutes. After 5 minutes, the surface of the solution was completely visible and only moderate bubble formation was observed.

In the case of lactic acid, foaming increased the volume in the beaker to approximately 75% after the addition of the acid. After about 2 minutes, the foam had settled to about 12% above the initial volume of the solution and remained relatively constant until about 4 minutes after the addition of the acid. After about 8 minutes, the foaming had substantially dissipated and the formation of bubbles became visible on the surface of the solution. When lactic acid was added to an aqueous suspension of calcium carbonate, foaming lasted for about 20 seconds and the volume in the beaker increased by approximately 38%. After 1 minute, the foam formation had dissipated significantly and the volume in the beaker was approximately 12% greater than its initial value. After 2 minutes, the volume had returned to its initial value and foam formation was no longer present. The formation of bubbles was visible on the surface of the solution after 2 minutes, gradually decreasing in magnitude until only a minimum bubble formation was observed after 8 minutes. Phosphoric acid had a similar behavior to organic acids; however, the initial foaming was more substantial, resulting in a 100% increase in the volume of the material in the beaker after approximately 10 seconds as a result of vigorous foaming. After about 30 seconds to 1 minute, foaming subsided, resulting in a suspension having a volume of approximately 12% greater than the initial value. After about 4 minutes, the liquid surface was visible and very little bubble formation was observed. EXAMPLE 2 This example provides a calcium additive according to the present invention. 30 L of water was added to the mixing bowl of a Hobart mixer. The mixing bowl was 18 inches in diameter and had straight sides of 36 inches, with a conical bottom and a volume of 60 L. To the water was added 12, 106 g of calcium carbonate powder (OMYA Cal Cab LL OC FG 15) having an average particle size of 15 μm and 2.422 g of citric acid. The ingredients were mixed for 5 minutes at a "high" speed of the mixer. The speed of the mixer was selected to form a deep vortex. In the case of the employed Hobart mixer, it was found that a mixer speed of 1, 440 revolutions per minute was adequate to produce a deep vortex. The initial foaming lasted for about 1 to 2 minutes and subsequently gave way to bubble formation which subsisted after about 4 to 5 minutes. After about 5 minutes, the speed of the mixer was lowered to about 720 revolutions per minute and the pH of the solution was measured using an STD pH meter. The pH of the solution was about 5. After an additional 5 minutes, the pH of the solution was measured again and found to be about 4.8. The calcium additive had the consistency of a uniform aqueous suspension of fine calcium carbonate powder. EXAMPLE 3 This example provides a white bread fortified with calcium made using the calcium additive of example 2. The bread was made with the cake and dough technique using the ingredients listed in Table II. In this example, the calcium additive was added to the dough technique instead of the biscuit technique. TABLE II % in Weight of Ingredient Biscuit Total Mass% in Weight Flour Flour 2 700.00 300.00 1000.00 100.00 53.46% Water 437.00 117.00 554.00 55.40 29.62% HFCS3 182.00 182.00 18.20 9.73% Yeast 4 14.00 6.00 20.00 2.00 1.07% Vegetable Oil 5 12.54 37.00 49.54 4.95 2.65% Salt 6 2.50 17.50 20.00 2.00 1.07% SSL7 3.00 0.00 3.00 0.30 0.16% Datem 8 1.00 1.00 0.10 0.05% Emulsifier 9 5.00 5.00 0.50 0.27% Calcium Additive 10 31.00 31.00 3.10 1.66% Calcium Propanol 11 1.10 1.10 0.11 0.06% Gluten 12 4.00 4.00 0.40 0.21% 1All weights are given in grams; ^ ADM patent flour; 3 High fructose corn syrup from AE Staley; 4Fleischmann's; 5 soya from Riceland Foods; 6sal US; 7-stearoyl-2-lactylate sold under the name of Emplex by American Ingredients; Diacetyl esters of tartaric acid of monoglycerides sold under the name of Panodan by Danisco; 9Soft Max 90 by American Ingredients; The calcium additive composition described in Example 2; 11 Fleischmann's; 12gluten of vital wheat of Manildra. The white bread fortified with calcium prepared in this example was made from patent flour having a protein content of 1 1% by weight. The sources of each ingredient are in table I I and are the same in all the following examples. The resulting bread contai330 mg of elemental calcium per 70 g of slice size. The bread had a texture, crumb structure, flavor and "mouth feel" substantially identical to white bread. EXAMPLE 4 This example provides another white bread fortified with calcium made using the calcium additive of example 2. The bread was made with the cake and dough technique using the ingredients listed in Table ll l. In this example, the calcium additive was added to the cake sponge.

TABLE l l l % in Weight of Biscuit Ingredient1 Total Weight% in Weight Flour Flour 700.00 300.00 1000.00 100.00 53.46% Water 437.00 117.00 554.00 55.40 29.62% HFCS 182.00 182.00 18.20 9.73% Yeast 14.00 6.00 20.00 2.00 1.07% Vegetable Oil 12.54 37.00 49.54 4.95 2.65% Salt 2.50 17.50 20.00 2.00 1.07% SSL 3.00 0.00 3.00 0.30 0.16% Datem 1.00 1.00 0.10 0.05% Emulsifier 5.00 5.00 0.50 0.27% Calcium Additive 2 31.00 0.00 31.00 3.10 1.66% Calcium Propionate 1.10 1.10 0.11 0.06% Gluten 4.00 4.00 0.40 0.21% 1 All weights are given in grams. 2 The calcium additive composition described in example 2. The white bread fortified with calcium prepared in this example was made from patent flour having a protein content of 1 1% or by weight. The resulting bread contai330 mg of elemental calcium for each slice size of 60 g. The bread had a texture, crumb structure, flavor and "mouth feel" substantially identical to white bread. EXAMPLE 5 This example provides a white bread fortified with calcium made using the calcium additive of example 2. The bread was made with a direct dough technique using the ingredients listed in table IV. In this example, all the ingredients including the calcium additive were combito form the dough. TABLE IV % in Weight of Total Ingredient% in Weight Flour Flour 1000.00 100.00 53.46% Water 554.00 55.40 29.62% HFCS 182.00 18.20 9.73% Yeast 20.00 2.00 1.07% Vegetable Oil 49.54 4.95 2.65% Salt 20.00 2.00 1.07% SSL 3.00 0.30 0.16% Datem 1.00 0.10 0.05 % Emulsifier 5.00 0.50 0.27% Calcium Additive 2 31.00 3.10 1.66% Calcium Propionate 1.10 0.11 0.06% Gluten 4.00 0.40 0.21% 1All weights are given in grams. 2 The calcium additive composition described in example 2. The white bread fortified with calcium prepared in this example was made from patent flour having a protein content of 1 1% > in weigh. The resulting bread had 330 mg of elemental calcium for each slice size of 60 g. The bread had a texture, crumb structure, flavor and "mouth feel" substantially identical to white bread. EXAMPLE 6 This example provides a white bread fortified with calcium made using the calcium additive of example 2. The bread was made with a timeless dough technique using the ingredients listed in table V. TABLE V % in Weight of Total Ingredient% in Weight Flour Flour 1200.00 100.00 54.23% Water 613.00 51.08 27.70% HFCS 219.00 18.25 9.90% Yeast 47.00 3.92 2.12% Vegetable Oil 47.00 3.92 2.12% Salt 22.00 1.83 0.99% SSL 3.50 0.29 0.16% Datem 1.20 0.10 0.05 % Emulsifier 12.00 1.00 0.54% L-Cysteine 4.00 0.33 0.18% Calcium Additive 2 36.50 3.04 1.65% Calcium Propionate 1.40 0.12 0.06% Gluten 6.00 0.50 0.27% 1 All weights are given in grams. 2 The calcium additive composition described in example 2. The white bread fortified with calcium prepared in this example was made from patent flour having a protein content of 1 1% > in weigh. The resulting bread contained 330 mg of elemental calcium for each size of 60 g slices. The bread had a texture, crumb structure, flavor, and "mouth feel" substantially identical to white bread. EXAMPLE 7 This example provides another white bread fortified with calcium made using the calcium additive of example 2. The bread was made with the "liquid biscuit" technique using the ingredients listed in Table 11. This technique is similar to the biscuit dough technique, however, most of the flour is added at the dough stage. In this example, the calcium additive was added at the stage of the mass. TABLE VI % in Weight of Ingredient Sponge Total Weight% in Weight Flour Flour 506.00 694.00 1200.00 100.00 54.35% Water 486.00 127.00 613.00 51.08 27.77% HFCS 219.00 219.00 18.25 9.92% Yeast 29.00 18.00 47.00 3.92 2.13% Vegetable Oil 12.54 34.11 46.65 3.89 2.11% Sai 5.01 16.47 21.48 1.79 0.97% SSL 3.50 3.50 0.29 0.16% Datem 1.20 1.20 0.10 0.05% Emulsifier 12.00 12.00 1.00 0.54% Calcium Additive 2 0.00 36.50 36.50 3.04 1.65% Calcium Propanol 1.40 1.40 0.12 0.06% Gluten 6.00 6.00 0.50 0.27% 1All the weights are They provide in grams. 2 The calcium additive composition described in example 2. The white bread fortified with calcium prepared in this example was made from patent flour having a protein content of 1 1% or by weight. The resulting bread contained 330 mg of elemental calcium for each slice size of 60 g. The bread had a texture, crumb structure, flavor, and "mouth feel" substantially identical to white bread. Having described the present invention by the foregoing description of the preferred embodiments, it should be understood by those skilled in the art that modifications and variations of these embodiments may be made without departing from the spirit or scope of the present invention, as establish the following claims.

Claims (47)

1. CLAIMS 1. A calcium additive for a bread dough, which comprises: (a) an aqueous solution of an inorganic acid or an organic acid; (b) a calcium carbonate powder suspended in said aqueous solution of an organic or inorganic acid; wherein the weight ratio of calcium carbonate acid is from about 4: 1 to about 7: 1 and the weight ratio of water of the combined weight of calcium carbonate of the acid is from about 1: 1 to about 10: 1 and the pH of the aqueous solution is from about 3 to about 6.5.
2. 2. The calcium additive as described in claim 1, characterized in that the acid is an organic acid.
3. 3. The calcium additive as described in claim 2, characterized in that the organic acid is selected from the group consisting of citric acid, fumaric acid, lactic acid and malic acid.
4. 4. The calcium additive as described in claim 3, characterized in that the acid is citric acid. 5. The calcium additive as described in claim 4, characterized in that the ratio of calcium carbonate to citric acid is from about 5: 1 to about 6: 1 by weight. The calcium additive as described in claim 5, characterized in that the aqueous solution comprises water in a weight ratio of from about 1: 1 to about 5: 1 based on the combined weight of the calcium carbonate and the acid citric. The calcium additive as described in claim 6, characterized in that the aqueous solution comprises water in a weight ratio of from about 1: 1 to about 3: 1 based on the combined weight of the calcium carbonate and the acid citric. 8. The calcium additive as described in claim 1, characterized in that the pH of the solution is from about 4.0 to about 6.5. 9. The calcium additive as described in claim 8, characterized in that the pH of the solution is from about 4.5 to about 5.6. The calcium additive as described in claim 1, characterized in that the calcium carbonate is provided in the form of a powder having an average particle diameter of about 0.05 μm to about 30 μm. eleven . The calcium additive as described in claim 10, characterized in that the calcium carbonate is provided as a powder having an average particle diameter from about 10 μm to about 15 μm. 12. A method for preparing a calcium additive, which comprises the steps of: (a) providing an aqueous solution of an inorganic acid or an organic acid; (b) providing a calcium carbonate powder suspended in said aqueous solution of an inorganic or organic acid; wherein the weight ratio of the calcium carbonate to the acid is from about 4: 1 to about 7: 1 and the weight ratio of water to the combined weight of the calcium carbonate and the acid is from about 1: 1 to about 10: 1; (c) mixing the resulting suspension of the calcium carbonate in an aqueous solution of an inorganic acid or an organic acid at a sufficiently high mixer speed to maintain the calcium carbonate powder as a substantially homogeneous suspension in said aqueous solution; and (d) allowing the aqueous solution to reach a pH of from about 3 to about 6.
5. 5. The method as described in claim 12, characterized in that the acid is an organic acid. The method as described in claim 13, characterized in that the organic acid is selected from the group consisting of citric acid, fumaric acid, lactic acid and malic acid. The method as described in claim 14, characterized in that the acid is citric acid. 16. The method as described in claim 1 5, characterized in that the ratio of calcium carbonate to citric acid is from about 5: 1 to about 6: 1 by weight. The method as described in claim 16, characterized in that the aqueous solution comprises water in a weight ratio of about 1: 1 to about 5: 1 based on the combined weight of calcium carbonate and citric acid . The method as described in claim 17, characterized in that the aqueous solution comprises water in a weight ratio of about 1: 1 to about 3: 1 based on the combined weight of calcium carbonate and citric acid . The method as described in claim 12, characterized in that the calcium carbonate is provided as a powder having an average particle size of about 0.05 μm to about 30 μm. The method as described in claim 13, characterized in that the calcium carbonate is provided as a powder having an average particle size of about 10 μm to about 15 μm. twenty-one . A method for fortifying a mass with calcium which comprises the steps of: (a) providing a calcium additive, which comprises: (i) an aqueous solution of an inorganic acid or an organic acid; and (ii) a calcium carbonate powder suspended in said aqueous solution of an organic or inorganic acid; wherein the weight ratio of calcium carbonate to said acid is from about 4: 1 to about 7: 1 and the weight ratio of water to the combined weight of calcium carbonate and the acid is from about 1: 1 to about 1. 0: 1; and wherein the pH of the aqueous solution is from about 3 to about 6.5; and (b) incorporating the calcium additive into the mass. 22. The method as described in claim 21, characterized in that the acid is an organic acid. 23. The method as described in claim 22, characterized in that the organic acid selected from the group consisting of citric acid, fumaric acid, lactic acid and malic acid. 24. The method as described in claim 23, characterized in that the acid is citric acid. The method as described in claim 24, characterized in that the ratio of calcium carbonate to citric acid is from about 5: 1 to about 6: 1 by weight. 26. The method as described in claim 25, characterized in that the aqueous solution comprises water in a weight ratio of about 1: 1 to about 5: 1 based on the combined weight of the calcium carbonate and the citric acid. The method as described in claim 26, characterized in that the aqueous solution comprises water in a weight ratio of from about 1: 1 to about 3: 1 based on the combined weight of the calcium carbonate and the citric acid. The method as described in claim 21, characterized in that the calcium carbonate is provided as a powder having an average particle size of about 0.05 μm to about 30 μm. 29. The method as described in claim 28, characterized in that the calcium carbonate is provided as a powder having an average particle size of about 1.0 μm to about 1 μm. 30. The method as described in claim 21, characterized in that the dough comprises a fermentation agent. 31 The method as described in claim 30, characterized in that the fermentation agent is yeast. 32. The method as described in claim 38, characterized in that the dough has a final pH of from about 3.0 to about 6.0. 33. The method as described in claim 21, characterized in that the mixture is added to the dough in an amount of about 1 to about 10% by weight of flour based on the total weight of the flour. 34. The method as described in claim 21, characterized in that the aqueous mixture is added to one of the group consisting of: the sponge cake in a biscuit dough process, the dough in a sponge cake process, the dough in a direct mass process, the mass in a liquid fermentation process, the mass in a mass process without time, or the mass in a continuous mixing process. 35. The dough prepared by the method as described in claim 21. 36. A baked product fortified with calcium comprising elemental calcium in an amount of about 0.1%) to about 2.2% > by weight, wherein the baked product comprises flour that is substantially free of husk and products of average wheat quality and wherein the baked product has a pH of from about 3.0 to about 6.5. 37. The baked product fortified with calcium as described in claim 36, characterized in that the bread has a pH of about 4.0 to about 5.8. 38. The baked product fortified with calcium as described in claim 37, characterized in that the bread has a pH of about 5.0 to about 5.4. 39. The baked product fortified with calcium as described in claim 36, characterized in that the bread product is selected from the group consisting of: white bread, wheat bread, hamburger bun, a roll, a bagel, a shell of pizza, a fast food, a Danish, and a muffin. 40. The baked product fortified with calcium as described in claim 39, characterized in that the bread product is selected from the group consisting of: a white bread, a hamburger bun, and a roll. 41. The calcium fortified baked product as described in claim 40, which comprises calcium in an amount of about 0.8% > to approximately 1.2% by weight. 42. A method for fortifying a burger bun with calcium, which comprises the steps of: (a) providing a calcium additive, which comprises: (i) an aqueous solution of citric acid; and (ii) a calcium carbonate powder suspended in said aqueous citric acid solution; wherein the weight ratio of calcium carbonate to citric acid is from about 4: 1 to about 7: 1, and the weight ratio of water to the combined weight of calcium carbonate and citric acid is about 1: 1 to approximately 10: 1; and wherein the pH of the aqueous solution is from about 3 to about 6.5; (b) providing a hamburger bun dough comprising wheat flour; and (c) incorporating the calcium additive into the hamburger bun dough in an amount sufficient to produce a hamburger bun at the time of baking having an elemental calcium content of from about 0.1% to about 2.2% by weight of the bun. Burger. 43. The method as described in claim 42, characterized in that the calcium additive is incorporated into the mass of the hamburger bun in an amount sufficient to produce a hamburger bun at the time of baking that has an elemental calcium content from about 0.8%) to about 1.8% by weight of the hamburger bun. 44. The method as described in claim 43, characterized in that the calcium additive is incorporated into the mass of the hamburger bun in an amount sufficient to produce a hamburger bun at the time of baking that has an elemental calcium content from about 1.0% to about 1.2% by weight of the hamburger bun. 45. The method as described in claim 42, characterized in that the aqueous solution comprises water in a weight ratio of about 1: 1 to about 5: 1 based on the combined weight of the calcium carbonate and the citric acid. 46. The method as described in claim 45, characterized in that the aqueous solution comprises water in a weight ratio of about 1: 1 to about 3: 1 based on the combined weight of the calcium carbonate and the citric acid. 47. The method as described in claim 42, characterized in that the wheat flour comprises patent flour.