CALCIUM/CALCIUM-MAGNESIUM FORTIFIED WATER, JUICES, BEVERAGES AND OTHER LIQUID FOOD PRODUCTS

Abstract: A composition comprising fortified water, juices, beverages or other liquid food products and a fortifying amount of a metastable Calcium Lactate-Citrate or Calcium-Magnesium Lactate-Citrate complexes formed by the interaction of an alkaline calcium source with a mixture of lactic and citric acids and optionally stabilized with carbohydrates.

Description: CALCIUM/CALCIUM-MAGNESIUM FORTIFIED WATER, JUICES, BEVERAGES AND OTHER LIQUID FOOD PRODUCTS FIELD OF INVENTION The present invention relates to the fortification of water, juices and beverages with meta-stable Calcium Lactate-Citrate or Calcium-Magnesium Lactate-Citrate complexes optionally stabilized with carbohydrates. BACKGROUND OF THE INVENTION Calcium, the most abundant mineral in body, is a major constituent of bone and teeth. This mineral also plays an important role in several physiological systems. Calcium is important for healthy bone and tooth development in the young and an adequate intake is essential. Calcium status may also be a factor in the development of osteoporosis in elderly people. Since the body does not produce minerals, it is totally dependent on an external supply of calcium, nutritional or supplementary. The importance of adequate calcium intake is recognized during the whole life of the human being. In 1994, the NIH Consensus Development Panel revised recommended daily allowances for calcium intake for each age group from 800-1200 mg per day to 1500 mg per day. It has been found that organic acids salts of calcium are more bioavailable in general than the inorganic salts. Calcium citrate has advantages over other calcium salts for use in fortified foods because of high bio-availability. Calcium citrate, as opposed to calcium in general, has only a marginal effect of interfering with the absorption of other minerals, especially iron. Also, long-term calcium supplementation with calcium lactate - citrate can reduce the risk of the formation of kidney and urinary stones since citrate ions are inhibitors of crystallization of stone-forming calcium salts. Magnesium also plays an important role in the human organism. The adult body contains 20-28 g of magnesium, approximately 60% of which is present in the skeleton, 40% resides in the muscles and soft tissues and about 1% in the fluid. Magnesium participates in numbers of biochemical and physiological processes such as biosynthesis, glycolysis, transmission of the genetic code, enzyme activation, etc. Further, extracellular magnesium is critical to the maintenance of electrical potential of nerve and muscle membranes and for transmission of impulses across neuromuscular junctions. The RDA for adults of both sexes is accepted to be 4.5 mg/kg, so 280 mg for women and 350 mg per day for men aged 19 and above (Recommended Dietary Allowances, National Academy Press, Washington, D.C., 1989, 10 th Edition). Addition of calcium to water or clear beverages presents very significant problems. Firstly, if highly soluble sources of calcium (calcium chloride, etc.) are used, a high level of soluble calcium leads to undesirable flavour and destabilisation of proteins. Secondly, slightly soluble sources of calcium will not cause destabilisation of protein micelles but they will precipitate rapidly. Accordingly, the solubility of the calcium sources has to be balanced within a very small range of solubility. Therefore, it would be highly desirable to have calcium and calcium-magnesium sources to fortify water, juices, beverages and other liquid food products without coagulation and sedimentation, with improved palatability, and without bitterness or off-flavor. SUMMARY OF THE PRIOR ART J09175994 discloses an liquid calcium drink prepared by dissolving a calcium source, calcium carbonate or pulverized shell of oyster with malic and /or citric and lactic acid, particularly at ratios 1 : 1-20, followed by heating at 50 -100 degree C. The advantage is to supply calcium with improved taste. DE4111040 describes fruit juice enriched with a mixture tri-potassium citrate, calcium lactate, magnesium gluconate and ferrous gluconate. The pH of the fruit juice is preferably adjusted to 4.3 with lemon or lime juices. The advantage is supply minerals which may be insufficient in the diet, in a drink, in a form with a pleasant taste. J55088685 describes a health drink composition containing calcium lactate, amino acid-rich vinegar, and optionally lactic acid, citric acid and/or apple vinegar in aqueous alkaline solution. The composition includes 500-1000 mg of calcium lactate and 500-3000 mg of amino acid-rich vinegar in 100 ml of solution and has a pH of 3.6-3.8 and a sugar content 6.5-10%. Optionally, 150-500 mg of lactic acid, 150-500 mg of citric acid and/or 500-2000 mg of apple vinegar are also combined in 100 ml of solution. Citric acid, honey, perfume, etc. are optionally combined. By using calcium lactate and amino acid-rich vinegar, the drink contains 1200 ppm of calcium. It is stated that calcium ions are easily absorbed and the drink prevents blood acidification and various diseases and disorders caused by calcium deficiency. Calcium and vitamin C containing beverages with improved color stability are described in US Patent 5,424,082. Stable nutritional vitamin and mineral supplemented beverages are described in US Patent 4,992,282. A majority of these patents do not address the issue of the quantities of these drinks required to get the daily recommended allowances of calcium and other nutrients from such preparations. Such nutritional drinks also lack organoleptic properties for good consumer acceptance. Accepted calcium salts like calcium carbonate, calcium phosphate and calcium citrate for biological use tend to have very poor water solubility resulting in precipitation. Most soluble calcium salts have a very unpleasant bitter taste, while others (e.g., calcium glycero-phosphate) are very expensive or, such as calcium lactate, have very low calcium content. Thus, there is a need for good tasting bottled water, juices and beverages with a sufficient amount of calcium to meet the US Daily Recommended Allowances. SUMMARY OF THE INVENTION We have found that metastable Calcium Lactate-Citrate complexes formed by the interaction of an alkaline calcium source such as calcium hydroxide, calcium oxide or calcium carbonate with a mixture of lactic and citric acids optionally stabilised with various carbohydrates such as sucrose, fructose, maltodextrins, corn syrup, etc. can be used to fortify carbonated and non-carbonated water, clear juices and low pH beverages which are stable at refrigeration, room and high temperature condition as well as withstanding freezing/thawing cycles without precipitation and changing organoleptic properties. According to the present invention, there is provided a composition comprising fortified water, a juice or a low pH beverage and a fortifying amount of a metastable Calcium Lactate-Citrate complex formed by the interaction of an alkaline calcium source with a mixture of lactic and citric acids. Optionally, the complex may be stabilised with a carbohydrate such as sucrose, fructose, maltodextrins, corn syrup, etc. DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly applicable to the fortification of juices and beverages which are clear, so that no gums and other stabilizers are required. The alkaline calcium source may be, for instance, calcium hydroxide, calcium oxide or calcium carbonate which is conveniently used in suspension or as dry powder. The mixture of lactic and citric acids is conveniently used as a solution especially an aqueous solution. A metastable Calcium Lactate-Citrate complex represents a form of calcium which is considerably more soluble than calcium citrate, minimizing precipitation of salts in calcium fortified beverages. On the other hand, complex formation leads to a decrease of free ionic calcium content, thereby increasing the heat stability of products fortified with calcium, as well as preventing protein coagulation during the heat treatment of beverages such as milk or other dairy based products. The preferred complex described in this application is a metastable complex having the formula of [CapfOOC - CH 2 - C(OH)(COO ) - CH 2 - COO-} q {CH 3 - CH(OH) - COO " } r ], wherein p, q and r represent the molarities of calcium hydroxide, citric and lactic acids, respectively. For every 1 mole of p, the molar ratios of q may vary from 20 to 0.2, and r - from 0.2 to 20, respectively. In this invention, it is to be understood that "Citr" denotes the formula OOC - CH 2 - COH(COO ) - CH 2 - COO- , and "Lact" denotes the formula CH 3 - CH(OH) - COO\ The composition of the Calcium Lactate-Citrate complex plays an important role in the thermostability and solubility of the product. Lower lactic acid containing complexes are more thermostable and better suited for whole protein based products because of the lower amount of free calcium introduced into the system. Calcium Lactate-Citrate complexes of the present invention are preferably formed by mixing a suspension of the alkaline calcium source, e.g. calcium hydroxide, calcium oxide or calcium carbonate with the desired amount of solution of citric and lactic acids. Further, the order of ingredient addition results in the formation of a more stable Calcium Lactate-Citrate complex and preferably lactic acid and calcium source are combined together first, then citric acid is added. These complexes possess all the advantages of the previous K 3 [CaCitrLact 2 ] complex described in US Patent No.5,928,691 but have minor or no bitterness due to elimination of the potassium content. The preferred formula of the metastable complexes without potassium are [Ca Citr 0 .2 Lact 1. 7 ] and [Ca Citr 0 . 4 5 Lactn. 95 ]. If desired, part of the calcium ions may be replaced by magnesium ions having the formula of [(Ca x Mg y )p{OOC - CH 2 - C(OH)(COO ) - CH 2 - COO } q {CH 3 - CH(OH) - COO " U where the ratio of x to y could be from 1 : 99 to 99 : 1, but most preferably from 3.0 to 3.5 : 1, and where the subscripts p, q and r represent molarities of calcium hydroxide or magnesium hydroxide, citric and lactic acids, respectively. For every 1 mole of p; molar ratios of q may vary from 20 to 0.2, and r may vary from 0.2 to 20, respectively. For reasons of simplicity, the Calcium Lactate-Citrate complexes referred to in this specification should be understood to include complexes where the metal ion is calcium or where some of the calcium is replaced by magnesium, i.e. the complexes may be Calcium Lactate-Citrate complexes or Calcium-Magnesium Lactate-Citrate complexes. The Calcium-Magnesium Lactate-Citrate complexes of the present invention are preferably formed by mixing a suspension of the alkaline calcium source, e.g. calcium hydroxide, calcium oxide or calcium carbonate with the appropriate quantity of a suspension of the alkaline magnesium source, e.g.magnesium hydroxide, magnesium oxide or magnesium carbonate, and then mixing with the desired amount of solution of citric and lactic acids. Advantageously, the Calcium Citrate-Lactate or Calcium-Magnesium Citrate- Lactate complexes may be used in combination with oligosaccharides or oligo- and polysaccharides, such as inulin or hydrolyzed inulin, e.g. Raftilose P95 or Raftilin GR. The amount of oligosaccharides or oligo- and polysaccharides may be from 0.1 to 25%, preferably from 0.2 to 2% and most preferably from 0.5 to 0.7% by weight based on the weight of the complex. This combination of the complex and inulin does not decrease the complex stability (no sediment formation). However, the combination of the metastable complex and inulin brings additional benefits since it has been shown that dietary fiber enhances calcium absorption. The amount of the complex present in the fortified water, low pH beverage or juice may be from 0.05 to 95%, preferably from 0.1 to 25%, and more preferably from 0.2 to 5% by weight based on the weight of the fortified water, beverage or juice. The present invention also provides a process of preparing a fortified water, low pH beverage or juice which comprises adding a fortifying amount of a metastable Calcium Lactate-Citrate complex formed by the interaction of an alkaline calcium source with a mixture of lactic and citric acids. Advantageously, carbohydrates may be added to the complex, preferably before the complex is added to the fortified water, low pH beverage or juice. The amount of carbohydrates (sucrose, fructose, maltodextrins, corn syrup, etc.) present in the complex can be 1-80%, preferably from 5.20% by weight based on the weight of the complex. The carbohydrates may also be added to the fortified water, beverage or juice in the form of an aqueous solution or as a dry powder. The Calcium Lactate-Citrate complex can be made in situ. Thus, instead of forming the complex first and then adding it to the ingredients of the complex (an alkaline calcium source with lactic and citric acids) may be added to the fortified water, low pH beverage or juice to be fortified, either simultaneously or one after the other (while acids should be added first, before addition of the calcium source), where they interact to form the complex. In this embodiment, one or both ingredients may be added in solid form, or as solutions or dispersions to give the fortified water, low pH beverage or juice. The present invention further provides a process of preparing a fortified, water beverage or juice which comprises adding an alkaline calcium source with lactic and citric acids to the foodstuff and forming the complex within the foodstuff. The following improvements and/or advantages are achieved using the hereinbefore defined complexes to fortify water, beverage or juice as in the present invention. Soluble/clear calcium source Improved palatability, no bitterness or off-flavor • Stable without precipitation at refrigeration, room and high (100°F) temperatures Heat stable (pasteurization, UHT pasteurization/sterilization) Freeze/Thaw resistant Decreased free calcium level, so does not cause protein coagulation • May be prepared in situ Calcium hydroxide provides higher level of calcium @ 54.09% (to compare, Calcium Lactate @13.0%) Could be used to fortify clear or translucent beverages and semi-liquid food products (e.g., jelly, yogurt, etc.) EXAMPLES The following examples further illustrate the present invention. Example 1. Citric acid (1.26 g) is dissolved in 80g of water at room temperature, and then 4.30 g of 88% lactic acid solution are added to the citric acid solution under agitation. A dispersion of 2.22 grams of calcium hydroxide in 20 g of water is prepared. The calcium hydroxide suspension, water (132.2 g) and the solution of the two acids are combined and mixed for 5-10 minutes until the metastable complex is formed as a clear solution. The level of calcium in the complex is 5,000 ppm. Example 2. The clear metastable complex (5,000 ppm Ca) formed in Example 1 was added to water up to a level of 1000 mg L and no sedimentation occurred over three months storage at low (40°F), room and high (100°F) temperatures. The fortified water was subjected to freeze/thaw cycles and no sedimentation occurred. Example 3. A clear metastable complex is prepared according to this invention containing 6,000 ppm Ca and stabilised withl0% sucrose. T e stabilised complex was added to Apricot Nectar @ 12 and 25% RDA up to a level of 1000 mg/L without causing sedimentation problems and no detectable calcium aftertaste. Example 4. A clear metastable complex is prepared according to this invention containing 2,000 ppm Ca and stabilised with inulin (Raftilose P95 and Raftilin GR). The stabilised complex was added to water to give final calcium 400 mg and 3 g inulin per serving (500 mL). Further, carbonated and/or sweetened/unsweetened versions were prepared. No sedimentation problems and no detectable calcium aftertaste were detected during 6 months storage at refrigeration (40°F), room and high (100°F) temperatures. Example 5. 8.9 g of 88% lactic acid solution added to 963 g of water at room temperature and then 8.9 g of citric acid is dissolved in this solution under agitation. The 6.9 g of calcium hydroxide and 3.0 g of magnesium hydroxide are mixed together, then added to the solution of the two acids and mixed for 5-10 minutes until the metastable complex is formed as a clear solution. Example 6. The clear metastable Calcium-Magnesium Lactate-Citrate complex formed in Example 5 was added to water up to a level of 900 mg/L of calcium and 300 mg/L magnesium and no sedimentation occurred over three months storage at low (40°F), room and high (100°F) temperatures. The Calcium-Magnesium fortified water was subjected to freeze/thaw cycles and no sedimentation occurred.

Claims: TO CLAIMS 1. A composition comprising fortified water, juices, beverages, or other liquid food products and a fortifying amount of a metastable Calcium Lactate-Citrate complex formed by the interaction of an alkaline calcium source with a mixture of lactic and citric acids. 2. A composition according to claim 1 wherein the complex is stabilized with a carbohydrate. 3. A composition according to claim 1 wherein the carbohydrate is sucrose, fructose, glucose, corn syrup, maltodextrin, oligo- and polysaccharides or mixture of thereof. 4. A composition according to claim 1 wherein the juice or beverage is clear. 5. A composition according to claim 1 wherein the alkaline calcium source is calcium hydroxide, calcium oxide or calcium carbonate. 6. A composition according to claim 1 wherein the complex is a metastable complex having the formula of [Ca p fOOC - CH 2 - C(OH)(COO " ) - CH 2 - COO " } q {CH 3 - CH(OH) - COO " } r ], wherein p, q and r represent the molarities of calcium hydroxide, citric and lactic acids, respectively and for every 1 mole of p, the molar ratios of q may vary from 20 to 0.2, and r may be from 0.2 to 20, respectively. 7. A composition according to claim 1 wherein the complex is a metastable complex having the formula of [Ca Citr 0 . 2 Lact ι .7 ] or [Ca Citio .45 Lacto. 95 ]. 8. A composition according to claim 1 wherein the alkaline calcium source is used in suspension or as dry powder and the mixture of lactic and citric acids is used as a solution. 9. A composition according to claim 1 wherein part of the calcium ions may be replaced by magnesium ions having the formula of [(Ca x Mg y ) p { ' OOC - CH 2 - C(OH)(COO ) - CH 2 - COO } q {CH 3 - CH(OH) - COO " where the ratio of x to y is from 1 : 99 to 99 : 1, and where the subscripts p, q and r represent molarities of calcium hydroxide or magnesium hydrohide, citric and lactic acids, respectively and where for every 1 mole of p, the molar ratio of q is from 20 to 0.2, and the molar ratio of r is from 0.2 to 20. 10. A composition according to claim 9 where the ratio of x to y is from 3.0 to 3.5 : 1. 11. A composition according to claim 1 wherein the complex is used in combination with oligosaccharides or oligo- and polysaccharides. 12. A composition according to claim 11 wherein the oligosaccharide or poiysaccharide is inulin or hydrolyzed inulin. 13. A composition according to claim 1 wherein the amount of the complex present in the fortified water, low pH beverage or juice is from 0.05 to 95% by weight based on the weight of the fortified water, low pH beverage or juice. 14. A process of preparing a fortified water, beverage, juice, or other liquid food products which comprises adding a fortifying amount of a metastable Calcium Lactate-Citrate or Calcium-Magnesium Lactate-Citrate complexes according to any of claims 1 to 13 formed by the interaction of an alkaline calcium source with a mixture of lactic and citric acids. 15. A process of preparing a fortified water, juice, beverage or other liquid food products according to claim 14 wherein a fortifying amount of a metastable Calcium Lactate-Citrate or Calcium-Magnesium Lactate-Citrate complexes is stabilized with carbohydrates. 16. A process according to claim 14 wherein carbohydrates are added to the complex before the complex is added to the fortified water, beverage or juice in an amount of from 1 -80% by weight based on the weight of the complex. 17. A process of preparing a fortified water, beverage, juice or other liquid food products which comprises adding an alkaline calcium source with lactic and citric acids to the foodstuff and forming the complex within the foodstuff. 18. A process of preparing a fortified water, juice, beverage or other liquid food products according to claim 14 wherein the acids one after another or mixture of acids are adding to water, juice, beverage or other liquid first before adding the powder or suspension of calcium source. 19. A process of preparing a fortified water, juice, beverage or other liquid food products according to claim 14 wherein the lactic acid and calcium or calcium/magnesium source are combined together first, then citric acid is added and this complex is then combined with water, juice, beverage or other liquid.

Inventors: MALLANGI CHANDRASEKHARA REDDY, PANYAM DINAKAR, SHER ALEXANDER, VADEHRA DHARAM VIR, MALLANGI, CHANDRASEKHARA, REDDY, PANYAM, DINAKAR, SHER, ALEXANDER, VADEHRA, DHARAM, VIR
Applicants: MALLANGI CHANDRASEKHARA REDDY, NESTLE SA, PANYAM DINAKAR, SHER ALEXANDER, VADEHRA DHARAM VIR, MALLANGI, CHANDRASEKHARA, REDDY, PANYAM, DINAKAR, SHER, ALEXANDER, SOCIETE DES PRODUITS NESTLE S.A., VADEHRA, DHARAM, VIR
Application year: 2000
Main classification: A23L1
IPC codes: A23L1, A23L2