USOO6576277B2 (12) United States Patent (10) Patent No.: US 6,576,277 B2 Livisay et al. (45) Date of Patent: Jun. 10, 2003 (54) CALCIUM-FORTIFIED, GRAPE-BASED 4,891,236 A 1/1990 Ohta et al. .................. 426/599 PRODUCTS AND METHODS FOR MAKING 4.919,963 A 4/1990 Heckert ...................... 426/599 THEM 4,992.282 A 2/1991 Mehansho et al. ............ 426/72 5,141,758. A 8/1992 Monte ................ ... 426/72 (75) Inventors: Stacy A. Livisay, Voorhees, NJ (US); 5,225.221 A 7/1993 Camden et al. ............... 426/74 James P. Lavoie, Billerica, MA (US) 5,322,702 A 6/1994 Selinger et al. ............. 426/583 s s 5,474,793 A 12/1995 Meyer et al. ............... 426/599 5,597,595 A 1/1997 DeWille et al. ............... 426/74 (73) Assignee: Welch Foods, Inc., Concord, MA (US) 5,641,531. A 6/1997 Liebrecht et al. ........... 426/583 6,106,874. A * 8/2000 Liebrecht et al. ............. 426/74 (*) Notice: Subject to any disclaimer, the term of this Lee et a patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS U.S.C. 154(b) by 119 days. EP O 397 232 4/1990 ............. A23L/2/26 EP O 486 425 10/1991 ............. A23L/1/29 (21) Appl. No.: 09/788,327 GB 10244.08 3/1966 ..... ... A23H71/OO WO WO 93/12672 7/1993 ..... ... A23L/2/38 (22) Filed: Feb. 16, 2001 WO WO OO/28838 5/2000 ..... ... A23L/2/OO (65) Prior Publication Data WO WO OO/53035 9/2000 ..... ... A23L/1/304 US 2002/0001642 A1 Jan. 3, 2002 OTHER PUBLICATIONS Ashurst, P. R. 1995, Production and packaging of Non-car Related U.S. Application Data b onated fruit juices and fruit beverage, Blackie Academic & (60) givisional application No. 60/183,299, filed on Feb. 17, Professional, 2" Ed., pp. 98, 99.* (51) Int. Cl." ............................ A23L 1/304; A23L 2/02 cited by examiner (52) -rr. 426/74; 426/599 Primary Examiner Helen Pratt (58) Field of Search .................................... 426/74, 599 (74) Attorney, Agent, or Firm-Bromberg & Sunstein LLP (56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS Methods of making a calcium fortified, tartaric acid 1915,273 A 6/1933 Eoff, Jr. ...................... 426/599 containing product that is essentially free of tartrate 3,922,375 A 11/1975 Dalan et al. ... ... 426/583 precipitates, and products made by this method. The tartaric 3,949,098 A 4/1976 Bangert ........ ... 426/324 acid concentration of a precursor is adjusted to form an 3,958,017 A 5/1976 Morse et al. ................. 426/72 adjusted precursor. An additive containing a calcium-based 4,309,417 A 1/1982 Staples ....................... 424/128 compound is mixed with the adjusted precursor to make the 4,486,413 A 12/1984 Wiesenberger et al. ..... 424/177 fortified product. The compound may be calcium gluconate, 4,722.847. A 2/1988 Heckert ....................... 426/74 a variety of other compounds or mixtures thereof. The 4.737,367 A 4/1988 Langer et al. ................ 426/72 fortified product, when stored at approximately 70 F., may E. A E", - - - - - - - - - - - - - - - - - - - - - - - -42... remain essentially free of tartrate precipitate for at least 2 Y-2 C. Kal ....... 4,786,510 A 11/1988 Nakel et al. .................. C, sixteen weeks. 4,830.862 A 5/1989 Braun et al. .................. 426/74 4,871,554. A 10/1989 Kalala et al. ................. 426/74 40 Claims, No Drawings US 6,576.277 B2 1 2 CALCIUM-FORTIFIED, GRAPE-BASED calcium Sources. U.S. Pat. No. 6,106,874 to Liebrecht et al. PRODUCTS AND METHODS FOR MAKING discloses a calcium-fortified nutritional beverage, which can THEM be made from Single Strength juice. Calcium Sources therein are natural milk mineral and Gluconal CALE (manufactured RELATED U.S. APPLICATION(S) by Glucona America). Calcium fortification of grape-based beverages is espe This application claims priority from U. S. Provisional cially challenging. The predominant organic acid in grape Application Ser. No. 60/183,299, filed Feb. 17, 2000, which based liquid (e.g. juice, wine, etc.) is, uniquely among is hereby incorporated herein by reference. fruit-derived liquids, tartaric acid. At pH levels above 2.8, tartaric acid will chemically dissociate into tartrate, bitar TECHNICAL FIELD trate and hydrogen ions. AS the pH of grape juice increases, the dissociation of tartaric acid becomes progressively more The embodiment relates to formulation of grape-based favored. AcroSS the typical pH range of about 2.8 to about products Such as, but not limited to, juice, juice-blended 3.9 for purple, red and white grape juices from Vitis beverages, and wine containing a Significant amount of labrusca, V. vinifera, and V. labrusca X V, vinifera hybrid bioavailable calcium as well as to processes for the manu 15 grapes, the availability of tartrate ions for reaction with any facture of the products. The field encompasses the added calcium to form insoluble crystalline calcium tartrate, production, Storage and distribution of Stable calcium is very high. Indeed, at relatively high pH and without the fortified purple, red and white grape juice and juice drinks, presence of calcium, potassium bitartrate crystals or "argol' in shelf-stable, refrigerated, frozen and concentrate forms. in juice (or “wine stones” in wine) may be formed due to the Beverages covered include grape-based liquids blended with naturally occurring concentration of potassium in grape non-grape liquids. based product. This is commonly found in winemaking and the pertinent literature is abundant in addressing ways to BACKGROUND ART solve this problem. Calcium is an essential mineral in the human diet for the The formation of calcium tartrate crystals in grape-based 25 liquids is known from past research on wines. This forma preservation of human health. Calcium has been established tion is dependent, for example, on the pH of the beverage, as a key nutrient for Skeletal rigidity; it is also known to the Storage temperature of the calcium plus beverage impact metabolic, muscular, neurological, circulatory, and mixture, the presence of inhibitors, the ionic strength of enzymatic processes. Calcium deficiency is a contributing Solution, agitation of Solution, and the length of time that the cause of Osteoporosis, a debilitating bone disease marked by mixture is held in Storage. Abgueguen and Boulton, (1993); a loSS of bone mass. McKinnon, 1993. Formation of calcium tartrate crystals may Calcium is naturally found in many foods. The primary occur instantly upon the cooling of a pasteurized juice Source of bioavailable calcium is milk and, more generally, calcium mixture, Alternatively, crystals may not occur for a dairy products. AS people enter early adulthood, their con Substantial period of time. However, because calcium tar Sumption of dairy products tends to decrease. This may lead trate crystals have very low Solubility in aqueous Solutions to a State of chronic calcium deficiency. This trend is 35 Such as grape juice, once formed, these crystals will tend to particularly found with young women and could contribute remain as an insoluble precipitate rendering the beverage to their high rates of Osteoporosis development in later life. organoleptically unacceptable with Significantly diminished Additionally, many people are, or become, lactose intolerant bioavailable calcium. After initial nucleation of these as they age, thus reducing their ability to obtain natural, crystals, they will generally grow in size until the point of traditionally rich Sources of this mineral. 40 Solution Saturation is reached. Therefore, many alternate Sources of food, drink, and SUMMARY OF THE INVENTION Supplements are currently being fortified with various In accordance with a first embodiment of the present organic and inorganic calcium Salts. These alternate Sources invention, a method of making a fortified, tartaric acid include pills, powders, food products, as well as a variety of 45 containing product is provided. The product is fortified with fruit and non-fruit based juices and beverages. Many plagu a predetermined amount of bioavailable calcium and the ing problems Surround the provision of organoleptic quali product is essentially free of tartrate precipitates. A tartaric ties and bioavailability of these calcium-fortified sources. A acid-containing precursor is provided. The concentration of common complaint with respect to fortified beverages is the tartaric acid in the precursor may be between approximately relative insolubility of some of the added calcium salts, 50 0.005 g per 100 mls and approximately 1.31 g per 100 mls. intolerable precipitation of Solids, and a “chalky' feeling in The precursor may be a grape-based liquid and may be the mouth upon drinking. Additionally, undesirable flavors derived from colored or white grapes. The predetermined and shelf instability contribute to a poor food product. amount of bioavailable calcium may be between 8% and The fortification of various liquids with calcium, includ approximately 35% of required daily intake for a human. ing Orange, apple and other juices and beverages is an art 55 The tartaric acid concentration of the precursor is adjusted to currently practiced by juice and beverage manufacturers. form an adjusted precursor. In an embodiment, the Patents describing calcium fortification of fruit juices measured, adjusted tartaric acid concentration might be no include Several granted to Heckert and assigned to the greater than 0.17g per 100 mls. An additive comprising a Proctor and Gamble Company (for example, U.S. Pat. No. calcium-based compound is mixed with the adjusted pre 4,722,847). These patents disclose calcium-citrate-malate 60 cursor to make the fortified product. The compound may be (CCM) technology and teach that various calcium citrate calcium gluconate, a variety of other compounds or mixtures and malate compounds, when combined in accordance with thereof. The fortified product, when Stored at approximately disclosed processing methods, will produce Stable, fortified 70 F.