Nutritional mineral supplements comprise a mixture of a calcium source, especially calcium citrate-malate, and an iron-sugar complex, especially iron sucrate-malate. Food and beverage compositions, especially juice beverages, supplemented with these calcium and iron materials are disclosed.

TECHNICAL FIELD 
The present invention relates to mineral supplements which contain certain 
calcium and iron compounds, and foods and beverages containing same. 
BACKGROUND OF THE INVENTION 
Vitamin and mineral supplements for human and veterinary use are 
commonplace. Recently, it has become recognized that certain groups of the 
human population may require quite high intakes of minerals, such as 
calcium, to prevent or alleviate certain disease states, for example, 
osteoporotic conditions. The medical management of certain anemias can be 
handled rather well by increasing the daily intake of iron. Some diets, or 
heavy physical exercise, may require the intake of considerable quantities 
of minerals apart from those generally obtained through what otherwise 
would be considered a balanced diet. 
Mineral supplements, such as those commercially available, are useful in 
many circumstances where enhanced mineral uptake is desirable. However, 
adhering to a regimen which requires the separate intake of mineral 
supplements can give sub-optimal results, simply because the regimen 
requires a change in the normal habits and practices of the user. It would 
be more convenient if the minerals could be included in ordinary foods and 
beverages, so that they would be ingested without extra attention, 
planning and implementation on the part of the user. 
There are well-recognized problems associated with adding mineral 
supplements to foods and beverages. For example, many calcium supplements 
tend to be rather insoluble, and, therefore, not very useful in beverages, 
or tend to have a "chalky" taste or mouth feel. Iron supplements tend to 
discolor foodstuffs, or to be organoleptically unsuitable. Moreover, it is 
particularly difficult to formulate foods and, especially, beverages, 
containing mixtures of calcium supplements and iron supplements, inasmuch 
as these minerals tend to interact. This interaction not only affects the 
organoleptic and aesthetic properties of the foods and beverages, but also 
undesirably affects the nutritional bioavailability of these minerals, 
themselves. 
It would be desirable, therefore, to have mixed calcium and iron 
supplements which are compatible and nutritionally available. It would 
also be quite useful to have such supplements which could be added to food 
and beverage compositions without undesirably affecting organoleptic or 
aesthetic properties. 
It is an object of the present invention to provide calcium-iron mineral 
supplements which fulfill these unmet needs. 
It is a further object of this invention to provide foodstuffs, beverages 
and beverage concentrates which are supplemented with calcium and iron. 
These and other objects are secured herein, as will be seen from the 
following disclosure. 
BACKGROUND ART 
Certain forms of calcium citrate-malate are disclosed for use as mineral 
supplements, including beverages; see Japanese Application No. Sho 
54-173172, date of application 28 Dec. 1979, laid-open No. Sho 56-97248, 5 
Aug., 1981; and see also French Pat. No. 2,219,778 (Application No. 
73.08643). 
Some form of iron sucrate has been administered to children and the effect 
on Hb reported; see the Russian reference Metreveli, E. G., PEDIATRIYA 
(Moscow) 1977, (12), 17-19; C. Abs. 89: 637. 
Remington's Pharmaceutical Sciences, 15th Ed., 393 (1975) indicates that 
ferrous and ferric ions form soluble coordination complexes with many 
agents such as ammonium salts, citrates, tartrates, amines, sugar and 
glycerine, which protect the iron from precipitation by the usual iron 
precipitants. Iron gluconate and fumarate salts are said to be employed as 
hematinics. 
Goodman and Gilman, The Pharmacological Basis of Therapeutics, 5th Ed., 
1315-1316 (1975) reports that iron salts have many incompatibilities and 
should be prescribed alone, preferably between meals, for maximal 
absorption, but just after meals if necessary to minimize gastric 
symptoms. Gastrointenstinal absorption of iron is reportedly adequate and 
essentially equal from the following six ferrous salts: sulfate, 
fuamarate, gluconate, succinate, glutamate, and lactate. Absorption of 
iron is lower from ferrous citrate, tartrate, pyrophosphate, etc. Reducing 
agents such as ascorbic acid and some chelating agents such as succinic 
acid may increase absorption of iron from ferrous sulfates, but are said 
to be not worth the extra cost because of the high efficacy of ferrous 
sulfate when administered alone. Ferrous sulfate is reported to have a 
saline, astringent taste, and is mixed with glucose or lactose to protect 
it against oxidation, when used as an iron supplement. 
European Pat. No. 164,657 to Pfeiffer and Langden relates to an iron 
dextran, which is obtained by adding precipitated ferric hydroxide to 
dextran produced by adding sucrose solution to a solution of D-glucose and 
dextran-sucrose enzyme. 
U.S. Pat. No. 4,582,709, to Peters and Derick, Apr. 15, 1986, relates to 
chewable mineral supplements, and lists, inter alia, various calcium and 
iron compounds. 
U.S. Pat. No. 4,351,735, to Buddemeyer, et al, Sept. 28, 1982, relates to 
mineral supplements which contain certain phosphate moieties. 
Dispersibility of the compositions is said to be enhanced by "hydroxyl 
sources", e.g., sugars. 
U.S. Pat. No. 4,214,996, to Buddemeyer, et al, July 29, 1980, relates 
generally to the same subject matter as the U.S. Pat. No. 4,351,735, 
above, but claims, inter alia, iron compositions and calcium compositions. 
The beneficial effect of orange juice on the uptake of iron from dietary 
sources is described by Carlson and Miller in JOURNAL OF FOOD SCIENCE 48, 
1211 (1983). 
U.S. Pat. No. 2,325,360, to Ayres et al, issued July 27, 1943, discloses a 
method for replacing gases removed during deaeration of fruit juices, such 
as orange juice, with carbon dioxide. In this method, dry calcium 
carbonate, or a mixture of calcium carbonate and citric acid, is dropped 
into a can which is then filled with deaerated orange juice. (Other 
organic acids such as malic and tartaric acid can be used in place of 
citric acid.) 
U.S. Pat. No. 3,657,424, to Akins et al, issued Apr. 18, 1972, discloses 
the fortification of citrus juices, including orange juice, with sodium, 
calcium and chloride ions in amounts beyond what is naturally present in 
the juice. Calcium salts which can be used in fortification include the 
chlorides, citrates or phosphates, although calcium chloride is preferred 
for providing the desired chloride ion. 
U.S. Pat. No. 3,114,641, to Sperti et al, issued Dec. 17, 1963, discloses 
extended orange juice products obtained by diluting single-strength orange 
juice or concentrated orange juice. To maintain the flavor of the diluted 
orange juice product, materials such as calcium chloride, magnesium 
chloride, sodium or potassium citrates, tartaric and malic acids (or their 
salts) are included. 
British patent specification No. 2,095,530, published Oct. 6, 1982, 
discloses a process for obtaining an acid beverage enriched in protein, 
particularly a fruit juice or fruit-flavored beverage. In this process, an 
aqueous suspension of soy protein is prepared using water and/or fruit 
juice. Calcium in a concentration of from 5 to 50 mM is added, after which 
the pH of the suspension is reduced and the insoluble material separated 
to yield a protein solution. A fruit juice or fruit flavoring can then be 
added to this protein solution . The calcium can be added in the form of 
the chloride, acetate, tartrate, malate or lactate salt. 
European patent application No. 75,114, published Mar. 30, 1983, discloses 
protein-containing fruit juice drinks enriched with vitamins and minerals. 
These drinks contain 30-90% fruit juice (a mixture of 20-70% apple juice, 
4-40% white grape juice, 1-10% passionfruit juice and 5-25% lemon juice), 
2 to 20% whey protein concentrate, and a mineral salt mixture of 
potassium, sodium, magnesium, calcium and phosphate. Calcium is present in 
these drinks at 0.01 to 0.3%, preferably at 0.02 to 0.03%. 
SUMMARY OF THE INVENTION 
The present invention encompasses nutritional mineral supplements which 
comprise a mixture of a nutritionally supplemental amount of a calcium 
source, especially calcium citrate-malate, and a nutritionally 
supplemental amount of an iron-sugar complex. The counterions associated 
with the iron-sugar complexes herein are preferably members selected from 
the group consisting of malate (most preferred), citrate, tartrate, 
ascorbate, and mixtures thereof. Preferred supplements contain iron 
sucrate-malate, iron fructate-malate, or mixtures thereof. Preferably, the 
iron in the complexes comprises ferrous iron, but ferric iron is also 
acceptable. 
The invention also encompasses food, beverage or beverage concentrate 
compositions which comprise: 
(a) a foodstuff, beverage or beverage concentrate; 
(b) a nutritionally supplemental amount of a calcium supplement, most 
preferably calcium citrate-malate; and 
(c) a nutritionally supplemental amount of an iron-sugar complex, 
preferably a member selected from the group consisting of iron 
sucrate-malate (most preferred), iron fructate-malate, iron 
sucrate-citrate, iron fructate-citrate, iron sucrate-ascorbate, iron 
fructate-ascorbate, or mixtures thereof. Again, the iron is preferably in 
the ferrous state. 
Typical of the compositions of this invention are beverage or beverage 
concentrates which comprise: 
(a) at least about about 0.1% by weight of fruit or cola flavor, or at 
least about 3% by weight of fruit juice; 
(b) a nutritionally supplemental amount of calcium citrate-malate; and 
(c) a nutritionally supplemental amount of an iron-sugar complex, most 
preferably iron II sucrate-malate. 
By way of example, the fruit juice in such compositions can be selected 
from grape juice, pear juice, passionfruit juice, pineapple juice, banana 
juice or banana puree, apricot juice, orange juice, lemon juice, 
grapefruit juice, apple juice, cranberry juice, tomato juice, tangarine 
juice, and mixtures thereof. 
The invention encompasses beverages, especially juice and cola beverages, 
which are carbonated in the manner of soft drinks, as well as "still" 
beverages. The invention also encompasses nectars and full-strength 
beverages or beverage concentrates which contain at least abvout 45% by 
weight of juice. 
The nutritional supplements herein are particularly useful with beverages 
or beverage concentrates made from orange juice or grapefruit juice. 
As will be disclosed more fully hereinafter, the mineral supplements of 
this invention can conveniently be used in powder, tablet, chewable 
lozenge, capsule or liquid form, for enteral or parenteral nutrition, and 
in combination with conventional foodstuffs, such as breads, cakes, 
snacks, infant formulations, meat analogs and extenders, spreads, and the 
like. 
All ratios, proportions and percentages herein are by weight, unless 
otherwise specified. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention involves the conjoint use of 
nutritionally-supplemental amounts of calcium and iron compounds in humans 
and lower animals. 
By "nutritional" or "nutritionally-supplemental amount" herein is meant 
that the mineral sources used in the practice of this invention provide a 
nourishing amount of said minerals. In mineral supplements such as tablets 
or powders, this supplemental amount will comprise at least 3% of the 
Recommended Daily Allowance (RDA) of the daily intake of said mineral, as 
defined in The United States of America (see Recommended Daily Dietary 
Allowance--Food and Nutrition Board, National Academy of 
Sciences--National Research Council). More generally, mineral supplements 
will contain at least 10%, more typically 50% to 300%, of the RDA per unit 
dose of the supplement. In food or beverage products of the type disclosed 
herein, the nutritionally supplemental amount will generally comprise more 
than 3% of the RDA, preferably 10%-100% RDA, most preferably 10%-30% of 
the RDA, per unit portion of the food or beverage product. Of course, it 
is recognized that the preferred daily intake of any mineral may vary with 
the user. For example, pregnant, lactating, or post-menopausal females may 
require an increased intake of calcium, over the usual RDA. Persons 
suffering with anemia may require an increased intake of iron. Such 
matters are familiar to physicians and nutritional experts, and usage of 
the compositions of the present invention may be adjusted accordingly. 
In general, the RDA (calcium) will range from 360 mg per 6 Kg for infants 
to 1200 mg/54-58 Kg female, depending somewhat on age. The RDA (iron) 
ranges from 10 mg per 6 Kg to 18 mg per 54-58 Kg female, depending 
somewhat on age. As is well-known, it is possible to overdose with iron 
supplements, especially in males, with deleterious effects to the liver. 
Typically, foods and beverages are supplemented with only about 10-15% RDA 
iron (based per serving) to account for iron which is available from other 
dietary sources (assuming a reasonably balanced diet), thereby avoiding 
this problem. Moreover, it can be difficult to supplement beverages with 
more than 20-30% RDA of calcium (based per serving) without encountering 
precipitation and/or organoleptic problems. However, this level of 
supplementation is equivalent to cow's milk in calcium value, and is quite 
acceptable. Of course, if iron toxicity and organoleptic quality are not 
deemed important considerations in individual circumstances, more of the 
supplements herein can be used. 
The preparation of the preferred calcium source used herein, "calcium 
citrate-malate", is described hereinafter in considerable detail. 
The "iron-sugar" complexes used in the practice of this invention are 
prepared in the manner described more fully hereinafter. (These materials 
are referred to herein as "complexes", but they may, in fact, exist in 
solution as complicated, highly-hydrated, protected colloids. However, the 
term "complex" is used herein for simplicity.) While the iron in these 
complexes can be in the ferric (iron III) state, it is more preferably in 
the ferrous (iron II) state. Ferrous iron is better tolerated and utilized 
by the body than ferric iron. Importantly, feric iron and common ferrous 
salts can cause off-flavors in some beverages, after storage; ferric iron 
can also oxidize and thus degrade ascorbic acid (Vitamin C) in citrus 
beverages. The preferred complexes used herein can conveniently be thought 
of as iron-sugar-carboxylate complexes, wherein the carboxylate provides 
the counterion for the ferrous (preferred) or ferric iron. While not 
intending to be limited by theory, it is believed that the acceptable 
taste of these iron complexes is due to the relatively large sizes of the 
sugar moiety and carboxylate counterion, which mask the usual "well-water" 
and/or brackish flavor of some iron supplements. 
The overall synthesis of the preferred iron-sugar-carboxylate complexes 
used in the practice of this invention involves: 
(a) forming a calcium-sugar moiety in aqueous media, for example, by 
reacting calcium hydroxide with a sugar; 
(b) reacting an iron source, such as ferrous ammonium sulfate, with the 
calcium-sugar moiety in aqueous media to provide an iron-sugar moiety; and 
(c) neutralizing the reaction system with a carboxylic acid, for example, 
malic acid, to provide the desired iron-sugar complex. 
The preferred iron II-sucrate-malate complex prepared in this manner is 
essentially equivalent to ferrous sulfate in iron bioavailability 
(measured as % change in hematocrit of test animals over the range of 0-9 
ppm Fe), and, most importantly, is organoleptically acceptable in 
beverages, especially citrus beverages. 
The "sugars" which can be employed in the practice of this invention 
include any of the ingestible saccharidic materials, and mixtures thereof, 
well-known in the culinary arts. For example, glucose, sucrose and 
fructose can conveniently be employed, with sucrose and fructose being the 
more preferred. However, other saccharidic materials can be used, for 
example mannose, galactose, lactose, maltose, and the like. 
The "carboxylate counterion" used in the preparation of the preferred 
iron-sugar complexes herein can be any ingestible carboxylate species. 
However, some judgment must be made with regard to flavor contribution. 
For example, citrate, malate and ascorbate yield ingestible complexes 
whose flavors are judged to be quite acceptable, particularly in fruit 
juice beverages. Tartaric acid is acceptable, particularly in grape juice 
beverages, as is lactic acid. Longer-chain fatty acids may be used in 
solid mineral supplements, but can affect flavor and water solubility. For 
essentially all purposes, the malate (preferred), citrate and ascorbate 
moieties suffice, although others can be selected, according to the 
desires of the formulator. 
In a less preferred mode, the counterion for the iron-sugar complex can be 
noncarboxylate moieties such as phosphate, chloride, sulfate, or the like. 
However, such counterions can undesirably interact with calcium ions, 
especially in beverages. In high concentrations, these counterions may 
contribute an undesirable flavor note, Accordingly, the carboxylate 
counterions noted above are preferred herein. 
The present invention is particularly suited for the preparation of juice 
beverages and beverage concentrates, particularly orange juice. The 
concentrated orange juice, orange juice aroma and flavor volatiles, pulp 
and peel oils used in the method of the present invention can be obtained 
from standard orange juice processing. See Nagy et al, Citrus Science and 
Technology, Volume 2, (AVI Publishing Co. 1977), pp 177-252 (herein 
incorporated by reference) for standard processing of oranges, grapefruit 
and tangerines. (See also Nelson et al, Fruit and Vegetable Juice 
Processing Technology (3rd Ed., AVI Publishing 1980), pp. 180-505 (herein 
incorporated by reference) for standard processing of noncitrus juices 
such as apple juice, grape juice, pineapple juice, etc. to provide sources 
of juice and juice materials for mineral-supplemented noncitrus juice 
products). Fresh juice is extracted from the oranges, principally of the 
Valencia type. (The peel of the oranges is initially rasped to provide 
peel oils which can be used in the method of the present invention.) 
Juices from different oranges are frequently blended to adjust the sugar 
to acid ratio. A sugar to acid ratio of from about 8:1 to about 20:1 is 
considered acceptable. However, preferred sugar to acid ratios are 
typically from about 11:1 to about 15:1. 
Juice is extracted from the oranges by using automatic juicing machines, or 
less often by hand squeezing of the oranges. The type of equipment used to 
extract the juice is not critical. The raw juice exiting from the 
squeezing device contains pulp, rag and seeds. The rag and seed are 
separated from the juice and pulp in a finisher. The juice is then 
typically separated into a pulp portion and a serum portion. (The pulp 
portion can be used as a source of pulp in the method of the present 
invention.) 
The serum portion can be concentrated by a variety of techniques which 
typically include evaporative concentration or freeze concentration. In 
evaporative concentration, the serum portion of the juice is passed 
through an evaporator (e.g., falling film or temperature accelerated short 
time evaporator [TASTE] type). Water vapor, as well as the aroma and 
flavor volatiles, are stripped from the juice. These stripped volatiles 
are then centrifuged to provide an upper layer (essence oils) and a lower 
layer (aqueous essence). (A portion of these essence oils and aqueous 
essence are typically used as the source of orange juice aroma and flavor 
volatiles for the method of the present invention.) The remaining stripped 
juice is then concentrated in the evaporator (by heat) to the appropriate 
amount of solids as measured by the sugar content of the concentrated 
juice. This concentrated juice can then be used in the method of present 
invention. 
Most concentrated orange juices are obtained by evaporative concentration. 
However, freeze concentration can also be used to obtain concentrated 
orange juice useful in the method of the present invention. Freeze 
concentration typically involves passing the serum portion of the juice 
through a scraped wall heat exchanger to form substantially pure ice 
crystals which are then separated from the concentrated juice. A preferred 
freeze concentration method is disclosed in U.S. Pat. No. 4,374,865 to 
Strobel, issued Feb. 22, 1983, which is incorporated by reference. Unlike 
evaporative concentration, concentrated orange juice obtained by freeze 
concentration typically contains the aroma and flavor volatiles as well. 
Method for Preparing Beverages and Beverage Concentrates Supplemented with 
Calcium and Iron 
The preferred overall method for preparing the liquid compositions herein 
involves preparing premix solutions of the calcium and iron complexes (see 
Examples I, II and III, hereinafter) and admixing the premixes to the 
liquid compositions. The following discussion of this method will 
generally be with regard to formation of orange juice beverages and juice 
concentrates, which are highly preferred fruit juice products according to 
the present invention. However, this method can also be used to prepare 
iron- and calcium-supplemented beverages and concentrates, especially 
those based on other citrus juices such as grapefruit juice, noncitrus 
juices such as apple juice, as well as mixtures of juices. 
In general, an acid component comprising citric acid and malic acid is 
typically dissolved in the appropriate quantity of water. (If desired, 
fruit juice or concentrated fruit juice such as lemon juice can be used to 
supply a portion of the acids.) Generally, this acid component comprises 
from 0 to about 90% by weight citric acid and from about 10 to 100% by 
weight malic acid. For orange juice, this acid component typically 
comprises from about 20 to about 90% by weight citric acid and from about 
10 to about 80% by weight malic acid. Preferably, this acid component 
comprises from about 5 to about 60% by weight citric acid and from about 
40 to about 95% by weight malic acid. (For noncitrus juices such as apple 
juice, this acid component typically comprises from about 5 to about 80% 
by weight citric acid and from about 20 to about 95% by weight malic acid, 
and preferably comprises from about 20 to about 50% by weight citric acid 
and from about 50 to about 80% by weight malic acid.) As a rule, the ratio 
of these acids is selected to provide optimum flavor character in the 
juice. 
Once the solution containing the dissolved acids is formed, a source of 
calcium is then added. Calcium carbonate (CaCO.sub.3) is a preferred 
calcium source. This calcium source leads to the greatest and most rapid 
initial solubilization of calcium and causes the least amount of 
off-flavor generation. Calcium hydroxide [Ca(OH).sub.2 ] and calcium oxide 
(CaO) are also acceptable calcium sources, but can cause more off-flavor 
generation than calcium carbonate. The weight ratio of total acids to 
calcium added in the solution is typically from about 0.5 to about 12. 
Preferably, this weight ratio is from about 1 to about 6. 
Addition of calcium carbonate, calcium oxide, or calcium hydroxide to the 
aqueous solution of acids provides a premix containing soluble and 
solubilizable calcium. This is due to the fact that highly soluble calcium 
citrate and malate species such as CaHcitrate, Ca(H.sub.2 citrate).sub.2, 
and CaHmalate are formed in the solution due to the reaction between the 
calcium source and the acids. Without added stabilizers, the highly 
soluble calcium citrate species are stable in the premix solution for 
periods up to only about a few hours. After this short period of time, the 
highly soluble citrate species tend to disproportionate to the 
corresponding acid and the more thermodynamically stable, insoluble 
calcium citrate salts, such as Ca.sub.3 citrate.sub.2. 
To improve the stability of the more soluble calcium malate and especially 
citrate species in the premix solution, it is preferred in the method of 
the present invention to include a premix stabilizer. Materials which can 
complex with calcium and/or act as crystallization inhibitors are useful 
as premix stabilizers. These materials include sugars, such as sucrose, 
glucose, fructose, high fructose corn syrup, invert sugar, and 
polysaccharides such as pectin, algins, hydrolyzed starches, xanthan gum, 
and other edible gums. Concentrated juices which naturally contain both 
sugars and polysaccharides are particularly suitable premix stabilizers. 
Preferred premix stabilizers are sucrose and high fructose corn syrup 
(especially for extended juice products) and concentrated orange juice 
having a sugar content of from about 35.degree. to about 80.degree. Brix 
whose source is described hereafter. 
The premix stabilizer can be added immediately after the calcium source is 
added to the aqueous solution containing the acids. (When calcium 
carbonate is the calcium source, carbon dioxide evolution is preferably 
allowed to substantially cease before the premix stabilizer is added.) 
However, if desired, the premix stabilizer (especially in the case of 
sugars and concentrated juice) can be added to the aqueous solution of the 
acids prior to addition of the calcium source. The amount of premix 
stabilizer included in the premix solution typically depends upon the 
stabilizer used. When sugars are used as the premix stabilizer, they are 
typically added in an amount sufficient to provide a sugar content of from 
about 2.degree. to about 40.degree. Brix. When polysaccharides are used, 
the amount can vary widely, but is typically from about 0.01 to about 0.5% 
on a weight/volume basis. When concentrated juice is used as the premix 
stabilizer, it is typically included in an amount sufficient to provide a 
sugar content of from about 2.degree. to about 40.degree. Brix (preferably 
from about 2.degree. to about 24.degree. Brix). 
The premix solution of solubilized and solubilizable calcium is typically 
prepared in a batch-type fashion, as in the description above, at room 
temperature. However, this premix solution can also be prepared in a 
continuous fashion. In this continuous method, the ingredients (water, 
acids, calcium source and optional premix stabilizer) are constantly 
metered together to form the premix solution. The level at which the 
ingredients are metered is adjusted, as necessary, to insure appropriate 
solubilization of the calcium in the premix solution and to provide the 
appropriate acidity. 
Separately, a premix solution of the iron-sugar complex is prepared. In 
general, this solution is somewhat simpler to prepare than the calcium 
citrate-malate solution, above, since precipitation is not a major 
problem. Thus, a calcium-sugar reaction product is treated with an iron 
(preferably iron II) source, and the reaction product is neutralized with 
a carboxylic acid, in the manner of Example III, below. 
The premix solution containing the solubilized calcium and the premix 
containing the solubilized iron are combined in a mix tank with chilled 
(e.g., below about 4.4.degree. C.) concentrated orange juice having a 
sugar content of from about 35.degree. to about 80.degree. Brix 
(preferably from about 60.degree. to about 70.degree. Brix), orange juice 
aroma and flavor volatiles, plus other orange juice materials such as pulp 
and peel oils, to provide iron- and calcium-supplemented orange juice 
products. The particular proportions of premix solution, concentrated 
juice, aroma and flavor volatiles, pulp and peel oils used will depend 
upon a number of different factors, including the type of orange juice 
product involved (single-strength juice beverage or juice concentrate). 
For example, iron- and calcium-supplemented 42.degree. Brix orange juice 
concentrates can be prepared by combining 65 parts concentrated orange 
juice (65.degree. Brix), 5 parts pulp, 15 parts of an aroma/flavor 
concentrate, 0.4 parts peel oil with the 15 parts Fe/Ca premix. Similar 
single-strength juice beverages can be prepared by appropriate variation 
of the amounts of concentrated orange juice, pulp, aroma/flavor 
concentrate, peel oil and premix solutions, as well as the inclusion of 
water. 
Juice compositions and other beverages are preferably formulated at a pH 
below about 4.3, generally about 3.7-4.0, for reasons of microbial 
stability. 
After the iron- and calcium-supplemented orange juice product is obtained, 
it is then filled into cans, cartons, bottles or other appropriate 
packaging. In the case of orange juice concentrates, these products are 
typically frozen after being filled into cans. 
The following examples illustrate the practice of this invention but are 
not intended to be limiting thereof.

EXAMPLE I 
Preparation of Calcium Citrate-Malate 
A calcium citrate-malate solution is prepared by dissolving 2 parts sucrose 
and then 0.1 part citric and 0.28 part malic acids in 28.19 parts water. 
Calcium hydroxide (0.22 part) is added and the mixture is agitated. This 
solution can be used directly to prepare beverages, or can be freeze-dried 
to use in solid mineral supplements. 
EXAMPLE II 
Preparation of Calcium Citrate-Malate Without Sugar 
In an alternate mode, the sucrose can be deleted from the above 
preparation. Thus, a calcium citrate-malate solution is prepared by 
admixing 62 g calcium carbonate with 11 g citric acid and 44 g malic acid 
in 1,040 g water. This solution can be used to prepare low calorie 
beverages, beverage concentrates, or freeze-dried for use in solid 
supplements. 
EXAMPLE III 
Preparation of Iron II Sucrate-Malate 
Sucrose (85.5 g) is dissolved in water (299.8 g), making sure that 
dissolution is complete. Calcium hydroxide (18.5 g) is then added, and the 
mixture is stirred for 5 minutes. Any clouding is observed, and the 
resulting solution is filtered through a glass filter paper. 
To the resulting calcium-sucrate solution is added ferrous ammonium sulfate 
hexa-hydrate (24.5 g), and the solution is covered air-tight (e.g., SARAN 
wrap). The green color indicates the iron is in the desired II oxidation 
state. 
To the above solution is added malic acid (33.5 g) in 3 batches, to pH 3-4. 
The precipitated calcium malate is filtered through standard filter paper, 
but the filter cake comprising calcium sulfate is not rinsed. The 
resulting solution comprises the iron sucrate-malate used in the practice 
of this invention. The solution can be used per se, or can be freeze-dried 
to provide the iron sucrate-malate in powder form. 
EXAMPLE IV 
Mixed Composition 
The calcium citrate-malate composition of Example II and the iron 
sucrate-malate composition of Example III are, separately, freeze-dried 
and ground to a fine powder. The powders are mixed to provide individual 
unit doses comprising 1,200 mg calcium and 20 mg iron. The mixed powders 
are packaged in soluble gelatin capsules for oral ingestion as a 
calcium-iron mineral supplement. 
EXAMPLE V 
Mixed Composition 
In an alternate mode, a calcium and iron supplement powder mixture is 
prepared from the calcium citrate-malate of Example I and the iron 
sucrate-malate of Example III, and adjusted in bulk with powered lactose 
to provide a mineral supplement powder which delivers 1,500 mg calcium and 
10 mg iron per 10 g dose. 
EXAMPLE VI 
Beverage Compositions 
The following beverage compositions (a-g) are fortified with the calcium 
and iron compositions of Examples I and III to provide 20% RDA of calcium 
and 10% RDA of iron per 180 ml serving: 
(a) "sparkling" orange juice comprising 55% orange juice and 45% carbonated 
water; 
(b) pear-grapefruit nectar comprising 25% pear juice, 20% grapefruit juice, 
the balance comprising 10% sucrose-water; 
(c) kiwi-grapefruit drink comprising 20% kiwi fruit juice, 15% grapefruit 
juice, the balance comprising water; 
(d) mixed fruit "cocktail" comprising 10% each of the juices of passion 
fruit, mango, guava, pineapple, papaya, banana, apricot, mandarin orange, 
pear and lime juices; 
(e) yogurt/fruit beverage comprising 20% milk products, 1% pectin, 20% 
pineapple juice, 10% shredded pineapple fruit pulp, 16% corn syrup, the 
balance comprising water; 
(f) cola beverage comprising 0.35% cola flavor emulsion, 11% sugar, 0.1% 
phosphoric acid, 0.1% citric and malic acids, caramel coloring, the 
balance comprising carbonated water; 
(g) full-strength apple juice (using the calcium citrate-malate of Example 
II in place of the Example I material). 
EXAMPLE VII 
Food Compositions 
The following food compositions (a-f) are fortified with the mixed 
calcium-iron composition of Example IV to provide 100% RDA of calcium and 
20% RDA of iron per 250 g serving; 
(a) salted potato snack product comprising moistened, comminuted potato 
flakes, shaped and deep-fried in the form of saddle-shaped chips; 
(b) peanut butter product comprising finely ground peanuts, up to 3% peanut 
oil, salt; 
(c) cookie product comprising inner core of flour, shortening, flavoring 
and fructose enrobed in outer layer of flour, shortening, flavoring and 
sucrose; 
(d) brownie snack product comprising commercial DUNCAN HINES brownie mix; 
(e) soy-based meat analog product comprising a 50:1 (wt.) mixture of 
de-oiled soybean meal and egg whites, extruded, in patty or chunk form; 
(f) infant formulation in powder or liquid form comprising sterilized soy 
powder or soy "milk", vanilla flavor, preservative. 
It should be appreciated that the calcium source in the solid food 
compositions and the solid unit dosage forms herein need not be restricted 
to calcium citrate-malate for organoleptic/stability reasons, as in the 
case of beverages and beverage concentrates. Materials such as calcium 
chloride, hydroxide, carbonate, etc., can alternatively be used. However, 
the superior bioavailability of calcium from calcium citrate-malate makes 
this the preferred calcium supplement for use in the practice of this 
invention with solid foods and supplements, as well as with beverages and 
beverage concentrates. 
EXAMPLE VIII 
Mineral Supplement 
A powdered mineral supplement comprises 2,000 mg calcium carbonate and 15 
mg iron (II) fructate-malate, prepared in the manner of Example XX, 
hereinafter. 
EXAMPLE IX 
Orange Juice Concentrate 
A highly preferred orange juice concentrate comprises: 
______________________________________ 
Ingredient Amount (g) 
______________________________________ 
65.degree. Brix orange juice concentrate 
2070 
Aqueous orange essences 
550 
Orange pulp 270 
Orange oil 2 
Orange flavor mix 14 
Calcium citrate-malate premix 
To 800 mg Ca.sup.++ / 
solution of Example I 
180 ml portion* 
Ferrous sucrose-malate premix 
To 7.2 mg Fe.sup.++ / 
solution of Example III 
180 ml portion* 
______________________________________ 
*When diluted to single strength 
EXAMPLE X 
Orange Juice or Nectar 
The concentrate of Example IX can be diluted with water to provide a 
single-strength orange juice. 
In an alternate mode, the concentrate of Example IX is diluted to 45% juice 
levels with sugar-water to provide an orange nectar. 
EXAMPLE XI 
Iron- and calcium-fortified chewable lozenges comprise: 
______________________________________ 
Ingredient Amount 
______________________________________ 
Iron II sucrate-ascorbate 
20 mg 
Calcium citrate-malate 
500 mg 
Dextrose 5 g 
Fruit flavor* 6 mg 
Color As desired 
______________________________________ 
*Fruit flavors used herein generally comprise synthetically reconstituted 
flavor esters. In this example, pineapple flavor is used, and comprises a 
synthetic mixture of ethyl acetate, acetaldehyde, methyl nvalerate, methy 
ivalerate, methyl icaproate and methyl caprylate. 
The lozenge of Example XI is prepared by mixing the ingredients and 
compacting the mixture in a standard press. 
FNT *Fruit flavors used herein generally comprises synthetically reconstituted 
flavor esters. In this example, pineapple flavor is used, and comprises a 
synthetic mixture of ethyl acetate, acetaldehyde, methyl n-valerate, 
methyl i-valerate, methyl i-caproate and methyl capyrlate. 
The following examples illustrate syntheses of various iron compositions 
which can be used in the practice of this invention. 
EXAMPLE XII 
Iron II Sucrate-Malate 
Sucrose (1368 g; 4 moles) is dissolved in water (3995 g), making sure all 
sugar is dissolved. Calcium hydroxide (148 g; 2 moles) is added to the 
sugar-water and stirred for 5 minutes. The solution is filtered through a 
glass filter. 
To the calcium-sucrate solution is added iron II ammonium sulfate (196 g; 
0.5 moles) and covered air-tight with SARAN WRAP. The color should remain 
green. Malic acid (268 g; 2 moles) is added in three batches. At each 
addition, a pH reading is taken with litmus paper to insure pH 3-4. The 
precipitate is filtered-off with a paper filter, and the filter cake is 
not rinsed. The compound is in the filter liquor. 
EXAMPLE XIII 
Iron II Sucrate-Malate 
Sucrose (684 g; 2 moles) is dissolved in water (2226 g), making sure all 
sugar is dissolved. Calcium hydroxide (74 g; 1 mole) is added to the 
sugar-water and stirred for 5 minutes. The solution is filtered through a 
glass filter. 
To the calcium-sucrate solution is added iron II ammonium sulfate (196 g; 
0.5 mole) and the solution is covered air-tight with SARAN WRAP. The color 
should remain green. Malic acid (268 g; 2 moles) is added in three 
batches. At each addition, a pH reading is taken with litmus paper to 
insure pH 3-4. The precipitate is filtered (paper filtered), and the 
filter cake is not rinsed. The title compound is in the filter liquor. 
EXAMPLE XIV 
Iron II Sucrate-Malate 
Sucrose (684 g; 2 moles) is dissolved in water (2856 g), making sure all 
sugar is dissolved. Calcium hydroxide (148 g; 2 moles) is added and the 
solution is stirred for 5 minutes. The solution is filtered through a 
glass filter. 
To the calcium sucrate solution is then added iron II ammonium sulfate (392 
g; 1 mole) and the system is covered air-tight with SARAN WRAP. The green 
color should remain. Malic acid (268 g; 2 moles), is added in three 
batches. At each addition, a pH reading is taken with litmus paper to 
insure pH 3-4. The precipitate is filtered (paper filter) and the filter 
cake is not rinsed. The title compound is in the filter liquor. 
EXAMPLE XV 
Iron II Fructate-Malate 
Fructose (360 g; 2 moles) is dissolved in water (1644 g), making sure all 
fructose is dissolved. Calcium hydroxide (148 g; 2 moles) is added to the 
fructose solution and stirred for 5 minutes. The solution is filtered 
through a glass filter. 
To the calcium fructose solution is added iron II ammonium sulfate (196 g; 
0.5 mole) and the solution is covered air-tight with SARAN WRAP. The color 
should remain green. Malic acid (268 g; 2 moles) is added in three 
batches. At each addition, a pH reading is taken with litmus paper to 
insure pH 3-4. The precipitate is filtered off (paper filter). The title 
compound is in the filter liquor. 
EXAMPLE XVI 
Iron II Sucrate-Citrate 
Sucrose (684 g; 2 moles) is dissolved in water (2399 g), making sure all 
sugar is dissolved. Calcium hydroxide (148 g; 2 moles) is added to the 
solution and stirred for five minutes. The solution is filtered through a 
glass filter. To the calcium-sucrate solution is added iron II ammonium 
sulfate (196 g; 0.5 mole) and the solution is covered air-tight with SARAN 
WRAP. The green color should persist. Citric acid (384 g; 2 moles) is 
added to the reaction mixture in three batches. At each point of addition, 
a pH reading is taken with litmus paper to insure pH 3-4. The precipitate 
is filtered-off (paper filter) and the filter cake is not rinsed. The 
title compound is in the filter liquor. 
EXAMPLE XVII 
Iron II Sucrate-Tartrate 
Sucrose (684 g; 2 moles) is dissolved in water (2399 g), making sure all 
sugar is dissolved. Calcium hydroxide (148 g; 2 moles) is added to the 
sugar solution and stirred for 5 minutes. The solution is filtered through 
a glass filter. 
To the calcium-sucrate solution is added iron II ammonium sulfate (196 g; 
0.5 mole) and the solution is covered air-tight with SARAN WRAP. The green 
color should persist. Tartaric acid (300 g; 2 moles) is added to the 
solution in three batches. At each time of addition, a pH reading is taken 
with litmus paper to insure pH 3-4. The precipiate is filtered (paper 
filter) and removed; the filter cake is not rinsed. The title compound is 
in the filter liquor. 
EXAMPLE XVIII 
Iron II Glucate/Fructate-Malate 
Glucose (360 g; 2 moles) and fructose (360 g; 2 moles) are co-dissolved in 
water (1643 g), making sure all sugar is dissolved. Calcium hydroxide (148 
g, 2 moles) is added to the sugar-water and stirred for 5 minutes. The 
solution is filtered through a glass filter. 
To the calcium/mixed sugars solution is added iron II ammonium sulfate (196 
g; 0.5 moles) and the solution is covered air-tight with SARAN WRAP. The 
green color should persist. Malic acid (268 g; 2 moles) is added in three 
batches. At each addition, a pH reading is taken with litmus to insure pH 
3-4. The precipitate is filtered-off (paper filter) and the filter cake is 
not rinsed. The title compound is in the filter liquor. 
EXAMPLE XIX 
Iron II Sucrate-Citrate/Ascorbate 
Sucrose (684 g; 2 moles) is dissolved in water (2399 g), making sure all 
sugar is dissolved. Calcium hydroxide (148 g; 2 moles) is added to the 
sugar water solution and stirred for 5 minutes. The solution is filtered 
through a glass filter. 
To the calcium-sucrate solution is added iron II ammonium sulfate (196 g; 
0.5 mole) and the solution is covered air-tight with SARAN WRAP. The green 
color should persist. The citric acid (192 g; 1 mole) is first added to 
the solution, then the ascorbic acid (352 g; 2 moles) is added in three 
batches. At each time of addition, a pH reading is taken with litmus paper 
to insure pH 3-4. The precipitate is filtered (paper filter). The title 
compound is in the filter liquor. 
EXAMPLE XX 
Iron II Fructate Malate 
Fructose (541 g; 3 moles) is dissolved in water (1672 g), making sure all 
is dissolved. Calcium hydroxide (37 g; 0.5 moles) is added and stirred for 
5 minutes. The solution is filtered through a glass filter. 
To the calcium-fructose solution is added iron II sulfate (139 g; 0.5 
mole), and the solution is covered air-tight with SARAN WRAP. The color 
should remain green. Malic acid (67 g; 0.5 moles) is added to the solution 
in three batches. At each addition, a pH reading is taken with litmus 
paper to insure pH 3-4. The precipitate is filtered-off (paper filter) and 
the filter cake is not rinsed. The title compound is in the filter liquor. 
Potentiators 
The foregoing compositions function exceptionally well as mixed 
iron-calcium supplements. However, it has now also been determined that 
certain materials act as "potentiators", which still further enhance the 
bioavailability of calcium. Fructose is one such potentiator, and other 
carbohydrates, such as sucrose, function similarly, albeit less well than 
fructose. 
However, iron bioavailability is somewhat impaired by the administration of 
calcium, and this impairment remains, even in the presence of 
usually-found levels of carbohydrates, including fructose. 
It has not been found that citric acid (or citrates) and tartaric acid 
(tartrates) partially alleviate calcium's inhibitory effect on iron, and 
mixtures of citric/ascorbic acid (or citrate/ascorbate mixtures), do 
overcome the inhibitory effect. 
Accordingly, in a preferred mode, this invention also uses a potentiating 
amount of citrate; or, preferably, citrate/ascorbate; or, 
citrate/fructose; or, citrate/ascorbate/fructose, or like tartrate 
combinations, to potentiate iron and calcium bioavailability when these 
minerals are administered conjointly. It will be appreciated by the 
formulator that these potentiators can simply be added to the 
above-exemplified compositions, if not already inherently present. 
By "potentiating amount" of the citrate, tartrate, ascorbate, carbohydrate 
(especially fructose), and mixtures thereof, materials used herein is 
meant an amount sufficient to enhance uptake and bioavailability of iron 
and calcium when administered to humans or lower animals. Of course, even 
small amounts of these potentiators have some beneficial effect. However, 
it is preferred to use sufficient potentiator to provide bioavailability 
levels of the iron/calcium mixtures which are essentially equivalent to 
iron and calcium supplements when administered separately, and several 
hours apart. Fortunately, the potentiators used herein are entirely safe 
for consumption, so there is essentially no upper limit to the amount that 
can be safely ingested. Moreover, in practical terms, the potentiators are 
inexpensive, so there is no need for the formulator to carefully balance 
benefit/cost ratios. Typically, then, the citrate, tartrate and ascorbate 
potentiators are used in a weight ratio with the minerals (calculated as 
iron and calcium per se, discounting associated ions or ligands) of 
potentiator:mineral ranging from 1000:1 to 1:3, generally 3:1 to 1:1. The 
fructose potentiator may be used in much higher ratios, say, 10.sup.6 :1, 
since the formulator may also find it useful to include fructose, not only 
for its potentiating effect, but also for its bulk sweetener effect. 
EXAMPLE XXI 
Mineral Supplement 
A powdered mineral supplement comprises 2,000 mg calcium citrate-malate, 15 
mg iron (II) fructate-malate prepared in the manner of Example XX, 250 mg 
citric acid and 100 mg ascorbic acid.