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Home , Calcium citrate, Calcium lactate, Tricalcium phosphate

Ingredients How to Fortify Beverages With by Dr. Gerhard Gerstner

Along with current developments of the overall functional foods market, the use of minerals and especially calcium is expected to exhibit strong growth rates. In contrary to other functional ingredients, calcium is widely known as being beneficial for human health and there is no need to explain its nutritional ad- vantages to the customer. According to Leatherhead International, future trends include growing consumer concern regarding osteoporosis and health, leading to increased sales of calcium salts. The con- observation is seen as being one of tinuous market growth drives the main factors causing osteo- Common calium sources suppliers to offer not only one porosis 2 .As a consequence, national for beverage fortification product but rather a range of different authorities all over the world have calcium salts and granulations to be recently reconsidered recommend- Table 1 shows a typical range of able to tune them to industrial cus- ations in order to take remedial calcium fortified beverages which tomers’ applications. This article measures against calcium deficiency have been seen in European and US discusses important nutritional, and accordingly, to reduce the risk of supermarkets recently. Practically technological as well as economical osteoporosis. In this respect, the US every type of beverage such as aspects of calcium in beverages with National Institute of Health (NIH) has mineral water, soy , energy drink, a focus on our company’s products increased the amounts of optimal nectar or juice does have a fortified Tricalcium Citrate, daily calcium intake and defined product line already. Looking at the and the new product development specific values for each population ingredients list, it is evident that there Gluconate. group 3. For example, calcium intake is not “the” calcium source but rather should be 1000 mg/day for adults (25- a range of different possibilities used Optimizing calcium intake 65 years of age) and as much as commercially: 1500 mg/day for seniors (older than ¾ inorganic salts like calcium Calcium is a key mineral in the human 65 years) or lactating women. carbonate and body, necessary for normal growth Harmonization of R ecommended ¾ organic salts like tricalcium citrate, and development of the skeleton as Daily A llowances (RDA) is under calcium lactate, calcium lactate well as for teeth, nerve, muscle and discussion also on EU level right now gluconate and calcium gluconate. enzyme functions. As the body’ s and in this context, the Scientific calcium absorption capabilities Committee on Food just recently The selection of the appropriate salt reduce with age, it is vital for the recommended a higher RDA of 1000 for a specific application is usually ageing to have a sufficient calcium mg vs. the existing level of 800 mg based on the consideration of a intake. Calcium requirements vary calcium per day 4. number of properties associated with throughout an individual’s life and for the respective product such as different population groups. However, There are several options to avoid , calcium content, taste and it is generally evident that a significant calcium deficiency by increasing the bioavailability . Economic consider- proportion of the population in daily calcium intake: A balanced diet ations are another important factor. Western countries fails to achieve the with calcium-rich foods like milk, dairy recommended calcium intakes. Poor products and certain vegetables Solubility vs. calcium dietary habits are seen to be respon- (broccoli, Chinese cabbage, leg- sible for this situation, especially if umes) would be the best solution. content consumption of fast food is domin- However, this would require a ating the daily menu. profound change in dietary habits of When fortifying beverages, solubility, western society. A further possibility dissolution characteristics and V arious studies showed that a sig- consists in taking stability of ingredients in solution are nificant proportion of the population products. A more elegant option is a major issue. There are calcium salts groups fails to achieve the calcium consuming “regular” food fortified with with good solubility like calcium glu- intakes in western countries 1. This calcium as an added value product. conate, calcium lactate, and calcium 16 Ingredients

Table 1. Calcium-fortified clear, cloudy as well as instant beverages found in European and US supermarkets

Products Calcium source added Serving size Calcium content Nutritional claim used (mL) (mg/L) on the product label 1. Clear beverages Still mineral water / 500 300 Source of calcium / sulphate Near water drink Tricalcium citrate 500 240 With calcium Apple juice I Calcium lactate 125 800 Calcium enriched Apple juice II Calcium lactate gluconate 250 1200 With calcium drink Tricalcium citrate 330 368 Plus minerals

2. Cloudy beverages Apricot nectar Calcium lactate 162 417 With calcium Tropical nectar Tricalcium citrate 200 500 - Soy milk I Calcium carbonate 250 1200 Added calcium Soy milk II , 500 1200 With calcium calcium carbonate Fruit Juice Calcium lactate gluconate 240 417 Fortified with calcium Cranberry juice Calcium lactate gluconate 240 417 Fortified with calcium juice Tricalcium citrate 240 1458 Plus calcium Orange/tangerine juice , 240 1458 As much calcium as milk calcium lactate I FruitCal® 240 1458 As much calcium as milk Orange juice II Tricalcium citrate 414 276 With added calcium Orange juice III Calcium lactate gluconate, 200 1600 Calcium+ tricalcium citrate 3. Instant beverages Instant tea drink Calcium lactate gluconate 100 1200 With calcium Beverage powder Calcium gluconate 113 ca. 3550 Fast absorbing calcium lactate gluconate but their drawback high concentrations of calcium (e.g. phate) that give insoluble salts with is a comparably low calcium content 1.5 g Ca/L) can be reached. calcium are present in the product. (Table 2). Calcium salts with a high Accordingly, tricalcium citrate still is Thus, although it is possible to add calcium content like calcium carbon- seen to be the main choice for fortified for example more calcium lactate ate and calcium phosphate, on the orange or grape juice. than tricalcium citrate to beverages, other hand, are poorly soluble and higher amounts of calcium in the for that reason not commonly used in Calcium lactate is provided as a product might be difficult to achieve beverages. pentahydrate, containing 13 % of without control of pH and addition of calcium. It shows good solubility chelating agents such as Tricalcium citrate of fers a good properties and is therefore mainly citrate 1,5 . In some applications, combination: The commonly used used in clear beverages to achieve combinations of calcium lactate with tetrahydrate form shows a high the necessary levels for nutritional other calcium salts can also have a calcium level (21 %) and moderate claims on calcium. It is known that stabilizing effect. solubility (0.9 g/L). Solubility is using calcium lactate in high con- strongly influenced by the pH of the centrations may lead to adverse Although calcium gluconate displays system since the solubility of calcium effects in certain applications 1,5 . Due a good solubility, it is not used salts typically increases with to the fact that with higher soluble frequently in ready-to-drink bever- decreasing pH. Tricalcium citrate salts, more free calcium are in ages, especially due to its low shows improved solubility at pH- solution and available for reaction calcium content (9 %). However, its values below 4.5 as found in most than with lower soluble ones, neutral taste properties, good beverages. If calcium content is complications in the form of calcium dissolution speed at higher temper- referred to per beverage serving of sediments can develop with time. atures and low water content makes 330 or 500 mL, 15 % of RDA (120 mg This is the case, when components especially the anhydrous form a valid calcium) can easily be reached with (e.g. free protein, tartrate or phos- calcium source for instant prepar- tricalcium citrate also for acidic clear beverages. Contrary to other salts, Table 2. Important characteristics of common calcium sources used tricalcium citrate is better soluble at in the food industry low temperatures which can be an advantage for processing because it Product Ca Solubility Taste Calcium Content can be dissolved at low temperatures at 25°C (g/L) and shows low reactivity at high Calcium carbonate Insoluble Soapy, lemony 40 % temperatures. To further increase the Calcium phosphate Insoluble Sandy, bland 17 - 38 % solubility and ease of dispersion, we Tricalcium citrate 0.2 Tart, clean 2 1 % (4 H O) have developed a particularly fine 2 Calcium lactate 9.3 Bland 13 % (micronized) tricalcium citrate grade. (5 H 2O) With this special granulation of min. Calcium lactate 45 - 50 Neutral 10 - 13 % 90 % < 20 microns, it can be sus- gluconate pended in cloudy beverages and Calcium gluconate 3.5 Mild, neutral 9 %

Food Marketing & Technology  October 2003 17 Ingredients

cium lactate gluconate and calcium gluconate are considered to be the most neutral calcium salts, as masking agents are not really necessary.

Since the particle size and solubility are linked with mouthfeel properties, we have developed micronized grades for tricalcium citrate com- bining excellent dispersion char- acteristics with a neutral taste profile in final applications.

Bioavailability

Any nutrient’s effectiveness depends on its bioavailability , which means how well the human body absorbs and utilizes it. On average, only about 10 to 30 % of calcium is absorbed from a mixed diet by healthy adults 7. Several different factors influence this level, among which the type of salt which provides the calcium.

Organic vs. inorganic salts

V arious scientific studies have shown that organic calcium salts outperform inorganic calcium sources such as ations such as fortified beverage calcium and 4 % water, our own calcium carbonate and calcium powders, enabling high calcium Calcium Lactate Gluconate can offer phosphate with regard to their relative amounts per serving size. an improved formulation compared to other calcium lactate gluconates bioavailability . Accordingly, the US National Institute of Health Compared to the above, calcium on the market. recommended calcium citrate for lactate gluconate is the most soluble  supplementation, especially for older salt showing very interesting prop- FruitCal is a patented mixture of individuals where absorbability can erties: its solubility is not between , malic acid and calcium be a limiting factor due to reduced the single components calcium invented by Procter & gastric acid production 3. Recently, lactate and calcium gluconate as one Gamble. This highly soluble blend, researchers at the University of Texas would expect, but it is synergistically also called is conducted a meta-analysis of enhanced to approx. 400 g/L water. currently used in beverages under calcium bioavailability, which This sums up to a calcium content of license e.g. for Tropicana’s (PepsiCo) evaluated studies on the bio- 45 to 50 g/L, depending on the ratio Pure Premium calcium fortified juices availability of two of the most common of the mixture. With this high calcium to reach RDA values of calcium forms of calcium supplements, value in mind, it is not surprising that comparable to milk. tricalcium citrate and calcium this salt is used when a high dis- carbonate 8. Over 90% of the studies solution speed is required. It is also Taste and mouthfeel reviewed showed greater absorption especially recommended for forti- of calcium from tricalcium citrate than fication of clear beverages. The Generally, high levels of calcium, calcium carbonate by an average of reason for this phenomenon of particularly insoluble forms like 22 to 27 %. extremely high solubility is inter- carbonates and phosphates, tend to preted as the ability of mixtures of produce a chalky mouthfeel and may Similarly , calcium phosphate has also lactate and gluconate ions to form promote astringency or bitter taste in been described in scientific studies metastable complexes with calcium the finished product. Calcium lactate to display lower bioavailability than ions in solution, which gives way for may impart some bitter or milk-like tricalcium citrate 9. Absorption of additional benefits in beverages: Due notes at high concentrations. Calcium calcium from soy milk fortified with to better stability of beverages fortified carbonate may come across as tricalcium phosphate reached only 75 via calcium lactate gluconate clear soapy or lemony. Calcium phosphate % of the efficiency of calcium from cow beverages can be fortified without the has a bland , but imparts a gritty milk 10. Furthermore, it is not con- addition of chelating agents 6 .And mouthfeel. Negative effects of calcium sidered to be an appropriate higher calcium concentrations can be on taste can be masked with chelating ingredient for calcium fortification due reached, even in critical applications agents (e.g. tripotassium citrate), and to the undesired characteristics of the such as grape and cranberry juice, the use of stabilizers (e.g. carra- phosphate anion. Intake of phos- tea beverages and also concentrated geenan) as well as with the addition phate is reported to exceed adult pre-blends. Containing approx. 13 % of flavorings. Tricalcium citrate, cal- RDAs in practically 100 % of the 18 Ingredients

population 11 . Therefore, further addi- calcium content (13 %). Due to its food/fs/sc/scf/out171_en.pdf tion of phosphate to food should be good solubility, it is a good alternative [5] Reddy, S.; Sher , A.; Van avoided in order to gain a higher for clear beverages, if the desired V adehra, D.; Wredal, E.R. Calcium calcium-to- ratio, which is amount of calcium does not affect complex and a process of making a considered to be favorable for stability and taste of the beverage. food fortified with calcium. US Patent sufficient calcium absorption. For those critical applications, 5,928,691 (1999) calcium lactate gluconate (available [6] Liebrecht J.W .; Phillips, K.M. Influence of solubility on with up to 13 % calcium) is worth the Calcium fortified juice-based bioavailability . premium price to achieve high nutritional supplement and process fortification levels, e.g. in clear soft of making. US Patent 6,106,874 drinks or concentrated pre-blends. (2000) Reviewing the various bioavailability Another possibility, having a calcium [7] National Research Council. studies which had been done on the price between the latter salts, is using Calcium, In: Recommended Dietary common organic salts listed in Table highly soluble and neutral tasting Allowances: 10th edition. Report of 1, it is concluded that they show calcium gluconate (9 % calcium), e.g. the Subcommittee on the Tenth 1 similar calcium absorption . This for instant beverage powders. Edition of the RDA. Food and Nutrition holds true even though there are Board and the Commission of Life significant solubility differences of Conclusion Sciences. Washington D.C.; National organic calcium salts in plain water. Academy Press, 174-184 (1989) Researchers agree that these [8] Sakhaee, K.; Bhuket; T., differences have no significant effect Consumers increasingly prefer food with added nutritional value rather Adams-Huet, B.; Rao, D.S. Meta- on absorbability in acidic analysis of calcium bioavailability: A environment such as in gastric acid than taking nutritional supplements to fill up their calcium needs. comparison of calcium citrate with in the human stomach as well as at calcium carbonate, Am. J. neutral conditions in the intestine 1,9,12 . Beverages with added calcium are seen to be one of the best means to Therapeutics 6, 313-321 (1999). Although for example tricalcium [9] Heaney, R.P.; Recker, R.R.; citrate displays only moderate help fighting calcium deficiency and represent a valid nutritional source W eaver, C.M. Absorbability of calcium solubility in water , it had been sources: the limited role of solubility , assessed as having the same for people who do not consume dairy or other products high in calcium on Calcified Tissue International 46 , solubility in artificial intestinal juice as 300-304 (1990) the calcium lactate 13. In a recent a regular basis. However, the challenge for food & beverage [10] Heney, R.P.; Dowell, M.S.; review of calcium lactate gluconate Rafferty, K.; Bierman, J. Bioavailability absorptionXX, it was concluded that manufactures is to provide a product having high calcium content with of the calcium in fortified soy imitation further to its excellent solubility , it milk, with some observations on showed a high bioavailability in good taste and appealing properties. Accordingly, Jungbunzlauer as one method. Am J Clin Nutr 71 , 1166-1169 human studies (30 %) and the most (2000) pronounced positive effect on bone of the leading producers of citrates and gluconates is further increasing [11] Anderson, J.J.B.; Garner, S.C. mineral compared to other Dietary issues of calcium and calcium salts. its efforts to provide a wide range of highly bioavailable organic calcium phosphorus, Calcium and sources for nutritional purposes. Phosphorus in Health and Disease, Economic considerations CRC Press, 7-23 (1995) [12] Hansen, C.; Werner, E.; Erbes, vs. calcium content Key No. 52286 H.-J.; Larrat, V.; and Kaltwasser, J.P. Intestinal calcium absorption from Although inorganic calcium salts are References more economic than organic ones different calcium preparations: [1] Flynn, A.; Cashman, K. influence of anion and solubility. due to their low price and high Calcium. In: Hurrel, R. (ed.) T h e calcium content, they are not Osteoporosis Int. 6, 386-393 (1996) Mineral Fortification of Foods , [13] T akamiya, K.; Atsugi, M. frequently used in beverages any- Leatherhead International Ltd, more. Comparing the mainly used Influence of saliva mucin on the Surrey, England (1999) digestibility of calcium compounds. organic sources on the other hand, [2] Matkovic, V. Calcium they are all in the same price range, Journal of Japanese Society of metabolism and calcium Nutrition and Food Science 47 (6), except for the premium mineral source requirements during skeletal calcium lactate gluconate. For this 447-451 (1994) modeling and consolidation. [14] Gerstner, G. How can we get reason, their wide range of calcium American Journal of Clinical Nutrition contents (9 to 21 %) has a con- more calcium? International Food 54 , 245-260 (1991) Ingredients June/July, 24-26 (2003) siderable impact on the raw material [3] National Institutes of Health, cost when the price of calcium added Optimal Calcium Intake, NIH is calculated for the product to be The Author Consens Statement Online 1994 Dr. Gerhard Gerstner is Technical fortified. Among the organic salts with June 6-8, 12 (4), 1-31, Bethesda, MD high bioavailability and more neutral Service Manager with Jungbunzlauer (1994) Ladenburg GmbH, Germany taste profiles, tricalcium citrate (21 % [4] Opinion of the Scientific calcium) clearly stands out as the Committee on Food on the revision most economic option for calcium of reference values for nutrition addition and is the main choice for labeling (expressed on 5 March cloudy beverages. Calcium lactate 2003) http://europa.eu.int/comm/ has about the same price but a lower Food Marketing & Technology October 2003 19