Product type Ca content Particle size Application
Tricalcium Citrate
M1098 21 % 98 % < 10 µm
For critical applications: high concentrations, low viscosity of products etc.
Tricalcium Citrate
M2090 21 % 90 % < 20 µm Standard product for dairy and soy
Tricalcium Citrate
M7090 21 % 90 % < 70 µm
For low pH products, e.g.
fruit preparations at low dosage levels
Calcium Lactate
Gluconate 13 13 % Not specified (soluble)
For acidified and low fat neutral dairy and soy drinks
food Marketing & Technology · February 2010
4
Ingredients
Introduction
The global market for dairy products with calcium claims is estimated to reach USD 3.8 billion in 2009. Yoghurts with calcium claims are driving growth with total sales of roughly 1 billion and a 5.1% increase in sales over 52 weeks ending August 2009. ‘Having an additional calcium claim on the label translates to increased sales’ according to Euromonitor International and Nielsen in 2007 [1].
On top of the standard nutritional claims such as “with calcium”, “high in calcium” etc, health claims are increasingly exploited both in dairy products to further highlight the health benefits of this well-known functional ingredient.
However, feasibility of calcium addition has to be considered as milk products represent a complex food matrix from the technological point of view. This challenge drives mineral salt suppliers such as Jungbunzlauer to offer not only one product but rather a range of different calcium salts (tricalcium citrate and calcium lactate gluconate) to be able to align with food manufacturers’
applications.
This article discusses important nutritional, technological as well as economical aspects of calcium in dairy products with a focus on micronized tricalcium citrate.
Common Calcium Sources for Fortification of Dairy Products Looking at the ingredients list of dairy products, it is evident that there is not
“the” calcium source but rather a range of different possibilities used commercially (see Table 1):
• inorganic salts such as calcium carbonate and calcium phosphate
• calcium from animal or vegetable origin, such as milk calcium (comprised mainly of calcium phosphate) and seaweed calcium (comprised mainly of calcium carbonate)
• organic salts such as tricalcium citrate, calcium lactate, calcium lactate gluconate and calcium gluconate.
The selection of the appropriate calcium source for a specific application is usually based on the consideration of a number of properties associated with the respective product such
as solubility, calcium content, taste and bioavailability. Economic considerations are another important factor.
Solubility vs. calcium content When fortifying liquid milk products, solubility, dissolution characteristics and stability of ingredients in solution are major issues. There are calcium salts with high solubility like calcium gluconate, calcium lactate, and calcium lactate gluconate, but their drawback is a comparably low calcium content (9-13 % calcium).
The inorganic calcium chloride (36 % calcium) displays good solubility, but its use is restricted due to its bitter and salty taste. Other inorganic calcium
Calcium Fortification in Dairy Products
Photos: Jungbunzlauer
by Dr. Miriam Münchbach and Dr. Gerhard Gerstner
AlmondBoard.com
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Key No. 71764
food Marketing & Technology · February 2010
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Ingredients
salts with a high calcium content like calcium carbonate and calcium phosphate (38-40 % calcium), have limited solubility.
Tricalcium citrate offers a good combination: The commonly used tetrahydrate form shows a high calcium level (21 %) and moderate solubility (1 g/L). Tricalcium citrate shows improved solubility at pH-values below 4.5 as found in fruit preparations or fruit juices. Contrary to other salts, tricalcium citrate is more soluble at low temperatures (so-called “inverse solubility”, Figure 1) which can be an advantage for cold and hot food processing, see below. To further increase the solubility and ease of dispersion, Jungbunzlauer has developed different micronized grades of fine tricalcium citrate.
At higher calcium levels the micronization grade of tricalcium citrate should be adapted for optimal dispersion and mouthfeel. With the finest micronization grade (M1098; 98 % < 10 µm)
tricalcium citrate could even be suspended in dairy products in concentrations of up to 425 mg Ca/100 ml without negative taste effects (see Table 1).
The highly soluble calcium lactate gluconate is known to be used in low fat milk or acidified milk drinks. This organic calcium source displays a neutral taste and shows a better stability during the heating step compared to other soluble calcium sources.
Taste and Mouthfeel
Generally, high levels of calcium, particularly insoluble forms like carbonates and phosphates, tend to produce a chalky mouthfeel and may promote astringency or bitter taste in the finished product. Calcium lactate may impart some bitter notes at high concentrations, comparable to characteristics found for calcium chloride [2]. Calcium carbonate may come across as soapy or lemony, and calcium phosphate has a bland flavor, but imparts a gritty mouthfeel. Negative effects of calcium on taste can be masked with chelating agents (e.g. tripotassium citrate), and the use of stabilizers
(e.g. carrageenan) as well as with the addition of flavorings. Tricalcium citrate is considered to be a very neutral tasting salt as masking agents are not necessary, which reduced formulation costs.
It is known that using highly soluble calcium salts at high concentrations may lead to adverse effects in dairy applications [3, 4]. The addition of mineral salts, especially calcium, has a strong impact on stability of these products during processing. Due to the fact that more soluble salts result in more free calcium ions in solution and are available for reaction than less soluble salts, complications in the form of calcium sediments can develop with time or when the product is heated during manufacturing. This is the case, if the natural milk components such as phosphate and proteins react with available calcium. Thus, although it might be easier to add
highly
soluble calcium salts rather than tricalcium citrate to milk products, higher amounts of calcium might be difficult to achieve without control of pH and addition of chelating agents such as potassium citrate [3, 4]. Due to its inverse solubility, tricalcium citrate is less reactive during the heating process, thus minimizing precipitates, fouling and cleaning intervals.
Since the particle size and solubility are linked with mouthfeel properties, Jungbunzlauer has developed micronized grades for tricalcium citrate combining excellent dispersion characteristics with a neutral taste profile in final applications. Even if it will sediment at the end of the shelf life, it can easily be re-dispersed by shaking the container, whereas tricalcium phosphate tends to form large particles or chunks which stick to the bottom.
Bioavailability
Any nutrient’s effectiveness depends on its bioavailability, which means how well the human body absorbs and utilises it. On average, only about 10 to 30 % of calcium is absorbed from a mixed diet by healthy adults [5]. Several different factors influence this level, including the type of salt which provides the calcium. Various scientific studies have shown that organic calcium salts outperform inorganic calcium sources such as calcium carbonate and calcium phosphate with regard to their relative bioavailability. Tricalcium citrate and calcium lactate gluconate belong to the highly bioavailable organic sources, proven by extensive human and animal studies and are at least as well absorbed as calcium from plain milk [3, 6].
Economic Considerations vs.
Calcium Content
Inorganic calcium salts are more economic than organic ones due to their low price and high calcium content.
They are chosen if milk beverages manufacturers give priority to price over nutritional value (bioavailability), given that product development and production have accepted or solved technological hurdles (e.g. sedimentation, mouthfeel).
Comparing the typical used organic sources on the other hand, they are all in the same price range per kg, except for the more expensive milk minerals. For this reason, the wide range of calcium content of calcium gluconate (9 %), calcium lactate (13 %) or calcium lactate gluconate (13 %) and tricalcium citrate (21 %) has a considerable impact on the raw material cost when the price of calcium is calculated for the product to be fortified. Among the organic salts with high bioavailability and more neutral taste profiles, tricalcium citrate (21 % calcium) clearly stands out as the most economic option for calcium addition and is the premium choice for milk products.
Processing and Applications To achieve a stable suspension in liquid milk products within seconds, a jet mixer (e.g. Ytron-Y, Ytron Germany) can be used at 50 °C. This temperature
is recommended for mixing to lower viscosity and also to avoid damage to the fat matrix of the milk. With conventional stirrers, homogeneous dispersion of tricalcium citrate will take longer, but can be done at cold temperatures (6-8 °C), preferably by using a concentrated pre- slurry with the calcium salt. At these temperatures, tricalcium citrate can also be added to the product stream together with other dry ingredients e.g. via a
Venturi blender. There is no particular sequence to be followed; however ingredients increasing viscosity such as thickening agents should be added at the end directly before heat treatment.
The described characteristics of micronized tricalcium citrate makes it an ideal calcium salt for all kinds of applications of calcium-fortified dairy products. Some examples from European
and US supermarkets are given in Table 1.
By adding extra calcium, these products can be fortified to higher levels or simply re-adjusted to the calcium levels of milk (120 mg/100 mL) where raw material selection and ingredients low in calcium result in lower mineral levels.
If fruits are used for dairy products, an indirect addition of tricalcium citrate to the milk product via the fruit preparation
Fortified product Ca salt Stabilizer Ca content
in 100 ml Nutritional Ca claim Ca health claim and labeld target group
Yoghurt drink TCC guar gum 425 mg fully satisfy daily needs of calcium
Yoghurt TCC modified starch,
guar gum 320 mg contains twice calcium as
a regular yoghurt Help keep bones strong
Fat free milk TCP carrageenan 250 mg added calcium Helps to build and maintain strong, healthy bones and teeth.
Yoghurt TCC, TCP guar gum, locust bean gum, corn
starch 250 mg added calcium For bone growth
Yoghurt TCC 240 mg added calcium For kids. Support healthy bone
growth
Milk drink TCC, CLG, sea algae
calcium pectin 200 mg added calcium
Low fat yoghurt TCC modified starch,
gelatine 180 mg enriched with calcium
Milk drink CLG 180 mg 50 % more calcium than
regular milk Evaporated milk CC carrageenan 169 mg contains 35 % more
calcium
Whole milk CGM 166 mg with extra calcium
The milk promotes healthy bones and teeth, growth and repair, vision and skin, release of energy, healthy blood and nervous system, and pregnancy.
Semi-Skim Milk TCP cellulose, CMC,
TSP 160 mg The product provides
35 % of the recommended
daily intake of calcium Helps to maintain healthy bones Semi-Skim Milk milk -Ca 160 mg calcium 100 % natural Is essential for keeping healthy and
strong bone.
Milk drink TCC carrageenan 160 mg + 20 % calcium
Milk drink TCP guar gum,
carrageenan,
xanthan 130 mg added calcium
Yoghurt CC guar gum,
xanthan gum 130 mg added calcium For kids
Quark drink TCC modified
cornstarch, guar
gum 122 mg calcium enriched For kids. For strong bones Low fat yoghurt
drink TCC, TCP,
CC 120 mg added calcium For kids
Milk drink CLG DSP 120 mg added calcium For pregnant and breastfeeding
women
Abbreviations: CC = calcium carbonate, CGM = calcium gluconate monohydrate, CLG = calcium lactate gluconate, TSP = trisodium phosphate, DSP = disodium phosphate, TCC = tricalcium citrate, TCP = tricalcium phoshate, TPC = tripotassium citrate, TSC = trisodium citrate, CMC = carboxymethylcellulose
Table 1: Examples of calcium fortified diary products according to Minel gnpd, 2007-2009
food Marketing & Technology · February 2010
8
Ingredients
might be the optimum solution. Fruit preparations generally have a lower pH and high citric acid/fruit acid concentration which has a positive effect on solubility/dispersibility of tricalcium citrate. In this application it is therefore possible to use tricalcium citrate M 7090 (90 % < 70 µm) which is also a micronized grade, but with a less strict particle size limit compared to M2090 (90 % < 20 µm) or M1098, which is more cost effective.
Besides the fortification aspect, tricalcium citrate also has a positive stabilising influence in the fruit preparation as calcium pectinate bridges are built which improve the firmness of the fruit texture.
Conclusions
The challenge for dairy product manufacturers is to provide a product having high calcium content with good taste and appealing properties. Since micronized tricalcium citrate has been available, it has replaced inorganic as well as organic salts in dairy applications. An important explanation from the technological standpoint is that especially in the milk matrix, a highly
dispersible calcium salt has advantages over highly soluble alternatives.
Among the organic salts with high bioavailability and more neutral taste profiles, tricalcium citrate (21 % calcium) clearly stands out as one of the most economic options for calcium addition and is seen to be the main choice for milk products.
Very recently, calcium health claims received an overall positive opinion, whereas probiotics or botanical substances received a negative rating from the EFSA. Thus, calcium with its beneficial effects on human health are here to stay as one of the top functional ingredients for dairy products.
Key No. 72557 The Authors
Dr. Gerhard Gerstner is Business Development Manager Health & Nutrition for Jungbunzlauer in Ladenburg, Germany.
Dr. Miriam Münchbach is Technical Service Manager for the food ingredients company Jungbunzlauer. She is the technical service contact for Jungbunzlauer’s HealthyChoices
portfolio of highly bioavailable organic mineral salts of calcium, magnesium, potassium and zinc which are produced in dedicated facilities in Ladenburg, Germany and Pernhofen, Austria.
References
[1] www.factsfiguresfuture.com; Euromonitor International and Nielsen.
[2] Tordoff, M.G. Some basic physophysics of calcium salt solutions. Chemical Senses 21, 417-424 (1996)
[3] Flynn, A.; Cashman, K. Calcium. In:
Hurrel, R. (ed.) The Mineral Fortification of Foods, Leatherhead International Ltd, Surrey, England (1999)
[4] Reddy, S.; Sher, A.; Van Vadehra, D.;
Wredal, E.R. Calcium complex and a process of making a food fortified with calcium. US Patent 5,928,691 (1999)
[5] National Research Council. Calcium, In:
Recommended Dietary Allowances: 10th edition. Report of the Subcomittee on the Tenth Edition of the RDA. Food and Nutrition Board and the Commission of Life Sciences. Washington D.C.; National Academy Press, 174-184 (1989)
[6] Gerstner, G How can we get more calcium?
International Food Ingredients 3, 24-26 (2003)
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Key No. 72vit
Photo: Vitiva
