Carrageenan – the future or the history.

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As you probably know, the National Organic Standards Board recommended recently that Carrageenan should be eliminated from organic food. It means that if any food containing Carrageenan cannot be considered as organic. (1) In the November of 2018, the United States Department of Agriculture has to decide if reapprove Carrageenan or ban it from allowed substances list. Can this change be difficult for the food industry? (you can find more at this Community Alert)

To answer this question, we should know first what Carrageenan is.

 

What is Carrageenan?

Carrageenan is a general name for polysaccharides extracted from certain kinds of algae (seaweed) which are composed only, from D-galactopyranose units (and this is a difference from agar). It is good to know that Carrageenan is not digestible, it is a soluble fibre, so has no nutritional value.

From a chemical structure point of view there are different types of Carrageenan, for example commercially important: kappa, iota and lambda (based historically on the solubility in 0.25M KCl). Different structure means different properties and uses. (2)

Kappa Carrageenan is predominantly found in Kappaphycus alvarezii and Eucheuma cottonii (called cottonii), iota Carrageenan is extracted largely from Eucheuma spinosum. Most seaweeds species contain mixtures of different types of Carrageenan. A mixture of kappa and lambda we can find in Chondrus crispus, Gigartina skottsbergii and Sarcothalia crispate. Some seaweed, like Gigartina, has various Carrageenan types mixed up even along the same polymer chain.(3-5)

 

Caution - Carrageenan is not poligeenan.

Many have confused carrageenan with poligeenan (known as “degraded Carrageenan”). Technically, only Carrageenan (“undegraded Carrageenan”) is approved for use in food. Poligeenan is produced by boiling Carrageenan in a strong acid.

 

Properties of Carrageenan

Carrageenan is stringy, salty and it can be a bit smelly (with seaweed odour). It has a high reactivity in order to milk proteins, so it is widely used at low concentrations in dairy products to prevent fractionation of milk constituents and keep all ingredients in suspension. These interesting properties give Carrageenan a huge applicability in the food manufacturing. If we consider the amount of used additive (like 4%) in the food product for sufficient gelling effect, Carrageenan is one of the best options. Although, it is good to know here that different types of Carrageenan provide a different gelling and emulsifying properties (ranging from a soft to a brittle gelation).

Carrageenan has also antimicrobial and antiviral properties.

Applications of Carrageenan

Carrageenan is commonly used as an emulsifier in foods, particularly dairy products and other viscous items (like toothpaste). In the food products often it replaces synthetic and animal-based gelling agents. (6) We can find it in:

  • processed meat, poultry and seafood –as water-binding agent for increasing product yields, improving texture, as well as, a fat replacement in meat/seafood products,
  • dairy products (like chocolate milk, frozen desserts, UHT milks, whipping cream, ice cream, non-fat sour cream, flans, puddings, low-fat cheese, cheese analogs, cottage cheese, ricotta cheese, yogurt, dips, spreads) - to provide ingredients (e.g. cocoa) suspensibility, milk stability, emulsion stability or milk gelling,
  • cold milk powders (like diet powder mixes or nutritional beverage mixes) - for better mouth feeling or taste hiding, as well as, to support solids suspensions,
  • water-gel desserts – for texturing and better flavour release,
  • dairy alternatives (soy milk, coconut milk, almond milk, dressings) – as a stabiliser,
  • frozen dinners – as a product texturant and antimicrobial agent,
  • nutritional drinks and supplements – for better appearance and mouth feeling,
  • infant formula – to stabilise powder suspensions,
  • pet foods – as water binding agent, which prevents fat separation in canned products.

As you can see, Carrageenan can be found in many foods, even foods labelled “natural” or “organic.” It is also a vegetarian and vegan alternative to gelatin in some applications.

 

Production of Carrageenan.

Carrageenan is produced from seaweeds. (2) The seaweed is extracted from the ocean, dried by spreading and air-drying or by using rotary dryers, and sent to the Carrageenan manufacturer, where it is grounded into a fine powder, sifted to remove sand and washed. At this step, it becomes what we call as a raw Carrageenan.

Carrageenan is purified usually by one of the four industrial processes:

  • Solid state process (known as natural grade or semi-refined process). The semi-refined process was developed originally to produce a high gel strength, cheap Carrageenan used in the pet-food industry. This process can be only performed using Eucheuma cottonii or Eucheuma spinosum. It allows using slurry as a source (not completely diluted raw material, reduced volume). The raw Carrageenan is treated with hot alkali solution with a very high potassium level (e.g., 5–8% potassium hydroxide). Then, minerals, proteins, fats and most of a cellulose are removed by washing, centrifugation and filtration. The resulting solution of Carrageenan is neutralised, concentrated by evaporation, dried and milled into powder for final blending and standardisation. Because, in this process, not all cellulose can be removed the semi-refined Carrageenan is opaque and never fully clear (contains residual cellulose and 5-6% KCl). This product is also called PNG (Philippine Natural Grade) or PES (Processed Eucheuma Seaweed). Today, it is mostly used in the meats industry and in the dairy industry where clarity is not an issue. The main advantage of semi-refined Carrageenan is the low cost.

  • Isopropanol process (alcohol coagulation, refined process). In this process, the raw Carrageenan is first dissolved and filtered to remove cell wall debris. The Carrageenan is then precipitated from the clear solution by isopropanol. The product of the process is called refined lambda Carrageenan, which is very soluble. This process is declining because of high costs, which involve installation of flameproof equipment and plant needed to re-distil the large volumes of alcohol. However, this process is still in use for South American weed (like Gigartina), which can be very cost effective due to high yield. Produced in this process, the refined Carrageenan, contains 5-6% KCl, but is free from sea-plant cellulose, so can creates clear gels.
  • Potassium chloride process (KCl precipitation, refined process). In this process, the raw Carrageenan is first dissolved and filtered to remove cellulose. Next, the Carrageenan is precipitated from the clear solution by isopropanol. The product of the process is called the refined Carrageenan  (it contains 15-20% KCl). The advantage of this process is an ability to produce the refined Carrageenan without the use of alcohol, but unfortunately, it can be applied only for Eucheuma cottonii processing. In this process, only kappa type Carrageenan gels can be manufactured. This process is popular in Asia.
  • Mixed process (hybrid technology, Danisco process). This is a semi-refined process in which alcohol or salt is added to inhibit dissolution of Carrageenan. Although this process is not as cheap as the semi-refining one, it allows a wider range of seaweeds to be processed. It is useful especially for naturally low cellulose levels seaweeds (present in South America).

 

Carrageenan manufacturing.

Carrageenan has been around for centuries. It was discovered as a food thickener along the Irish coasts, where locals boiled seaweeds and use the extracted material to transform their milk into thick pudding. It was used also in China. Later cultures around the world used this thickener for centuries. (6)

In the 18th and 19th centuries, Carrageenan production was developed slowly. Small processing plants were developed in Ireland, Philippines and China, where they expanded enormously during World War II, mainly to replace agar (the supply agar from Japan had been cut off by the war). After the war, carrageenan gradually became a major food additive in seaweed extracts and other gelling agents group.

In other countries including Indonesia, Malaysia, Tanzania, Kiribati, Fiji, Kenya, and Madagascar production of Carrageenan developed also. Farmers used mainly two species of red algae: Kappaphycus alvarezii and Eucheuma cottonii (called for Carrageen processors cottonii) and Eucheuma denticulatum (called for Carrageen processors spinosum). In Canada production originated from Canadian Carrageen Moss (Chondrus crispus), similar to this in Ireland. In the South America, farmers are using mostly Gigartina species. Today, primarily wild-harvested species for producing Carrageenan raw materials are: Chondrus, Furcellaria, Gigartina, Sarcothalia, Mazzaella, Iridaea, Mastocarpus and Tichocarpus. The majority of these naturally occurring ocean plants are sustainably cultivated on small family farms, primarily off the coast of Southeast Asia and East Africa.

 

Carrageenan market.

At the moment, the main producers of refined Carrageenan are in USA, France, Denmark, China and Philippines. Besides these countries, production of Carrageenan is continued also in Argentina, Canada, Chile, Ireland, Japan, Mexico, Morocco, Portugal, North Korea, South Korea, Spain and Russia.(7)

In 2009 total market volume exceeds 140,000 commercially dried tonnes of algae per annum at a value of more than $70 million. At this time, the world Carrageenan production exceeded 50,000 tonnes with a value of over 527 million USD. In 2013 the global Carrageenan industry was worth 762.35 million USD.

In last decade export from China grows faster. For example, in 2012 imports from China into EU/USA have increased to nearly 6000 tonnes (up 107% since 2006), where import from the Philippines grown only slightly (from 5000t/yr in 2006 to 5800t/yr in 2011).

Now production of Carrageenan is not increasing or is even decreasing due controversy related to its use in food.

Current main producers of Carrageenan are: Agarmex SA, Andi Johnson Group, Cargill Food Ingredients, Ceamsa, CP Kelco, Dupont / Danisco, Est-Agar AS, Exandal Corp., FMC Biopolymer, Geltech Hayco Inc, Gelymar SA, Green Fresh (Fujian) Foodstuff Co., Ltd, Hainan Kaiyang Trade Co. Ltd, Hispanagar, Iberagar, Ina Food Industry Co. Ltd, Kerry Group, Lucid Colloids Ltd, Marcel Carrageenan, Mitsubishi, MSC Co. Ltd, Pt Galic Artabahari, Pt Gumindo Perkasa Industri / Indo Gum Carrageenans, Shanghai Beilian Foodstuff Co., Shemberg Corporation, Soriano SA, Tacara, TBK Manufacturing Corporation and Yantai Sheli Hydrocolloids Co. Ltd.

 

Carrageenan controversy.

Carrageenan has been successfully used by the food industry in the USA since the 1950s. During years it was widely used for stabilisation, thickening and gelation, so increasing demand has been observed. It was driven by the consumers' needs for convenient, advanced food appealing in new textures.

An intrinsically "organic" nature of Carrageenan was not so much in question. It was recognised as safe. In the 1970's, food manufacturers have even been relying on Carrageenan as a stabilising and thickening agent. Carrageenan was widely used as highly functional food additive. While the U.S. Food and Drug Administration, European Commission, and the World Health Organization give Carrageenan the green light, since the beginning of the 1960s, some scientists and activist raised health concerns, especially regarding intestinal inflammation and inflammatory bowel disease. The situation is still not clear and we don’t know if Carrageenan is safe.

More about recent debate related to a safety of Carrageenan you can read in this Community Alert.

 

Carrageenan as an ingredient in the food.

Based on the seaweed source, Carrageenan was an organic ingredient and was very popular in organic food. It is still a vegetarian and vegan alternative to gelatin. Technically Carrageenan is considered as a dietary fibre and it is usually certified as halal and kosher.

In the USA, Carrageenan is allowed under FDA regulations to use in the amount necessary as an emulsifier, stabilizer, or thickener in foods. (8-9) Also, the European Food Safety Authority allowed using it. (10) In the EU it is marked on label as E407 or E407a (when present as "processed eucheuma seaweed"). (11) In 2014, the Joint FAO/WHO expert committee on food additives approved Carrageenan in infant formula or formula for special medical purposes at concentrations up to 1000 mg/L. (12)

In relation to its “organic” character situation is changing. In 2003, the National Organic Program (NOP) had added Carrageenan to its National List of additives allowed to be included in organic foods. However in 2016, the NOP removed it from this list. Since that, the food products containing Carrageenan no longer may be labelled as "organic". (13)

Many people negatively react after consumption of Carrageenan. There have been reported symptoms like digestive troubles, skin rashes and other health problems. But, we have to remember that Carrageenan is found mostly in processed and packaged foods. These products should make up only a small part of our diet. However, if Carrageenan is consumed regularly in relatively high amount, it can be harmful. For people sensitive for Carrageenan it is advised to change diet to more unprocessed food.

 

References

1. National Organic Standards Board Meeting Agenda – November 2016

2. http://www.fao.org/docrep/006/y4765e/y4765e0a.htm

3. Philp K, Defreitus Z, Nicholson D, Hoffman R, Tiger striping in injected poultry - causes and cures, Gums and Stabilisers 9, The Royal Society of Chemistry Cambridge, pp276-285

4. Rees DA, Steele IW, Williamson FB, Conformational analysis of polysaccharides III, Polymer Sci Part C: Polymer Symposia, 28(1), pp261–276 (1969)

5. Rees DA, Welsh EJ, Secondary and tertiary structure of polysaccharides in solutions and gels, Angewandte Chemie International Ed, 16(4), pp214–224 (1977)

6. http://www.seaweed.ie/uses_general/carrageenans.php

7. https://www.cybercolloids.net

8. 21 Code of Federal Regulations 172.620

9. Generally Recognized As Safe 21 CRF §182.7255 GRAS ID Code 9000-07-1 (1973)

10. Opinion of the Scientific Committee on Food on Carrageenan (2003) [2] p. 5

11. "Current EU approved additives and their E Numbers". Food Standards Agency. 26 November 2010. Retrieved 12 August 2014.

12. Joint FAO/WHO Expert Committee on Food Additives. Who.int. Retrieved on 2014-8-11

13. https://www.cornucopia.org/2016/11/follow-national-organic-standards-board-meeting-st-louis-mo-nosb