Underwater Eucheuma farming in the Philippines for carrageenan production

Carrageenans or carrageenins (/ˌkærəˈɡiːnənz/ KARR-ə-GHEE-nənz; from Irish carraigín 'little rock') are a family of natural linear sulfated polysaccharides that are extracted from red edible seaweeds. Carrageenans are widely used in the food industry, for their gelling, thickening, and stabilizing properties. Their main application is in dairy and meat products, due to their strong binding to food proteins. In recent years, carrageenans have emerged as a promising candidate in tissue engineering and regenerative medicine applications as they resemble native glycosaminoglycans (GAGs). They have been mainly used for tissue engineering, wound coverage, and drug delivery.[1]

Carrageenans contain 15–40% ester-sulfate content, which makes them anionic polysaccharides. They can be mainly categorized into three different classes based on their sulfate content. Kappa-carrageenan has one sulfate group per disaccharide, iota-carrageenan has two, and lambda-carrageenan has three.[2]

A common red seaweed used for manufacturing the hydrophilic colloids to produce carrageenan is Chondrus crispus (Irish moss), which is a dark red parsley-like alga that grows attached to rocks. Gelatinous extracts of the Chondrus crispus seaweed have been used as food additives since approximately the fifteenth century.[3] Carrageenan is a vegetarian and vegan alternative to gelatin in some applications, so may be used to replace gelatin in confectionery and other food. There is no clinical evidence for carrageenan as an unsafe food ingredient, mainly because its fate after digestion is inadequately determined.[4]

The first industrial scale commercial cultivation of Eucheuma and Kappaphycus spp. for carrageenan was developed in the Philippines. The global top producers of carrageenan are the Philippines and Indonesia.[5][6][7] Carrageenan, along with agar, are used to produce traditional jelly desserts in the Philippines called gulaman.[8]

Properties

The molecular structures of different types of carrageenan

Carrageenans are large, highly flexible molecules that form curling helical structures. This gives them the ability to form a variety of different gels at room temperature. They are widely used in the food and other industries as thickening and stabilizing agents.

All carrageenans are high-molecular-weight polysaccharides and mainly made up of alternating 3-linked b-D-galactopyranose (G-units) and 4-linked a-D-galactopyranose (D-units) or 4-linked 3,6-anhydro-a-D-galactopyranose (DA-units), forming the disaccharide repeating unit of carrageenans.[9]

There are three main commercial classes of carrageenan:

  • Kappa forms strong, rigid gels in the presence of potassium ions, and reacts with dairy proteins. It is sourced mainly from Kappaphycus alvarezii.[10]
  • Iota forms soft gels in the presence of calcium ions. It is produced mainly from Eucheuma denticulatum.[10]
  • Lambda does not gel, and is used to thicken dairy products.

The primary differences that influence the properties of kappa, iota, and lambda carrageenan are the number and position of the ester sulfate groups on the repeating galactose units. Higher levels of ester sulfate lower the solubility temperature of the carrageenan and produce lower strength gels, or contribute to gel inhibition (lambda carrageenan).

Many red algal species produce different types of carrageenans during their developmental history. For instance, the genus Gigartina produces mainly kappa carrageenans during its gametophytic stage, and lambda carrageenans during its sporophytic stage. All are soluble in hot water, but in cold water, only the lambda form (and the sodium salts of the other two) are soluble.

When used in food products, carrageenan has the EU additive E numbers E407 or E407a when present as "processed eucheuma seaweed".[11] Technically carrageenan is considered a dietary fibre.[12][13]

In parts of Scotland and Ireland, where it is known by a variety of local and native names, Chondrus crispus is boiled in milk and strained, before sugar and other flavourings such as vanilla, cinnamon, brandy, or whisky are added. The end-product is a kind of jelly similar to panna cotta, tapioca, or blancmange.

Production

Eucheuma denticulatum being farmed for iota-carrageenan in an off-bottom cultivation in Tanzania

Although carrageenans were introduced on an industrial scale in the 1930s, they were known to be used in China since around 600 BCE (where Gigartina was used) and in Ireland around 400 CE[14][15]

Carrageenan derived from Eucheuma spp. (today one of the main cultivated sources of carrageenan), known as gusô or tambalang in the Visayan languages, has also been traditionally used as food in the Philippines. They were first recorded in the Diccionario De La Lengua Bisaya, Hiligueina y Haraia de la isla de Panay y Sugbu y para las demas islas (c.1637) of the Augustinian missionary Alonso de Méntrida (in Spanish). In the book, Méntrida describes gusô as being cooked until it melts, and then allowed to congeal into a sour dish.[16]

The most commonly used sources are Eucheuma cottonii, Kappaphycus alvarezii, and Eucheuma spinosum, which together provide about three-quarters of the world production. These grow from the sea surface to a depth of about 2 m (6.6 ft). The seaweed is normally grown on nylon lines strung between bamboo floats, and it is harvested after three months or so, when each plant weighs approximately 1 kg (2.2 lb).

After harvest, the seaweed is dried, baled, and sent to the carrageenan manufacturer. There the seaweed is ground, sifted to remove impurities such as sand, and washed thoroughly. After treatment with hot alkali solution (e.g., 5–8% potassium hydroxide), the cellulose is removed from the carrageenan by centrifugation and filtration. The resulting carrageenan solution is then concentrated by evaporation. It is dried and ground to specification.

There are three types of industrial processing:

Semi-refined

This is only produced from E. cottonii or E. spinosum. The raw weed is first sorted and crude contaminants are removed by hand. The weed is then washed to remove salt and sand, and then cooked in hot alkali to increase the gel strength. The cooked weed is washed, dried, and milled. E. spinosum undergoes a much milder cooking cycle, as it dissolves quite readily. The product is called semi-refined carrageenan, Philippines natural grade, or, in the U.S., it simply falls under the common carrageenan specification.[17]

                           cleaned and washed seaweed 
                                   ↓
                                extraction
                                   ↓
                             coarse filtration   → seaweed residue
                                   ↓ 
                              fine filtration    → used filter aids
                                   ↓
            ↓-------------- concentration --------------↓
   preparation with KCl                        preparation with alcohol
            ↓                                           ↓
       gel pressing                                alcohol recovery 
            ↓                                           ↓
         drying                                      drying
            ↓                                           ↓ 
         milling                                     milling 
            ↓                                           ↓ 
         blending                                    blending
            ↓                                           ↓
    gel refined carrageenan                     refined carrageenan

Refined

The essential difference in the refining process is that the carrageenan is first dissolved and filtered to remove cell wall debris. The carrageenan is then precipitated from the clear solution, either by isopropyl alcohol (propan-2-ol) or by potassium chloride.[18]

Mixed processing

A hybrid technology in which seaweed is treated heterogeneously as in the semirefined process exists, but alcohol or high salt levels are used to inhibit dissolution. This process is often used on South American seaweeds and gives some of the cost benefits of semirefined processing, while allowing a wider range of seaweeds to be processed, however, the naturally low cellulose levels in some South American seaweeds allow them to be heterogeneously processed and still be sold under the EU refined specification.

Grades

There are two basic grades of carrageenan, refined (RC) and semi-refined (SRC). In the United States, both grades are labeled as carrageenan. In the European Union, refined carrageenan is designated by the E number E-407 and semi-refined carrageenan as E-407a.[11] Refined carrageenan has a 2% maximum for acid-insoluble material and is produced by alcohol precipitation or potassium chloride gel press process. Semi-refined carrageenan has a much higher cellulose content and is produced in a less complex process. Indonesia, the Philippines, and Chile are three main sources of raw material and extracted carrageenan.

Uses and applications

Food and other domestic uses

  • Desserts, ice cream, cream, milkshakes, yogurts, salad dressings, sweetened condensed milks
  • Sauces: to increase viscosity
  • Beer: clarifier to remove haze-causing proteins
  • Pâtés and processed meats (e.g., ham): substitute for fat, increase water retention, increase volume, or improve slicing
  • Toothpaste: stabilizer to prevent constituents separating

Regulatory status

In the U.S., carrageenan is allowed under FDA regulations[19] as a direct food additive and is considered safe[20] when used in the amount necessary as an emulsifier, stabilizer, or thickener in foods, except those standardized foods that do not provide for such use. FDA also reviewed carrageenan safety for infant formula.[21] The European Food Safety Authority concluded "there is no evidence of any adverse effects in humans from exposure to food-grade carrageenan, or that exposure to degraded carrageenan from use of food-grade carrageenan is occurring",[22] Furthermore, the Joint FAO/WHO expert committee on food additives stated in a July 2014 review of carrageenan "that the use of carrageenan in infant formula or formula for special medical purposes at concentrations up to 1000 mg/L is not of concern".[23]

Although the National Organic Program (NOP) had added carrageenan to its National List of additives allowed to be included in organic foods in 2003,[24] and reviewed and reauthorized it in 2008,[25] noting it as "critical to organic production and handling operations",[26] on November 18, 2016, the NOP's National Organic Standards Board (NOSB) voted to recommend carrageenan be removed from the National List of additives allowed in organic food production.[27]

On April 4, 2018, the Agricultural Marketing Service (AMS) (USDA) published a document to announce the renewal of carrageenan on the National List, allowing its continued use in food products. The document states,

The NOSB recommended removing carrageenan because they determined that alternative materials, such as gellan gum, guar gum, or xanthan gum, are available for use in organic products ... AMS found sufficient evidence in public comments to the NOSB that carrageenan continues to be necessary for handling agricultural products because of the unavailability of wholly natural substitutes (§ 6517(c)(1)(ii)). Carrageenan has specific uses in an array of agricultural products, and public comments reported that potential substitutes do not adequately replicate the functions of carrageenan across the broad scope of use. Therefore, carrageenan continues to meet the OFPA criteria for inclusion on the National List.[28]

The rule went into effect May 29, 2018.

In a 2015 review, the Joint Expert Committee of the Food and Agriculture Organization of the United Nations and World Health Organization on Food Additives released a technical report in 2015 on the use of carrageenan in infant formula and found that the additive was "not of concern" in infant formula as food for special medical purposes at concentrations up to 1000 milligrams per litre.[29] The use of carrageenan in infant formula, organic or otherwise, is prohibited in the EU for precautionary reasons, but is permitted in other food items.[30] In 2018, the European Food Safety Authority (EFSA) reported that safety of carrageenan in food products is based on an ADI of 75 mg/kg body weight per day.[4]

In the UK, the Food Standards Agency issued a product recall for sweets containing carrageenan, stating that carrageenan "is not permitted as an ingredient in jelly confectionery products as it presents a choking hazard".[31]

Toxicity research

As of 2018, carrageenan was deemed non-toxic under certain consumption levels (75 mg/kg bw per day), although further research was recommended, mainly focused on the fate of carrageenan during and after digestion, and on any subsequent metabolites.[4][32]

See also

References

  1. ↑ Yegappan, Ramanathan; Selvaprithiviraj, Vignesh; Amirthalingam, Sivashanmugam; Jayakumar, R. (October 2018). "Carrageenan based hydrogels for drug delivery, tissue engineering and wound healing". Carbohydrate Polymers. 198: 385–400. doi:10.1016/j.carbpol.2018.06.086. PMID 30093014. S2CID 51953085.
  2. ↑ Tuvikene, R. (2021), Phillips, Glyn O.; Williams, Peter A. (eds.), "Carrageenans", Handbook of Hydrocolloids (Third Edition), Elsevier, pp. 767–804, doi:10.1016/b978-0-12-820104-6.00006-1, ISBN 978-0-12-820104-6
  3. ↑ FAO Agar and Carrageenan Manual. Food and Agriculture Organization of the United Nations (1965-01-01). Retrieved on 2011-12-10.
  4. 1 2 3 EFSA Panel on Food Additives and Nutrient Sources added to Food (2018). "Re‐evaluation of carrageenan (E 407) and processed Eucheuma seaweed (E 407a) as food additives". EFSA Journal. 16 (4): e05238. doi:10.2903/j.efsa.2018.5238. ISSN 1831-4732. PMC 7009739. PMID 32625873.
  5. ↑ Buschmann, Alejandro H.; Camus, Carolina; Infante, Javier; et al. (2 October 2017). "Seaweed production: overview of the global state of exploitation, farming and emerging research activity". European Journal of Phycology. 52 (4): 391–406. doi:10.1080/09670262.2017.1365175. ISSN 0967-0262. S2CID 53640917.
  6. ↑ Impact Investment for a Business Venture for Community-Based Seaweed Farming in Northern Palawan, Philippines (PDF). Blue Economy Impact Investment East Asia & Partnerships in Environmental Management for the Seas of East Asia. 2017. Retrieved 8 February 2021.
  7. ↑ Habito, Cielito F. (1 November 2011). "Sustaining seaweeds". Philippine Daily Inquirer. Retrieved 8 February 2021.
  8. ↑ Montaño, Marco Nemesio (16 September 2004). "Gelatin, gulaman, 'JellyAce,' atbp". PhilStar Global. Retrieved 10 February 2021.
  9. ↑ Campo, Vanessa Leiria; Kawano, Daniel Fábio; Silva, Dílson Braz da; Carvalho, Ivone (2009-06-10). "Carrageenans: Biological properties, chemical modifications and structural analysis – A review". Carbohydrate Polymers. 77 (2): 167–180. doi:10.1016/j.carbpol.2009.01.020. ISSN 0144-8617.
  10. 1 2 McHugh, Dennis J. (2003). "A guide to the seaweed industry: FAO Fisheries Technical Paper 441". www.fao.org. Food and Agriculture Organization of the United Nations. Retrieved 2017-07-29.
  11. 1 2 "Current EU approved additives and their E Numbers". Food Standards Agency. 26 November 2010. Retrieved 12 August 2014.
  12. ↑ http://www.marine-science.co.jp/english/goods/carra.html Archived 2018-11-03 at the Wayback Machine, Marine Science Co. Ltd.
  13. ↑ DeSilver, Drew (April 1993). "Answering Machine: Carra-what?". Vegetarian Times: 28. Retrieved 12 August 2014.
  14. ↑ Loureiro, Rafael R.; Cornish, M.L.; Neish, Iain C. (2017). "Applications of carrageenan: With special reference to iota and kappa forms as derived from the Eucheumatoid seaweeds". In Hurtado, Anicia Q.; Critchley, Alan T.; Neish, Iain C. (eds.). Tropical Seaweed Farming Trends, Problems and Opportunities: …. Berlin, Germany: Springer International Publishing. p. 165. ISBN 9783319634982.
  15. ↑ Mitchell, M.E.; Guiry, M.D. (December 1983). "Carrageen: A local habitation or a name?". Journal of Ethnopharmacology. 9 (2–3): 347–351. doi:10.1016/0378-8741(83)90043-0. PMID 6677826.
  16. ↑ de Mentrida, Alonso (1841). Diccionario De La Lengua Bisaya, Hiligueina Y Haraya de la isla de Panay. En La Imprenta De D. Manuel Y De D. Felis Dayot. p. 380.
  17. ↑ CyberColloids: E407 Specification Carrageenan, CyberColloids, Hydrocolloids research and development webpage.
  18. ↑ CyberColloids: E407a Specification Processed Eucheuma Seaweed, Hydrocolloids research and development webpage.
  19. ↑ 21 Code of Federal Regulations 172.620
  20. ↑ Generally Recognized As Safe 21 CRF §182.7255 GRAS ID Code 9000-07-1 (1973)
  21. ↑ Federal Food, Drug, and Cosmetic Act 21 U.S.C. 350(a) §412
  22. ↑ Opinion of the Scientific Committee on Food on Carrageenan (2003) p. 5
  23. ↑ Joint FAO/WHO Expert Committee on Food Additives. Who.int. Retrieved on 2014-8-11.
  24. ↑ 68 FR 61993 (2003)
  25. ↑ 65 FR 80548
  26. ↑ 73 FR 59481
  27. ↑ "Sunset 2018 Review Summary NOSB Final Review" (PDF). USDA Agricultural Marketing Service. 2016-11-30. Retrieved 2017-02-15.
  28. ↑ "83 FR 14347". USDA Agricultural Marketing Service. 2018-04-04. Retrieved 2018-04-21.
  29. ↑ Safety Evaluation of Certain Food Additives, 3. Joint Expert Committee on Food Additives, WHO Food Additive Series: 70. 2015. hdl:10665/171781. ISBN 9789241660709.
  30. ↑ "Opinion of the Scientific Committee on Food on Carrageenan" (PDF). European Commission, Scientific Committee on Food. 2003.
  31. ↑ "Tees Ltd recalls Sweetworld Yummys Jelly Cones because of a choking hazard". Archived from the original on 2021-01-21. Retrieved 2018-05-17.
  32. ↑ David, Shlomit; Shani Levi, Carmit; Fahoum, Lulu; Ungar, Yael; Meyron-Holtz, Esther G.; Shpigelman, Avi; Lesmes, Uri (2018-03-01). "Revisiting the carrageenan controversy: Do we really understand the digestive fate and safety of carrageenan in our foods?". Food & Function. 9 (3): 1344–1352. doi:10.1039/c7fo01721a. ISSN 2042-6496. PMID 29469913.

Further reading

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