12 BRITISH FOOD JOURNAL 96,3
Arguments are presented to bring all
carrageenans into a single regulatory
classification.
The
Carrageenan
Connection IV
H.J. Bixler
British Food Journal, Vol. 96 No. 3, 1994, pp. 12-17
MCB University Press Limited, 0007-070X
Introduction
In previous articles appearing in this journal, D.M.W.
Anderson has offered his views on carrageenan[1]. In his
most recent publication, Anderson speculated that it
would be prudent to classify refined and semi-refined
carrageenans as the same substance, or very similar
substances for better regulatory control. In this article, a
rationale is developed for bringing two forms of
carrageenan in closer regulatory alignment.
Several natural hydrocolloids are extracted from sea or
land plants and are widely used in processed foods. They
are on the market as products of varying degrees of post-
harvest processing which vary from virtually native (only
mechanically separated from impurities after harvesting)
to highly refined (dissolved, purified and precipitated).
In this context, native and refined are not quality-ranking
terms, but refer only to degree of processing. Native
products can be made by a simple but sophisticated
process and must be of high quality for food use. On the
other hand, some refined products are of lesser quality,
particularly if they are being formulated into industrial
Received 10 December 1993
Accepted 5 March 1994
products. Refining is often accompanied by chemical
modification. Extractive processes are widely used.
Some examples of food hydrocolloids with their EC
numbers and common names[2] are given in Table I. This
diversity of product types, made by a diversity of
processes, under a common name extends to foods that
are also food ingredients, e.g. starch which as an item of
commerce may be sold as flour, starch or cold water
soluble starch. For labelling purposes on foods, the
different grades of these food additives require
sufficiently informative common names, E-numbers and
definitive specifications to inform food processors,
regulatory authorities and consumers sufficiently.
In the case of E-numbers, the letters (a) and (b) following
the number are used to differentiate variations of a
substance which might be important to the consumer[3].
On the other hand, the letters (i), (ii) following the number
are given to individual market forms of a substance with
specifications which differ only slightly[3]. This latter
differentiation, while important to food processors, is not
felt to be sufficient to require consumer notification, so it
does not have to be listed separately on a food package
label. In this article we will focus on the carrageenans and
the forms that are being produced, marketed and used in
various parts of the world. The authors will try to put
some order into the confusion that has arisen over some of
the forms.
The Various Types of Carrageenan
A potent thickening and gelling agent is extracted from
various species of red algae growing naturally in our
oceans. It is widely used under the food ingredient
identification carrageenan or E407. The origin of its
name, carrageenan, is lost in history, but may have
derived from a small village, Carragheen, on the Irish
coast, where the carrageenan-bearing seaweed Chondrus
crispus or Irish moss grows. The following names are
used more or synonymously for one or more of its
variants:
carraghenate;
Danish agar;
eucheuman;
furcellaran;
gelose;
hypnean;
Irish moss;
The ideas behind this article were originally developed by Peter
Kuhnert and were first published in Gordian. This condensed
English version was prepared by the author who continues to
be indebted to Mr Kuhnert for his advice and guidance.
 THE CARRAGEENAN CONNECTION IV 13

Table I. Examples of Food Hydrocolloids Different applications require blends of different amounts
of each limit carrageenan. Other types, differentiated
primarily by more or less sulphate ester, also exist but
E400-405 Alginates in acid, salt or propylene glycol ester play only a subordinate commercial role, except for a
form (refined and modified) hybrid that occurs in certain cold water seaweeds. This is
a copolymer of kappa and iota carrageenan that finds
E407 Carrageenans (refined and native or semi-
widespread use in dairy applications, and is sometimes
refined)
referred to as kappa-2-carrageenan.
E410 Carob gum (native or semi-refined and refined)
Differentiated by Their Origin
E412 Guar gum (native) Carrageenans come from naturally growing red algae
(Rhodophyceae). Botanists classify commercially
E414 Gum arabic (native and refined) significant carrageenan-bearing seaweeds into the
following families and genuses[4]:
E440 Pectins
Furcellariaceae, e.g. Furcellaria;
in salt or methylester form (refined)
in acid amide form (refined and modified) Gigartinaceae, e.g. Chondrus, Gigartina, Iridaea;
Hypnaceae, e.g. Hypnea;
E460 Cellulose
in acid washed, microcrystalline form Phyllophoraceae, e.g. Ahnfeltia, Gymnogongrus;
(refined by extraction and degradation) Solieraceae, e.g. Eucheuma.
in powdered form (refined by extraction)
These classifications, however, are of lesser
importance for commercial products, since several
algae may yield extracts with similar properties and
thus they may be processed together. Furthermore,
carragheen;
they do not all contain pure iota, kappa or lambda
refined carrageenan; carrageenan, but varying mixtures of them.
semi-refined carrageenan; Toxicological evaluations have shown that the
sulphate content and molecular weight of carrageenan
Philippine natural grade (PNG) carrageenan; is more important in food safety than is the seaweed
processed eucheuma seaweed (PES); source; although this premiss is not accepted by all
red algae extract. regulatory bodies, e.g. the US Food and Dr ugs
Administration (FDA), where carrageenan is still
The E407 carrageenans designation includes a variety of defined as the extract of only certain species of red
products (and their blends); they are explained and seaweeds listed in the regulation.
described in the following sections from different
technical perspectives. Differentiated by the Way They Are Processed
Type A
Differentiated by Their Chemistry Dried ground red algae yield greyish green to brown
All carrageenans consist of very long straight chains of powders which, after heating in an aqueous solution,
D-galactose and D-anhydrogalactose with ester sulphates display good qualities of suspension and thickening, and
attached to them. The ester sulphates are neutralized by may be used in industrial applications such as
sodium, potassium, calcium, etc. cations. According to the suspending, grinding or polishing grits, thickening paint,
number of ester sulphates and their positions, the so- or in flocculating solids in wastewater. These seaweed
called limit carrageenans are classified as follows[4]: flours are not suitable for use in foods, cosmetics and
pharmaceuticals. This product grade is not part of E407
iota carrageenan: [1-4(D--galactose-4- carrageenan.
sulphate)-->1-3 (3,6
anhydro-D-galactose-2- Type B
sulphate)] n Dried algae are extracted at a concentration of 100 kg of
kappa carrageenan: [1-4(D--galactose-4- algae in 1,000 to 1,500 kg of 10 per cent K2CO3 or KOH
sulphate) -->1-3 (3,6 solution for two hours at 70-80C. This extraction process
removes most pigments, proteins and other alkali-soluble,
anhydro-D-galactose)] n
low molecular weight molecules; the solid left
lambda carrageenan: [1-4(D--galactose-2- undissolved is further processed into a food grade quality
sulphate) -->1-3 (D-- white to yellowish powder, by washing, drying,
galactose-2,6-disulphate)]n. aseptizing, grinding and blending. This process yields a
14 BRITISH FOOD JOURNAL 96,3

semi-refined carrageenan containing about 80 per cent
carrageenan.
Type C
Dried algae are extracted at a concentration of 5 kg of
algae in about 1,000 kg of 0.1 per cent NaOH or 0.7 per
cent Ca(OH) 2 solutions, thereby dissolving the
carrageenan (forming a ca. 1 per cent solution). After
filtering and clarifying, the solution is concentrated to
about 2 per cent carrageenan; the carrageenan is then:
precipitated with potassium or calcium salts;
precipitated with alcohol;
dewatered by freezing or pressing; or
drum roll dried.
The solids from each of these dewatering steps are
washed, dried, ground and blended into a white to
yellowish powder of food grade quality. This process
yields a more refined carrageenan than Type B, but one
that also contains about 80 per cent carrageenan.
Figure 1 shows the steps in the various processes. Owing
to lower capital investment and less energy usage, semi-
refined carrageenan offers approximately 20 per cent cost
savings over refined carrageenan. In both Type A and C
processes, optional steps are included which affect the
product purity. For instance, a petfood grade carrageenan
can be made via the Type B process, but for this
application the colour removal and aseptizing steps
would not be required.
Differentiated by the Requirements for a Particular
Application
The suitability of a particular carrageenan product in a
particular application is mainly due to the iota, kappa,
and lambda carrageenan content of the product:
Iota carrageenan is either hot- or cold-soluble and
forms pastes or soft elastic gels;
Kappa carrageenan dissolves only when heated
and forms strong gels that tend to be brittle;
Lambda carrageenan is very easily cold-soluble,
and is a strong thickener, but forms no gel.
The thickening and gelling power of all types of
carrageenan is usually improved by heating solutions to
80-90C; gels start to form after cooling to ca. 50C, and
the gels will melt again if re-heated to 80-90C. The gels
are thus said to be thermally reversible.

Figure 1. Carrageenan Processes The ability to form clear solutions or gels is another
decisive factor for a particular application. Semi-refined
Fresh seaweed carrageenan (Type B) will always produce a cloudy
solution or gel owing to the cellulose contained in it. Type
Cleaning/drying C carrageenan can form solutions and gels that range
from slightly cloudy to sparklingly clear.
Grinding KOH Alkaline
Extraction extraction Clarity is of no importance for food products containing
milk, meat, fruit or other cloudy food ingredients such as
Size Freshwater Filtration starch. Cake glazes, sparkling clear dessert gels and clear
separation washing
salad dressings, however, can be produced only by
refined carrageenans of type C.
Colour Concentration
removal

Freshwater
washing
Precipitate
(optional) Suggested Regulatory Classifications
As described above, E407 carrageenan covers a variety of
Drying products. This poses the question of whether and how far
must the nomenclature and additive numbering be
Aseptizing Drying extended to differentiate the carrageenans in their uses as
(optional) additives. Classification may be done in different ways as
detailed below.
Grinding Grinding
Classification by the Fractions Iota, Kappa, Kappa/Iota
Hybrid, Lambda Carrageenan
Standardize Standardize Physiologically, the individual types are all equally
indigestible[5] but they differ chemically as well as in
their applications. They do not all occur naturally in pure
Type A Type B Type C
Seaweed flour Native CGN Refined CGN form, and are mixed to suit specific applications.
25% + 10% CGN 80% + 10% CGN 80% + 10% CGN Therefore this differentiation is not suitable to describe
commercial products and is unimportant to the consumer.

Classification by Algae Species
The source seaweed is equally unsuitable as a
distinguishing criterion, since the properties of the
additive E407 are only partially due to from which algal
species they are extracted. A former separation of E407
carrageenan and E408 furcellaran, based primarily on
algae species differentiation, was abandoned in 1975.
Toxicology studies on carrageenans from separate algal
species have shown only minor differences that are of no
consequence in determining food safety.
Classification by Salt Type
Being a very acidic ester sulphate, carrageenan is always
offered commercially in salt form, which means,
stoichiometrically, it contains at least 10-12 per cent by
weight of sodium, potassium or calcium. Even higher salt
contents are encountered in commercial products where
the salts enter the product as processing aids used to
control gelling properties during processing. Since this is
an intentionally produced differentiation, the following
classifying description, which follows the one for
alginates could be used:
E407a Sodium-carrageenate,
E407b Potassium-carrageenate,
E407c Calcium-carrageenate, etc.
Carrageenan is used in such small quantities and its
sodium or calcium concentration is so low, that these
designations are of no importance to the consumer.
Classification by Their Manufacturing Process or by
Which Substances Other Than Sulphated Polygalactose
They Contain
Depending on the method used to extract E407, it
contains a variety of substances apart from the 70-85 per
cent of polygalactose sulphates:
When precipitated from a solution (type C),
carrageenan is accompanied by 15-20 per cent of
mineral salts and up to 1 per cent crude protein.
When separated from other components by
extraction and washing (type B), carrageenan is
accompanied by 8-12 per cent cellulose originating
as cell wall fragments, i.e. crude fibre, and up to 2
per cent crude protein.
Figure 2 shows the equivalence in carrageenan content of
type B and C carrageenans as well as the other
components present[6].
These minute differences are of no importance to the
consumer, since they have been proven not to cause food
safety differences[6]. Therefore, following the precedent
for numbering different commercially processed or
chemically distinguishable types of E460 cellulose:
E460(i) microcrystalline cellulose;
E460(ii) powdered cellulose,
THE CARRAGEENAN CONNECTION IV 15
Figure 2. Carrageenan Compositions (Dry Basis) (Averages
for 20 Commercial Samples)
100
90
80
70
60
Percentage
50
40
30
20
10
0
Refined native/semi-refined
Key:
Carrageenan A.I.M. Salts Protein
a logical way of differentiating distinguishable types of
E407 carrageenan would be:
E407(i) refined (or precipitated, filtered or clear-
soluble) carrageenan;
E407(ii) native (or semi-refined, washed, with
cellulose or PNG) carrageenan.
It seems to be an unwritten practice within the Food and
Agriculture Organization and the World Health
Organization (FAO/WHO) that both variations have the
same ADI value (safe threshold or allowable daily intake),
but the origin and force of this practice need to be further
researched.
Allowable Daily Intakes
Undegraded carrageenan is not digestible[3] and thus is a
soluble dietary fibre. As such, carrageenan may be
beneficial to the digestive process and retard resorption of
some food ingredients.
Strongly degraded carrageenan can promote colonic
ulceration in mammals and is absorbed[5]. Based on the
assumption that undegraded carrageenan posed a
similar, albeit diminished threat, the Joint Expert
Committee on Food Additives (JECFA) originally
imposed an ADI limit of 50 mg/kg/day[7]. After this
assumption had been proved wrong JECFA raised the
ADI value, first to 75 mg/kg/day[8] which represents a
no-effect-level of 10 to 15 per cent in the human diet!
Finally the ADI was raised to the best possible value of
not specified[9], but explicitly only for un-degraded
carrageenan of high molecular weight. The high
viscosity/high molecular weight requirement, which is
part of the purity specifications[4], prevents the use of
partially degraded, i.e. low molecular weight
carrageenan. At the time of writing the EC ADI remains
at 75 mg/kg/day[10]. Questions have been raised recently
16 BRITISH FOOD JOURNAL 96,3
by the Ministry of Agriculture, Fisheries, and Food in the
UK and by the FDA in the USA, concerning the potential
degradation of carrageenan during food processing and
its impact on food safety, especially for young
children[11,12]. Until these issues are satisfactorily
resolved, it is doubtful that the EC ADI will be changed.
There could also be a change (increase) in the
viscosity/molecular weight specification.
Efforts have been made
to propose new and
unusual names
The source algal species are not mentioned by Codex
Alimentarius or in the EC specifications, although this
limitation does exist in the US FDA definition of
carrageenan. JECFA includes furcellaran within its
definition of carrageenan, although occasionally it is still
listed separately, e.g. in the US Food Chemical Codex.
This non-uniform treatment results from the nearly
identical chemical composition of these two
polysaccharides on the one hand, and the fact that
furcellaran has never been tested per se for toxicological
effects on the other.
JECFA is currently evaluating native or semi-refined
carrageenan. As expected, the toxicological results
submitted for processed Eucheuma seaweed, the
temporary name assigned in 1984 by JECFA, showed no
significant differentiation in histopathology from other
carrageenans[13]. However, these results are new, and
have so far been used to establish a preliminary
specification only. A tentative ADI of 20 mg/kg/day has
been assigned based on the guideline of a 100-fold factor
of safety below the no-effect level, or the maximum
feeding level, whichever is lower. In this case, 5 per cent of
the diet was the maximum feeding level and the level
used to establish the ADI. Presumably, as more
information becomes available on the safety of native
carrageenan, the ADI will be elevated to the same value
accorded to filtered or refined carrageenan, and the
E407(ii) designation will be approved[14].
Specifications
A detailed revised specification for semi-refined
carrageenan was recently published by FAO/WHO[15].
This revision closely tracks the specification for refined
carrageenan[4] in contrast with earlier versions which
contained extraneous and contradictory entries. The only
significant remaining difference in purity is the level of
acid insoluble matter (15 per cent for semi-refined and
2 per cent for refined) and a modification of the viscosity
procedure to remove the cellulose (acid insoluble material)
from solution prior to measuring the viscosity. In keeping
with the recent JECFA specifications, the 1993 revision
for semi-refined carrageenan contains microbiological
criteria of purity which are absent from the 1986 revision
for refined carrageenan. In the identification test, refined
carrageenan is said to form a clear to slightly opalescent
solution, whereas semi-refined carrageenan forms a
cloudy opalescent solution.
Conclusions
Efforts are being made by the Philippines and other
countries to reunite both types of carrageenan under E
or INS 407 in the EC and within FAO/WHO[16]. There
is, however, an opposing strategy. Recent efforts have
been made, principally by certain manufacturers of
refined carrageenan and their trade organizations, to
propose new and unusual names and numbers for semi-
refined carrageenans. They have also lobbied, for
purely economic gain, to change the specifications in
favour of refined grades in order to deny immediate
food grade status to less expensive semi-refined grades
and/or exclude them from existing food specifications.
These activities are especially welcomed by circles who
have always condemned any food additive. However,
one of the most vocal critics of the Philippines efforts
has recently gone on record as supporting the reuniting
of these additives in which the carrageenan
polysaccharide is the only physiologically active
ingredient[1].
Notes and References
1. Anderson, D.M.W., The Carrageenan Connection,
British Food Journal, Vol. 94 No. 2, 1992, pp. 37-8; Vol. 94
No. 6, 1992, pp. 3-4; Vol. 95 No. 6, 1993, pp. 22-4.
2. Commission of the European Communities, Proposal for
Council Directive on Food Additives Other than Colours
and Sweeteners, Official Journal of the European
Communities, 92/C206/03, 1992.
3. Food and Agriculture Organization, International
Numbering System for Food Additives, Codex
Alimentarius, Volume I, General Requirements, Section
5.1, Rome, 1992.
4. Food and Agriculture Organization, Carrageenan,
Compendium of Food Additive Specifications, Volume I,
JECFA, Rome, 1992.
5. Pittman, K., Goldberg, L. and Coulson, F., Carrageenan:
The Effect of Molecular Weight and Polymer Type on its
Uptake, Excretion and Degradation in Animals, Food
and Cosmetic Toxicology, Vol. 14 No. 85, 1976, pp. 85-93.

6. Seaweed Industry Association of the Philippines (SIAP),
PES/PNG Carrageenan Dossier (Addendum),
submitted to EC-Scientific Committee for Food, 1993.
7. Food and Agriculture Organization, Carrageenan and
Furcellaran, Nutrition Meetings Report, Series No. 46A,
Rome, 1970.
8. Food and Agriculture Organization, Carrageenan and
Furcellaran, Nutrition Meetings Report, Series No. 53A,
Toxicological Evaluation of Some Food Additives, Rome,
1974.
9. World Health Organization, Carrageenan and
Furcellaran Technical Report, Series 710, Evaluation of
Certain Food Additives and Contaminants, Geneva, 1984.
10. Commission of the European Communities,
Carrageenan and Furcellaran Reports of the Scientific
Committee for Food, Seventh Series, Commission of the
European Communities, Brussels, 1978.
11. Ministry of Agriculture, Fisheries, and Food, Report on
the Review of the Emulsifiers and Stabilizers in Food
H.J. Bixler is Technical Adviser to the Philippines Government and resides in Belfast, Maine, USA.
THE CARRAGEENAN CONNECTION IV 17
Regulations, Food Advisory Committee Report, No. 11,
HMSO, London, 1992.
12. Ministry of Agriculture, Fisheries, and Food, Report on
the Review of the Use of Additives in Foods Specially
Prepared for Infants and Young Children, Food Advisory
Committee, Report No. 12, HMSO, London, 1992.
13. Vavasour, E., Processed Eucheuma Seaweed WHO
Food Additives Series, No. 32, Toxicological Evaluation of
Certain Food Additives and Contaminants, Geneva, 1993.
14. At its plenary meeting in March 1994 the European
Scientific Committee for Food assigned an ADI for semi-
refined carrageenan of 75mg/hg/day, the same value it
has confirmed for refined carrageenan.
15. Food and Agriculture Organization, Processed
Eucheuma Seaweed, Compendium of Food Additive
Specifications, Addendum 2, JECFA, Rome, 1993.
16. At its meeting in March 1994 the Codex Committee for
Food Additives and Contaminants (FAO/WHO) approved
INS 407a for semi-refined carrageenan.