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Seaweed Applications : tradition & innovations

J-F Sassi,
J-F Sassi, H
H Marfaing,
Marfaing, A
A Menguy,
Menguy, P
P Dion
Dion &
& YY Lerat
Lerat
CEVA, Presqu’île
CEVA, Presqu’île de
de Pen
Pen Lan–
Lan– 22610
22610 Pleubian,
Pleubian, France
France
Seaweed market segmentation

other : agriculture, cosmetics


12,5% industrial ingredients, animal feed
World
8.5 million metric tons
phycocolloids
12,5%

5.5-6 billion US$

sea vegetable
75,0%

sea veg
1,0%
agriculture other
industrial ingredients 24,0%
France animal feed
cosmetics

74 000 tons

phycocolloids
75,0%
FAO, 2005 & CSNAVM, 2007
The french crop

Seaweeds for hydrocolloids 47 946 tons


L. digitata, L. hyperborea, Chondrus crispus
Himanthalia elongata

Fucaeae (seaweed meal) 5 860 tons


Ascophyllum nodosum, Fucus sp.

Edible seaweeds (vegetables) 856 tons


Himanthalia elongata (60%)
Palmaria palmata (26% ), Ulva sp. (9% )
Porphyra sp.(3%)

Data from CSNAVM, 2007


Main seaweed-processimg companies in France

• Phycocolloids : Cargill, Danisco, Hispanagar

• meals : Setalg, Agrimer, Lessonia, Penn Ar Bed

• Extracts : Goemar, Codif, Secma, Algues et Mer,


Penn Ar Bed, Timac

• Sea Vegs : Bretalg, LRCB, Biocéan, Algues de


Bretagne, Algoplus, Algaïa, Algue Service,
Aqua B, Bretagne Ocean, …
Seaweed applications

health complements

sea
phycocolloids vegetables green chemistry

materials

agriculture cosmetics

crop animal feed cosmeceuticals


protection
feed complements
Industrial algal colloids

Name Alginic acid and AGAR CARRAGEENANS SEMI-RAFFINED


alginates CARRAGEENANS

European E 400 to E 405 E 406 E 407 E 407 a


additives
code

Function Thickening Gelling Gelling Gelling

Gelling agent

E 4OO : ALGINIC ACID


E 4O1 : SODIUM ALGINATE
E 4O2 : POTASSIUM ALGINATE
E 4O3 : AMMONIUM ALGINATE
E 4O4 : CALCIUM ALGINATE
E 4O5 : PROPYLENE GLYCOL ALGINATE
An underexploited diversity

Red seaweeds Brown seaweeds Green seaweeds

Cell wall polysaccharides


Agars and agaroids (precursor) Alginates Rhamnans
carrageenans and carrageenoids fucans Arabinogalactans
xylans Cellulose Ulvans
mannans hemicellulose Cellulose and hemicelluloses
cellulose and hemicelluloses

phycocolloids
Agars and agaroids Alginates Rhamnans
carrageenans et carrageenoids Fucans Arabinogalactans
xylans Laminaran Ulvans

industrial phycocolloids (large scale exploitation)


Agars Alginates
Carrageenans
Seaweed applications

health complements

phycocolloids sea
green chemistry
vegetables
materials

agriculture cosmetics

crop animal feed cosmeceuticals


protection
feed complements
Nutritional
Biological functional foods,
claims nutraceuticals

Texture gelling &


viscosity
ingredients

taste
smell
Colour,
vegetables,
color aromates
odour
Seaweed as a vegetable

In Europe : seaweed use for human food has always been scarce
(limited to coastal areas, in war or hunger periods)

Seaweed-based food imported from Japan appeared in the 70s :


• in stores specialized in dietetic foods
• in japanese restaurants

1980 : production structures appear in Europe

French regulation
• seaweed is a non traditional food product
• positive list of 16 macroalgae and microalgae
• toxicological criteria : heavy metals and microbiological standards
Positive list (France)

Nom scientifique Nom commun


 Algues brunes
- Ascophyllum nodosum (1990)
- Fucus vesiculosus (1990)
- Himanthalia elongata (1990) Spaghetti de mer, Haricot de mer
- Undaria pinnatifida (1990) Wakamé
- Laminaria digitata (1997) Kombu
- Laminaria saccharina (1997) Kombu Royal
 Algues rouges
- Palmaria palmata (1990) Dulse
- Porphyra umbilicalis (1990) Nori
- Chondrus crispus (1990) Pioca, lichen
- Gracilaria verrucosa (1990) Ogonori
 Algues vertes
- Ulva sp.(1990) Laitue de mer
- Enteromorpha sp. (1990) Aonori
 Microalgues
- Spirulina sp. (1990)
- Ondontella aurita (2002)
- Chlorella
+ calcified seaweed lithothamnium calcareum
French regulations regarding iodine

3 seaweeds with restriction of use :


maximum 30 mg of dry matter or 210 mg of wet matter per
day (15mg & 150 mg for the children) for high iodine contents

Laminaria digitata
Laminaria saccharina
Gracilaria verrucosa
Toxicological criteria

Maximal level of heavy metals and iodine authorized in seaweeds

Maximal level authorized


mg/kg

Arsenic inorganic (As) 3

Cadmium (Cd) 0,5

Mercury (Hg) 0,1

Lead (Pb) 5

Tin (Sn) 5
2 000
Iodine (I) 6 000 for Laminaria and Gracilaria
Toxicological criteria

Microbiological criteria for dry products

Mesophili aerobic bacteria < 105 / gram

Fecal coliform < 10 / gram

Sulfiroreducteur anaerobes < 102 / gram

Staphylococcus aureus < 102 / gram

Clostridium perfringens < 1 / gram

Salmonella absence in 25 grams

-
Main forms of commercial seaweeds

Fresh
the market is small since preservation is not easy (few days at +4°C)

Salted
elimination of 50% water by mixing with salt
can be stored for at least 6 months at +4°C
to be washed with tap water before use

Dried
the most popular form
in a piece, crushed in pieces or as a flour

Sterilised
for Himanthalia elongata
Food product: seaweeds flakes
Food product: seaweed salt
Food product:sea spaghetti
Delicatessen : seaweed tapenade

Mix of seaweeds with olive oil, pickles, onion


Food product: seaweed marmelade
Food product:cooked meals (fish)
Food product: drinks, liquors, beer
Seaweeds in food and health benefits
In Asia, epidemiological studies (Teas, 1981, Carper, 1989) led to
the conclusion that a regular seaweed consumption could be linked to
better health (lower incidence of breast, colon, prostate cancers)

Origin of health benefits ?


fibers, sterols : reduction of plasma cholesterol
sulfated polysaccharides : antitumor & immunostimulation
alginate : ability to bind metal and pollutants
halogenated phenolic compounds : antibiotic activity, inhibition
of carcinogenic fecal flora
inorganic elements : fight against mineral deficiency (iodine,
calcium)
 secondary metabolites with antioxidant activity : prevention
of atherosclerosis, cardiovascular diseases and cancer
Food complement

Fucus
oligoelements + vitamins +
iodine + fibers for satiety

Suggestions for use


2 doses / day (2 * 10 ml)
Prevention of cardiovascular diseases with brown
seaweed extracts
EU project 2002–2005 - Seaweed antioxidants as novel
ingredients for better health and food quality
OHHO HO
Partnership
HO O OH
 CEVA (F)
OHHO HO
 University of Bonn (D)
 German Cancer Research Center (D)
Fucophlorethol A
 University of Milano (I)
 University of Barcelona (S) OHHO

 A&F (NL)
HO OH
 Institute for Systems and Innovation (D) OHHO
 Diana Végétal (F) OHHO
HO OH
 Karlsruhe Technical University (IWW) (D)
OHHO

Tetrafucol A
Results :
 the extraction & purification processes of seaweed antioxidants were optimized.
 some extracts exhibited a high activity in vitro (DPPH & ORAC tests) and in vivo.
human clinical tests demonstrated that the phlorotannins found in the fucus extract
contribute to the prevention of atherosclerosis
 2007-11-26 : Diana Naturals introduces New Phytonutriance® HealSeaTM
Cardiovascular Ingredient From Fucus
Seaweed applications

health complements

phycocolloids sea
green chemistry
vegetables
materials

agriculture cosmetics

crop animal feed cosmeceuticals


protection
feed complements
Seaweeds in animal nutrition

Seaweed meal

History
•additive to animal feed has been introduced in Norway
•made from brown seaweeds (collected, dried and milled)
Algae in animal nutrition

• Microalgae
 Feeding of fish larva and rotifers

 Pigmentation in salmon aquaculture

 Enrichment of eggs in omega 3


Seaweeds in animal nutrition

Iodine enriched hen-eggs for an healthier nutrition

Patent FR 2 831 396 :

• Feed for egg-laying hens


• Flax seed : 6 to 8%
• Seaweed : 2.5 to 7%

• Eggs : 350 µg iodine/egg


6.4 mg PUFAs
(ratio omega 3/omega 6 = 2.9)
Seaweeds in animal nutrition

Interest of Ulva sp

 carotenoids : - egg-yolk pigmentation


- shrimp pigmentation

 DMSP : dimethylsulfoniopropionate
Protective agent against gastric ulcer
Feeding stimulator for turbot, salmon

 Ulvans O
OH3C O
Increase mucin secretion
O OH
HO2C O HO2C O O
O OH3C O OH
X+ -O3S

 Immunostimulation : shrimp
HO
OH O OH
O
X+ -O3S OH
n n
-D-1,4-glucuronic acid -L-1,4-iduronic acid
-L-1,4-rhamnose 3-sulfate -L-1,4-rhamnose 3-
sulfate
Seaweeds in animal nutrition

Hybrid clay-seaweed extracts

Ulva extract Activated clay


Amadéite ®
Montmorillonite WO2006/030075
Clay

adsorption of Gas Reinforcing


UV filter barrier nanofiller
fungal toxins

animal engineering
cosmetics packaging
nutrition plastics
Seaweed applications

health complements

phycocolloids sea
green chemistry
vegetables
materials

agriculture cosmetics

crop animal feed


cosmeceuticals
protection
feed complements
Seaweeds in cosmetics

 THALASSOTHERAPY

 TEXTURE AGENTS

 ACTIVE INGREDIENTS
VALUE
ADDED
Highly purified
Extracts - active
agents
High
Seaweed Raw water/glycol
Extracts
extracts
Species collected
by diving, or
cultivated
Seaweeds
Species with
as raw low
materials availability

Common
Low species :
mechanical
harvesting
Cosmetic actives from phycocolloids :
Oligoalginates

Alginate from brown seaweeds was depolymerized using


mild aqueous process and CEVA’s proprietary enzyme
AL951
ONa
O
OH OH
HO O HO
O
O HO O
O
OH O OH
O ONa
ONa x = 0-5

Oligo alginate : MM block

 PHYCOSACCHARIDE® (CODIF)
 PHYCOSACCHARIDE® anti-pollution (DP50)
 PHYCOSACCHARIDE® anti-rash (DP9)
+ Zn  PHYCOSACCHARIDE® anti-acnea
+ Mg + Mn  PHYCOSACCHARIDE® anti-ageing
Seaweed applications

health complements

phycocolloids sea
green chemistry
vegetables
materials

agriculture cosmetics

animal feed
crop cosmeceuticals
protection
feed complements
Agriculture : seaweeds as fertilizers

Background
•dates back to the 17th century
•high colloid content acts as a soil conditioner and helps moisture retention
•mineral content : useful fertilizer (K, N, P) and source of oligoelements

Today
growth area : liquid seaweed extracts
•10 000 tons wet seaweeds (1991)
•to yield 1 000tonnes of seaweed extracts
•which is sold for US$ 5 million
Tonialg -Goémar Maxicrop Pro Liquid Seaweed
Agriculture : crop protection

High value product : elicitor


activity from oligosaccharides
Discovery (1980) : elicitor
activity induces defense
reactions in plants

An example : Laminarin from


GOEMAR labs
polysaccharide extracted from
Laminaria digitata, -1,3-glucan
(average DP=33)
ALBERSHEIM, P., B. S. VALENT:. J. Cell Biol. 78,
78, 627-
627-642 (1978)
ALBERSHEIM, P., A. G. DARVILL: Oligosaccharins.
Oligosaccharins. Sci.
Sci. American, Sept. 1985
Seaweed applications

health complements

phycocolloids sea
vegetables green chemistry

materials

agriculture cosmetics

animal feed
crop cosmeceuticals
protection
feed complements
“Algae and Zostera as raw material for production of
bioplastics and biocomposites contributing to
sustainable development of European coastal regions”
Contract n° QLK5-CT-2002-02431 (2003-2006)

Automotive parts
Zostera based
composites

Tomato clips :
Ulva based composites Mechanical
properties

Biodegradability
properties
Seaweed pulp for carboard mfg

Grinding +
wet mixing
molding
séchage

démoulage

Calender draining Drying


Biodegradable Ulva Flowerpot

Peat
Flowerpot

Ulva
Flowerpot
USE OF ZOSTERA BRICKS FOR SOIL-LESS CULTIVATION
patent WO2008/065124 Publication date: 2008-06-05

Zostera stranding on beach - Arcachon area

Zostera advantages
stable in aquatic medium
water retention
bacteriostatic
inhibits fungi adhesion
Seaweed applications

health complements

phycocolloids sea
vegetables BLUE chemistry
green

materials

agriculture cosmetics

animal feed
crop cosmeceuticals
protection
feed complements
Cracking Approach to multiply application potential
Materials
Hemicellulose

Fertilizers

phytosanitary
phycocolloids

Cosmetic

Animal
Protein Feeding
Human
Food
Other
Chemicals Fine
Chemistry
Drain Minerals
Water Ca, K, Mg, Pharma
I, Fe, …
Cell Water
Green Surfactants
X
ONa
O O
OH OH
O OH
HO O HO HO O
O HO O HO
O
OH O OH
O ONa
ONa x = 0-5 WO 03/01586 O (C H ) n C H
2 3
Oligo alginate : MM block WO 03/01584

HO2C O OH OH3C O O
O O H 3C
O OH3C O HO2C O O OH O
HO OH HO 2C O O
OH O X+ -O3S
X+ -O3S O(CH2nCH3)
OH O OH
X+ -O3S
n
n WO2007/045795 O OH

n
Oligo Ulvan

Properties :
• Specific Bioactivity of the hydrophilic sugar head
(ulvan, oligoM), Biosurfactant mimicking.
• Associative properties (alginate / Ca)
• new physico-chemical delivery systems with enhanced
protection and tunable targeting
Seaweed applications….

health complements

phycocolloids sea
vegetables BLUE chemistry

agriculture cosmetics

animal feed
crop cosmeceuticals
protection
feed complements

… and MUCH more to discover !


Thank you for your attention !!

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… to value-added
ingredients

Centre
d’Étude et de
Valorisation
des Algues

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