WEFTA 2008, Florence – Italy, 17-19 September 2008 1

Aromatic upgrading of marine by-products

Sardine (Sardina pilchardus) hydrolysates example

L. Tripoteau1,2, C. Prost2, M. Cardinal1, JP Bergé1

1 Département Sciences et Technologie Alimentaires Marines, IFREMER centre de Nantes, BP 21105, 44311 Nantes cedex 03, France

2 ENITIAA– Equipe de recherche Arôme UMR CNRS 6144 Nantes,

France

Members of the SEApro network

WEFTA 2008, Florence – Italy, 17-19 September 2008 2

BiomassPrimary

Products

By-products &Wastes

Processing

By-catch

40-60%

Secondary

ProductsConversion

CONTEXTCONTEXT

WEFTA 2008, Florence – Italy, 17-19 September 2008 3

By-products of sardina

Secondary

ProductsConversion

CONTEXTCONTEXT

WEFTA 2008, Florence – Italy, 17-19 September 2008 4

By-products of sardina

Secondary

ProductsEnzymatic Hydrolysis

CONTEXTCONTEXT

WEFTA 2008, Florence – Italy, 17-19 September 2008 5

AromaEnzymatic Hydrolysis

By-products of sardina

CONTEXTCONTEXT

WEFTA 2008, Florence – Italy, 17-19 September 2008 6

Raw material (100)

(sardina heads & viscera)

Enzyme (x)

(large spectra protease)Water (50)

Temperature(-1 / +1)

Time(-1 / +1)

Reaction

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 7

Sensory analysis

Experimental conditions

- Trained panel of 13 people- 5 samples :

- T30 t30 A0 S0- T60 t6 A1 S1- T60 t6 A0 S1- T60 t6 A0 S0- Central point

- “sniffing” characterization

Strategy

Descriptors

ANOVA

Notation

Validation : consensus

PCA

Discriminative descriptors

Characterization of samples

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 8

Extraction of volatile components :

Solid phase micro-extraction (SPME)

Head space

Volatile components adsorbed on SPME CAR/PDMS fiber

- 20 min equilibrium

- 30 min adsorption

Water bath at 30°C

20 ml of hydrolysate

Aromatic characterization

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 9

Identification – Semi-quantification

GC - MS - FID

- Identification by MS and RI

- Internal standard

- Semi-quantification

Aromatic characterization

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 10

PRELIMINARY RESULTSPRELIMINARY RESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 11

Aroma fromhydrolysates

Maillard reaction

Polysaccharides degradation

PUFA oxydation

(ω3 et ω6)

MUFA oxydation

(ω9)

Carotenoids degradation

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 12

Aroma fromhydrolysates

Maillard reaction

Polysaccharides degradation

PUFA oxydation

(ω3 et ω6)

MUFA oxydation

(ω9)

Carotenoids degradation

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 13

Raw material (100)

(sardina heads & viscera) Water (50)

Enzyme (x)

(large spectra protease)

Reaction

Antioxydants (-1 / +1)

(complementary actions)

Sugar (-1 / +1)

Temperature(-1 / +1)

Time(-1 / +1)

Reaction

Reaction

METHODOLOGYMETHODOLOGY

WEFTA 2008, Florence – Italy, 17-19 September 2008 14

Parameters Low Center High

Temperature (°C) 30 45 60

Time (min) 30 195 360

Antioxydant -1 0 1

Sugar -1 0 1

METHODOLOGYMETHODOLOGY

Experimental design

WEFTA 2008, Florence – Italy, 17-19 September 2008 15

Réactions de Maillard

Oxydation lipidique

2-pentene x2-methyl-furan x

3-methyl-butanal x2-ethyl-furan x

1-penten-3-one x2,3-pentanedione x

Hexanal x1-Penten-3-ol x(E)-2-hexenal x1-pentanol x

octanal x 2-penten-1-ol x2-nonanone x

2,4-hexadienal x2-furancarboxaldehyde x(5Z)-octa-1,5-dien-3-ol x

2,4-heptadienal xbenzaldehyde x x

2-furan-methanol x1,3-cyclo-octadiene x

Composé

Origine principaleMajor originCompound

MaillardLipid

Oxydation

70 molecules identified

20 molecules studied

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 16

Processing parameters influence:

11 molecules were significantly influenced

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 17

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 18

Maillard reaction products

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 19

Lipid oxydation products

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 20

Lipid oxydation productsMaillard reaction products

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 21

Central points

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 22

DH

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 23

Maillard reaction(++)

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 24

Lipid oxydation (++)

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 25

Maillard reaction(-)Lipid oxydation (-)

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 26

« grilled, burnt »

« marine, vegetal »

« fatty fish, rancid »

+

RESULTSRESULTS

WEFTA 2008, Florence – Italy, 17-19 September 2008 27

Aroma perception of an hydrolysate can be modulated:

– Aldehyds from lipid oxydation � “fatty and vegetal”

– Aldehyds from Maillard reaction � “grilled”

Positive correlation between hydrolysis degree (DG) and Maillard reaction

CONCLUSIONCONCLUSION

WEFTA 2008, Florence – Italy, 17-19 September 2008 28

Sensory analysis on all the samples

Identification and quantification of all the molecules

Experimental design interpretation

Feed and Food applications

���� Modulate and control the aroma properties

PERSPECTIVESPERSPECTIVES

WEFTA 2008, Florence – Italy, 17-19 September 2008 29

Many thanks to:

Charlotte Jacobsen (DTU)

Sensory analysis panel

ACKNOWLEDGEMENTACKNOWLEDGEMENT

WEFTA 2008, Florence – Italy, 17-19 September 2008 30

THANK YOU FOR YOUR ATTENTIONTHANK YOU FOR YOUR ATTENTION