FROM FISH TO NUTRACEUTICALSThe Potential of ‘Green Solvents’ to add
Value to Fish By‐products
Francisca Mano, Susana Barreiros, Pedro Simões, Steve Bowra and Alexandre Paiva
June 21 th‐24 th, Athens , Greece
FACULDADE DE CIÊNCIAS E TECNOLOGIAUNIVERISDADE NOVA DE LISBOA
FISH INDUSTRY 2009 2010 2011 2012 2013 2014(1)
PRODUCTION (Million tonnes) 145.9 148.1 155.5 157.8 162.9 167.2 UTILIZATION Human consumption 123.8 128.1 130.8 136.9 141.5 146.3 Non‐food uses 22.0 20.0 24.7 20.9 21.4 20.9 Population (billions) 6.8 6.9 7.0 7.1 7.2 7.3 Per capita food fish supply (kg) 18.1 18.5 18.6 19.3 19.7 20.1
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• Aquaculture (worldwide):♓ 73.8 million tonnes of fish (50% of the fish production)
FAO STATISTICS
FISH BY‐PRODUCTS
• Considered of low value:
• Gelatine, fish sauce, fish sausages (and others snacks)
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Component Weight (%) Head 21 Gut 7 Liver 5 Roe 4 Backbone 14 Fins and Lungs 10 Skin 3 Fillet 36
• Fish is processed in various steps, producing various by‐products:
LOW CONSUMER ACCEPTANCE OR SANITARY REGULATIONS RESTRICTION
ANIMAL FEEDING DISCARDED
FERTILIZATION
APPLICATIONS
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Fish protein hydrolysates
Bioactive products
Biomedical materials
Bioplastics Emulsifiers
Cryopreservatives
Nitrogen source for broth media
A wide range of applications…
APPLICATIONS
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A wide range of applications…
Conventional extractions methods:
• Chemical
• Enzymatic
Other extraction processes are alsoused...
Fish protein hydrolysatesBioactive products
Biomedical materials
Bioplastics Emulsifiers
Cryopreservatives
Nitrogen source for broth media
SUBCRITICAL WATER
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• Across the years subcritical water(SCW) is gaining attention as amethod of valuable materialrecovery.
• Literature shows the efficiency onextracting and/or hydrolyse proteinsand amino acids.
• Overcomes a few drawbacks of thechemical and enzymatic methods.
• It is possible to tailor its properties:
IONIC PRODUCT
DIELECTRIC CONSTANT
Increases the power of the hydrolysis reaction
High solubility of less polar compounds
AT TEMPERATURES ABOVE 100 °C AND AT PRESSURESABOVE THE VAPOUR PRESSURE:
THE BY PRODUCT USED…• Sardine heads (SH) that results fromthe canning industry
• Freeze‐dry and stored at ‐20 ˚C• Comparing the protein extractionbetween a conventional method andthe subcritical water process
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ACIDIC & ALKALINE EXTRACTION
SOLUBLE PROTEIN
SOLUBLE PROTEINS
SOLUBLE PROTEINS
SARDINE HEADS (SH)
MINCED, 1:10 BUFFER/WATER
SUPERNATANT
pH 5.5 (1M HCl/NaOH), 30’
PELLETSUSPEND IN WATER (1:5), HEAT 60’
15’, 5000xg
SUPERNATANTpH 5.5 (1M HCl/NaOH), 30’
pH ADJUSTSTIR, 30’
SUPERNATANT
pH 5.5 (1M HCl/NaOH), 30’
15’, 5000Xg
15’, 5000xg
PELLET
SUSPEND IN BUFFER, ≤0.5 M NaCl
ACIDIC & ALKALINE EXTRACTION
Extraction yield
Extraction yield
pH 2pH 2
15 g protein/ 100 g SH
15 g protein/ 100 g SH
pH 12pH 12
31 g protein/ 100 g SH
31 g protein/ 100 g SH
pH 12, defattedpH 12, defatted
35 g protein/ 100 g SH
35 g protein/ 100 g SHSOLUBLE
PROTEINSOLUBLE PROTEINS
SOLUBLE PROTEINS
SARDINE HEADS (SH)
MINCED, 1:10 BUFFER/WATER
SUPERNATANT
pH 5.5 (1M HCl/NaOH), 30’
PELLETSUSPEND IN WATER (1:5), HEAT 60’
15’, 5000xg
SUPERNATANTpH 5.5 (1M HCl/NaOH), 30’
pH ADJUSTSTIR, 30’
SUPERNATANT
pH 5.5 (1M HCl/NaOH), 30’
15’, 5000Xg
15’, 5000xg
PELLET
SUSPEND IN BUFFER, ≤0.5 M NaCl
SCW EXTRACTION
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water extract collector
SCW Conditions
Flow rate 10 mL/min
Pressure 70 bar
Temperature 20 – 220 ˚C
EXTRACTION YIELDEXTRACTION YIELD
Deionized water (pH 5.5)Deionized
water (pH 5.5)
41 g protein/ 100 g SH
41 g protein/ 100 g SH
Water w/ NaOH (pH 8)Water w/
NaOH (pH 8)
26 g protein/ 100 g SH
26 g protein/ 100 g SH
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0
50
100
150
200
250
0 25 50 75 100 125 150 175 200 225 250 275 300
g protein/
g fish
Temperature
(°C)
Time (min)
Temperature Temperature Deionized water (g protein) pH 8 (g protein)
CONCLUSIONS• Fish residue is a good source of proteins, with a wide range of applications
• Alkaline extraction shows better extraction results than the acidic extraction.
• SCW has similar extraction yields when compared to the conventional alkalineextraction and better than the acidic extraction.
• SCW shows to be very efficient for extracting proteins, having a lowenvironmental impact (when compared to the chemical extraction).
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ACKNOWLEDGEMENTS• My supervisors – Dr. Alexandre Paiva, Steve Bowra and Prof. Pedro Simões
• Phytatec UK Lda for funding
• Associate Laboratory for Green Chemistry LAQV which is financed by national funds from FCT/MEC (UID/QUI/50006/2013) and co‐financed by the ERDF under the PT2020 Partnership Agreement (POCI‐01‐0145‐FEDER ‐ 007265).
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FACULDADE DE CIÊNCIAS E TECNOLOGIAUNIVERISDADE NOVA DE LISBOA
Thank you for your attention
