6.marine Commodities

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INTRODUCTION

• Fish  aquatic vertebrates that are typically


ectothermic (cold-blooded), and equipped
with two sets of paired fins and several
unpaired fins.
INTRODUCTION
• Fisheries  16% of the world population’s
protein
• The flesh  the most valuable part as food
• Fish, shellfish, crustaceans, sea cucumber,
seaweed
EDIBLE FISH SPECIES
SHELLFISH

MUSSEL
CRUSTACEANS
SEACUCUMBER
SEAWEED
INTRODUCTION
• Seafood products from various tissues:
– Muscle
– Roe
Gas bladder
– Stomach
– Kidney Intestine
Liver
– Liver Roe
– Skin Stomach

– Fins Duodenum
CHEMICAL COMPOSITION
• Varies greatly from species to species,
depends on:
– Age
– Sex
– Environment
– Season
• Variations are closely related to the feed
intake
• Lipid  show the greatest variation
CHEMICAL COMPOSITION

Herring (Clupea harengus) Mackerel fillets (Scomber scombrus)


CHEMICAL COMPOSITION
• Water
• Protein
• Fat
• Minor Composition
– Carbohydrate
– Minerals
– Vitamins
– Extractives
CHEMICAL COMPOSITION
Constituents Fish (fillet) Beef
Min Normal Max (isolated muscle)
variation
Protein 6 16 – 21 28 20
Lipid 0.1 0.2 – 25 67 3
Carbohydrate < 0.5 1
Ash 0.4 1.2 – 1.5 1.5 1
Water 28 66 – 81 96 75
PROTEIN & OTHER NITROGEN
COMPOUNDS
• Muscle tissue proteins + NPN
• Muscle proteins:
– Sarcoplasmic (water soluble)
– Myofibrillar (salt soluble)
– Stroma (insoluble in water & salt)
• NPN:
– Amino acids, peptides, amines, trimethylamine
oxide
• Protein + NPN = “crude protein”
Sarcoplasmic protein
• Water soluble
• 18-20% of total muscle protein
• Enzymes + oxygen carriers + heme proteins (myoglobin
& hemoglobin)
• Can be used for species identification
• Most are coagulated when heated above 50oC
• Have an adverse effect on the strength & deformability
of myofibril protein gels
• Interfere with myosin cross-linking during gel matrix
formation  do not form gels & poor WHC
MYOFIBRILLAR protein
• Compose of actin & myosin  responsible in the
contraction-relaxation cycle
• 60-80% of the total protein
• Proportion of myrofibril:total muscle protein is
higher than in land animals
• Myosin (thick filaments)
• Paramyosin (central core of thick filaments)
• Actin (thin filaments)
• Tropomyosin
• Troponin
STROMA
• Insoluble matter remaining after removing
sarcoplasmic & myofibrillar proteins
• Two major type of connective tissue:
– Collagen
– Elastin
NON-PROTEIN NITROGENOUS
COMPOUNDS
• NPN content in seafood is higher than in
other food myosystems
• The importance of these compounds:
– Influence the unique, delicate taste of seafood
– Contribute to the spoilage of fishery products
• Free amino acids, peptides, nuceotides,
guanidino compounds (cp etc), urea &
quarternary ammonium compounds
LIPIDS
• LIPIDS
– Depot fat
– Phospholipid
– Cholesterol
DEPOT FAT
• Depot fat  If lipid content exceed 1% it function as
an energy
• Fish lipid usually in liquid form
• Consist of long-chain fatty acids which are highly
unsaturated
• Mammalian fat rarely contain more than two double
bond per fatty acids while fish contain many fatty
acids with five or six double bonds
• “dark” muscle fish (mackerel) usually higher in
triglyceride than “white” muscle fish
DEPOT FAT
• The total number of PUFA with 4, 5 or 6
double bonds is slightly lower in freshwater
than marine fish
• Linoleic & linolenic are essential for human,
but constitute only 2% from total lipid
• Ω-3  member of linolenic acid,  growth-
promoting in children
PHOSPHOLIPIDS
• A small portion of lipids (< 1% of fish muscle) serves
as essential structural parts of cell
• “non-depot lipids” = phospholipids (phosphorus-
nitrogen-containing fat)
• Not function as energy reserve
• Distributed unevenly in the tissues
• “dark” muscle rich in these compounds
• Also contain PUFA with 5 or 6 double bonds
CHOLESTEROL
• Main sterol in fish muscle
• Usually under 100 mg/ 100 g
• Not much higher than in mammalian tissue
SHELLFISH & OTHER
INVERTEBRATES -LIPIDS
• Lipid in all shellfish food = 1 – 2 %
• Low – not store energy as fat depot, but in glycogen
(bivalves) or in digestive glands (squid)
• Most molluscs = 20 – 40 mg 100 g-1 fresh meats are
actual cholesterol
• Octopus = 48 mg cholesterol / 100 g
• Squid = 233 mg cholesterol / 100 g
• Crab = 100 mg cholesterol / 100 g
• Crustaceans = 0.1 – 0.2 g cholesterol / 100 g
VITAMINS & MINERALS
• Vitamins & minerals  species-specific & vary
with season
• Fish meat  good source of B vitamins & in
fatty species, also A & D vitamins
• Saltwater  high content of iodine
CHANGES IN RAW FISH
• RIGOR MORTIS
• AUTOLYSIS CHANGES
• FAT OXIDATION

• AFTER CATCH;
– Drop in degree of freshness
– Drop in consumer acceptance
– Drop in commercial value
CHANGES IN RAW FISH
• Appearance, odour, texture & taste
• During storage  Q concerned are
appearance & texture
• Taste  developed the first couple of days
during storage in ice
• Immediately after death, muscle are totally
relaxed
• Fish is soft & pliable + texture is firm & elastic
to the touch.
CHANGES IN RAW FISH
• After some time, the muscle tissue contract &
becomes hard & stiff  & the whole body
becomes inflexible
• This condition usually lasts for a day or more
then rigor resolves.
• If filleted pre-rigor  muscle contract freely &
shorten & have a wrinkled surface
• Dark muscle shrink up to 52% & white muscle up
to 15%
CHANGES IN RAW FISH
Immediately after
DEATH After A DAY or MORE

Muscle RELAXED & LIMP Rigor resolves


ELASTIC TEXTURE (persist
for some hours) Muscle RELAX again &
becomes LIMP but
After a few hours NOT ELASTIC

Muscle CONTRACT

STIFF & whole body


INFLEXIBLE (RIGOR MORTIS)
CHANGES IN RAW FISH
• The rate of onset & resolution of rigor is
affected by:
– Species
– Temperature
– Catching method
– Handling
– Size
– Physical condition of the fish
Species Condition Temperature Time from Time from
death to the death to the
onset of end of rigor
rigor (hours) (hours)
Cod (Gadus Trawled 0 2–8 20 – 65
morhua) Trawled 10 – 12 1 20 – 30
Trawled 30 0.5 1–2
Rested 0 14 – 15 72 – 96

Grouper Rested 2 2 18
(Epinephelus
malabaricus)

Tilapia (T.
mossambica) Rested 0–2 2–9 26.5
CHANGES IN RAW FISH
• Rigor mortis  important aspect in filleting industry
• Pre-rigor  shorten fish muscle, & when frozen,
enhanced drip loss  but can give good product if
carefully thawed at low temperature to give rigor
mortis time to pass while the muscle is still frozen
• In rigor  usually good quality, but machine
filleting is more difficult & results in lower yield 
rough handling will also cause gaping
• “In principle”, safer to fillet the fish post-rigor, but it
is not possible as it requires a large chill storage
capacity for the whole fish
Good appearance of “Gaping” appearance
fish muscle of fish muscle
CHANGES IN RAW FISH
• Rigor mortis start immediately if:
– The fish is starved & the glycogen reserves depleted
– Or if the fish is stressed
• Stunning & killing by hypothermia (killed in iced
water)  give the fastest onset of rigor
• A blow on the head  delay rigor up to 18 hours
• If the fish is cooked:
– Pre-rigor  very soft texture & pasty
– In rigor  tough but not dry
– Post-rigor  flesh becomes firm, succulent & elastic
FROZEN WHOLE FISH

advantages disadvantages

frozen • buffer store not •thaw rigor gaping possible


pre- required •high drip loss may occur
rigor • no gaping, except •large processing capacity required to cope
possibly from thaw with high catching rates
rigor

frozen • uniformly good •buffer store required


in rigor quality obtainable •texture variation possible
generally •gaping or broken fillets when fish are forcibly
straightened or rigor temperature is high
•pack less well in freezer
frozen • uniformly good •buffer store required
post- quality obtainable •gaping may occur when held too long or at
rigor generally too high a temperature before freezing
• danger of
contraction damage
avoidable
FROZEN FILLET
advantages disadvantages

frozen pre- buffer store not • large processing capacity required to


rigor required deal with high catching rates
fillets can be • fillets shrink when awaiting freezing
cut by hand or or after thawing
machine • rough cut surface
• particularly unsuitable for smoking
• may be high drip loss

frozen in rigor excellent quality • buffer store required


possible • difficult to fillet by machine or by hand
• less yield from hand filleting
no shrinkage • usually unsuitable for smoking
• bent fish yield gaping fillets

frozen post- uniformly high quality • large buffer store required for up to 3
rigor no shrinkage days
machine or hand • usually unsuitable for smoking
filleting
CHANGES IN EATING
QUALITY
• Phase 1
– Fish is very fresh, sweet, seaweedy & delicate taste.
• Phase 2
– A loss of the characteristic odor & taste.
– Flesh becomes neutral but no off-flavors.
– The texture still pleasant.
• Phase 3
– There is a sign of spoilage and range of volatile, unpleasant-smell is
produced depends on species & type of spoilage (aerobic and
anaerobic).
– The volatile compounds may be trimethylamine (TMA- fishy smell)
derived from bacterial reduction of trimethyl-aminoxide (TMAO)
– At the beginning of “off-flavor” phase may be slightly sour, fruitty &
slightly bitter, especially in fatty fish.
– Later stages  cabbage-like, ammoniacal or sulphurous flavours
• Phase 4
– The fish is spoiled & putrid
Changes in eating quality of iced (0ºC) cod (Huss, 1976)

10 – absolutely fresh, 8 – Good quality, 6 – the neutral


(tasteless) fish, 4 - reject
AUTOLYTIC CHANGES
• Autolytic = “self-digestion”
• Two types of fish spoilage:
– Bacterial
– Enzymatic
• At death of an organism, normal regulation system
stop to function  supply of oxygen & energy stop
• Start new series of process characterized by the
breakdown of glycogen (glycolysis) & the
degradation of energy-rich compounds
Normal pathway for the production of muscle energy
AUTOLYTIC CHANGES
• Normal pathway, glycogen  CO2 + H2O + ATP
• Under anaerobic condition, ATP be
synthesized by two pathways:
– Creatine phosphate
– Arginine phosphate
• Cephalopods  the end product is not acidic
  any changes in post-mortem pH is not
related to lactic acid from glycogen
AUTOLYTIC CHANGES
DEATH
ATP drops, muscle
enter rigor mortis
Glycolysis

Anaerobic – 2 moles
ATP produced
Aerobic – 36 moles
ATP produced

Anaerobic muscle
cannot maintain its
normal level of ATP
AUTOLYTIC CHANGES
Glycolysis Lactic acid produced
depends on glycogen
Accumulation amount
of lactic acid
In fish, the amount of
Lowers the pH of
glycogen is relatively
the muscle
low compared to
mammals
6.8 to U pH 6.1 – 6.5  cod
U pH 5.8 – 6.0  large mackerel U pH Beef  5.1
U pH 5.4 – 5.6  tuna & halibut 
too low, unusual in marine teleost
AUTOLYSIS & NUCLEOTIDE
CATABOLISM
• The softening of the muscle during resolution of rigor
(& eventually spoilage processes) is coincidental with
the autolytic changes  ATP degradation
• ATP  ADP  AMP  IMP  HxR  Hx
• IMP = inosine monophosphate, HxR = inosine, Hx =
hypoxanthine
• The speed of degradation varies between species
• Formula of fish freshness develop from these
autolytic changes
AUTOLYSIS & NUCLEOTIDE
CATABOLISM

• K = freshness index, a relative freshness rating based


primarily on the autolytic changes which take place
during post-mortem storage of the muscle
•  K value,  the freshness level
• Hx = bitter off-flavor of spoiled fish
• IMP = Responsible for the desirable fresh fish flavor
which only present in top quality seafood
Changes in IMP, Ino, and HX in sterile cod fillets at 3°C

Figures indicate the catabolic pathway for the degradation of ATP


through the inosine which is entirely due to autolytic enzymes.
AUTOLYTIC CHANGES INVOLVING
PROTEOLYTIC ENZYMES
• Proteolytic breakdown often related to extensive softening
of the tissue
• “belly-bursting” in pelagic fish (herring & capelin)
• Autolysis accelerate the growth of spoilage bacteria
(caused by availability of low molecular weight of peptides
& AA)
• Bacterial spoilage  decarboxylation of AA  produce
biogenic amines  lower the nutritive value
• Cathepsins (‘acid’ protease) & calpains (“calcium activated
factor” & found in meat, finfish & crustaceans)
AUTOLYTIC CHANGES DURING FROZEN
STORAGE
• The reduction of TMAO is usually due to bacterial action
• But, in some muscle tissue, “an enzyme” is able to breakdown
TMAO into dimethylamine (DMA) & formaldehyde (FA)
• (CH3)3NO  (CH3)2NH + HCHO
• FA  cause muscle tough & loss WHC
• Enzyme = TMAO-ase or TMAO demethylase usually found in
gadoid fish (cod family / cold temperate fishes)
• Before frozen storage, make sure the fish free from organ
tissue such as kidney
• Store at <-30oC can prevent autolytic production of FA
Enzyme(s) Substrate Changes Encountered Prevention/Inhibition

production of lactic acid, pH of fish should be allowed to pass


tissue drops, loss of water- through rigor at temperatures as
glycolytic enzymes glycogen holding capacity in muscle close to 0°C as practically
high temperature rigor may possible
result in gaping pre-rigor stress must be avoided
autolytic loss of fresh fish flavour,
ATP ADP  same as above
enzymes, involved gradual production of 
AMP IMP rough handling or crushing
in nucleotide bitternes with Hx (later
accelerates breakdown
breakdown stages)
softening of tissue making
proteins, rough handling during storage and
cathepsins processing difficult or
peptides discharge
impossible
chymotrypsin,
problem increased with
trypsin, proteins, autolysis of visceral cavity in
freezing/thawing or long- term
carboxy- peptides pelagics (belly- bursting)
chill storage
peptidases
myofibrillar softening, molt-induced removal of calcium thus preventing
calpain
proteins softening in crustaceans activation?
connective tissue degradation related
connective gaping" of fillets
collagenases to time and temperature of chilled
tissue softening
storage
store fish at temperature <= -30°C
formaldehyde-induced
TMAO physical abuse and freezing/thawing
TMAO toughening of frozen
demethylase accelerate formaldehyde-induced
gadoid fish
toughening
BACTERIOLOGICAL CHANGES
• Bacterial flora of live fish – skin, gills and intestine
• Degradation of TMAO
Typical spoilage compounds during spoilage of fresh fish stored
aerobically or packed in ice or at ambient temperature

Specific spoilage organism Typical spoilage compounds

Shewanella putrefaciens  TMA, H2S, CH3SH, (CH3)2S, Hx

Photobacterium phosphoreum TMA, Hx


Pseudomonas spp.  ketones, aldehydes, esters, non-H2S sulphides
Vibrionaceae TMA, H2S
anaerobic spoilers NH3, acetic, butyric and propionic acid
Substrate and off-odour/off-flavour compounds produced by bacteria during
spoilage of fish

Substrate Compounds produced by bacterial action


TMAO TMA
cysteine H2S
methionine CH3SH, (CH3)2S
carbohydrates and lactate acetate, CO2, H2O
inosine, IMP hypoxanthine
amino-acid s (glycine, serine, leucine) esters, ketones, aldehydes
amino-acids, urea NH3
LIPID OXiDATION &
HYDROLYSIS
• Autoxidation = oxygen + unsaturated lipid 
rancidity
• Lipid autolysis = enzymatic hydrolysis  free fatty
acid + glycerol  rancidity
• Autoxidation
– Accelerated by heat, light & several organic & inorganic
substances
• Lipid autolysis
– By microbial or endogenous lipases
– Separates triglycerides into glycerol & FFA
– Minor importance during chilling storage of eviscerated
fish
WHICH IS BEST? PRE RIGOR,
RIGOR OR POST RIGOR?
• There is no simple answer to this question
• Rigor occur before the fish is frozen may affect the
quality in three main ways:
– Toughness & high drip loss in frozen whole fish & fillets
– Gaping in fillets taken from frozen whole fish
– Shrinkage of frozen fillets
• The undesirable effects can be reduced by:
– Keeping the fish cool particularly before it goes into rigor
– Handling it carefully when in rigor
– Freezing fillets taken from pre-rigor fish as soon as they
are cut
INTRODUCTION
• Death  spoilage produce the development of
undesirable flavors, softening of the flesh and losses of
the fluid containing protein and fat.
• Lower T  spoilage retarded  low enough 
spoilage stop
• Rigor mortis  the reaction can be strong if the fish has
not been chilled
• If cut muscle before or during rigor  fillet shrink
• However, in many species, rigor mortis not strong
enough to be significant
INFLUENCE OF

TEMPERATURE
Fish – largely water content of 60-80%
• Freezing – convert most of this water into ice
INFLUENCE OF
TEMPERATURE
• Rapid freezing  at first was unsatisfactory since sudden
cooling could disrupt & tear the muscle tissue
• Water expand during freezing  cell walls burst under
induced pressure
• Smaller ice crystals  little damage  little fluid loss on
thawing
• Slow freezing  formation of large ice crystals  damage the
cell walls  loss fluid when the fish thawed
• However, still not provide full explanation :
– Cell walls are sufficiently elastic to accommodate the larger ice
crystals without excessive damage
– Most water bound to protein in the form of a gel, & little fluid would
be lost even if damage of the above nature did occur
INFLUENCE OF
TEMPERATURE
• Slow freezing  result in an inferior quality product 
mainly due to denaturation of protein
• Some protein fraction changed during freezing  altered
their “native” state  “denaturated”
• Typical freezing point of fish is -1 to -2oC  optimal range
of protein denaturation
• -1 to -5oC (known as critical/ freezing zone) where the
largest part of water become frozen
• Once passing the critical zone, the temperature drops
quickly
• Quick Freezing – reduce temperature from 0 to -5oC in 2 h
or less
• Slow freezing  longer time is spent in this zone of
maximum activity
CHILLING
• Enzymic & microbiological activity  greatly influenced by temperature
• Temperature changes  greater impact on microbial growth
• 0-25oC  microbial activity is greatly important
CHILLING
• Microbial activity  responsible in the
spoilage of fresh fish   store at lower
temperature, extend the shelf life
• Industrial practice  store fish at 0oC
• If at different temperature, the shelf life has
been expressed as Relative Rate of Spoilage
(RRS)
• RRS at toC = keeping time at 0oC
keeping time at toC
CHILLING
  0°C 5°C 10°C
  shelf RRS shelf RRS shelf RRS
life life life
Craba 10.1 1 5.5 1.8 2.6 3.9
Salmonb 11.8 1 8.0 1.5 3.0 3.9
Sea 32.0 1 - - 8.0 4.0
breamc
Packed 14 1 6.0 2.3 3.0 4.7
codd)
RRS = Relative rate of spoilage
Shelf life = days
CHILLING
• Delay before chilling  great importance
• Fish enter rigor at temperature > 17oC 
muscle tissue ruptured (muscle contraction &
weakening of the connective tissue)
• The flakes in the fillets separate  “gaping”
 ruins appearance
• Fish difficult to fillet + WHC 
Fillet yield of gutted cod (delay before chilling)

  Percentage fillet yield


  Iced 1 hour after Iced 6 ½ hour after
catch catch
Yield of fillets 48.4 46.5
Yield after 43.3 40.4
trimming
CHILLING
• Rapid chilling  very crucial for the quality of
fish
• Exposed to sun & wind for 4-6 hours before
chilling  oxidation of lipid  rancidity & off-
flavour
• Direct sunlight & wind  initiate autocatalytic
oxidation  once have been initiated, very
difficult to stop
FISH UTILIZATION
• 72% of total catch human consumption
• 26% remained  fish meal & oil
• From the total of human consumption:
– 31%  eaten fresh
– 35%  frozen
– 16%  processed; cured (dried, salted, smoked)
– 18%  canned
• Thus, 31% consumed within 2 weeks
• 69% preserved for later consumption
• Poor handling technique  lower the quality
– Not enough ice used
– Lack of infrastructure
FISH PROCESS & PRESERVATION
• Drying
• Salting
• Smoking
• Fermentation
• Canning
• Surimi
• Cooking
• Freezing
• Value-add
•Remove water to longer the
shelf-life
•Air drying
•Vacuum drying
•Freeze drying
Fish Salting….

Cutting fish.. Salting fish..


-Head, gut & scales -Rub fish with salt
have to be removed and packed into a
large jar or a
barrel

Cooking eel pie


SURIMI
• Originated from Japan, a traditional food
source for centuries
• surimi is “mechanically-deboned fish flesh
that is washed with water and mixed with
cryoprotectants for good frozen shelf life”
• Surimi is produced from low value white
flesh fish, with a typical yield of 25-28% of
the body weight of the fish
Nature of muscle proteins
• Two main types, dark & white depending on
the life-cycle of the species concerned
• Strong swimming species –tuna & mackerel
 larger portion of dark muscle,higher
content of haem pigments (myoglobin) &
non structural lipids
• Higher lipids & metabolites – effect flavour &
colour of surimi
Sarcoplasmic protein
• water soluble  did not contribute to gel
formation & usually removed by leaching
process
• 18-20% of total muscle protein
• enzymes + oxygen carriers + heme proteins
(myoglobin & hemoglobin)
• Protease  attack muscle protein resulting
in a mushy, rather than firm gel texture.
Myofibrillar Proteins
• 65-80% of total protein, give the muscle its fibre-
like structure & muscular activity
• Myosin & actin are soluble in mild salt (NaCl)
solutions (1-8%), but are largely insoluble in water
of lower ionic strength (~0.05 to ~0.5%)
• important for gel formation, recovery,
concentration & protection of these proteins is very
important in surimi production
Stroma
• The connective tissue, primarily collagen
• Totally insoluble in water or saline
• Collagen can convert to gelatin when heated,
depending on the structure of the collagen
present
• 3-5% of total protein
LIPID Components

• Small percentage of membrane phospholipids


in fish muscle  difficult to remove by
washing
• Phospholipid
– Highly unsaturated, often in contact with muscle
heme iron   very easy to oxidize
• Oxidation  causes off-flavour & may hasten
denaturation of the myofibrillar protein
Surimi-Based Products
• Surimi-based products are made possible because of gel
formation due to the presence of actin & myosin
• When heated at moderate temperatures  the protein
react to form actomyosin gel
• According to Japanese, a good, resilient, texture is called
“ashi”.
• Added colours & flavours  allows the creation of many
different products
• Kamaboko (referred to steamed products), tempura (fried
products), chikuwa (broiled products)  all these cooked
& seasoned products also called “neriseihin” in Japan
Quality of Surimi
• Japanese set strict standards;
– Colour / blandness of flavour (affected by impurities)
– Gel formation (actin & myosin properties)
• Other test;
– pH & moisture
– Drip loss & viscosity
• The gel quality so measured with reflect:
– The quality of raw material
– The effect of washing cycles in concentrating the actin and
myosin
– Any changes brought about by frozen storage
Skin products…

Shark skin

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