Gellan gum: an alternative to

carrageenan in heat-processed
petfood products?
(Rowena) Jane Newton

Supervisors: Dr C Speirs (Masterfoods)
Dr S Hill and Dr C Dodd (University of Nottingham)
Gellan : the vision

Manufacture
of gelled
petfoods
In-house
fermentation
process to
produce semi-
refined gellan
Direct supply to
the factory,
eliminating need
to buy seaweed
from Far East
Result: control of gelling agent supply and cost savings
Project objectives

To show that gelled petfood can be made from
gellan gum
To determine if this has any advantages over
carrageenan mixed gels

To produce gellan by fermentation
Development of downstream processing of
fermentation broth to give a crude material for
direct use in petfood products
Work carried out so far

Use of commercial gellan to study:
Viscosity properties
Gelling properties
Different pHs
Effect of different cations and anions

Fermentation behaviour in 1l culture vessel
Choice of starting culture
Today will talk on:
Overview

History of gellan gum
Properties
Benefits
Could gellan work as a replacement for
carrageenan?

Gellan: discovery

Discovered 1981
Search for environmental microorganism which
could make an exopolysaccharide resembling
agar
Found a strain of P. elodea (now called S.
paucimobilis) growing on plants collected in
Pennsylvania
Developed by Kelco
Gellan: how they grew it

Kang et al (1982). Appl. Env. Micro. 43 (5), 1086-
1091.
Grew bacteria on a medium containing 30g/l
glucose, K
2
HPO
4
, MgSO
4
and soy protein isolate
as a nitrogen source
Also added a solution of salts to provide
necessary metals
Grown at 30
O
C in a 30 litre fermentor at pH6.5 for
3 days
After this time, the fermentation broth was
treated to precipitate any polysaccharide present:
Gellan: how they collected it

Boiling
waterbath,
10mins
Then: native or
deacetylated?
native
3 volumes
ice cold
isopropanol
, overnight
Dry to constant weight at
80
O
C
deacetylated
adjust pH to 10
Heat to 90
O
C, 15
mins
Lower pH to 7
Gellan: how they analysed it

Use of Brookfield to measure fermentation liquor
viscosity
GC for analysis of sugars
Heating gum in presence of cations and
performing texture analysis
Using the gum to try and solidify microbiological
media
Gellan: the findings
Contains glucose, rhamnose and glucoronic acid.
Later shown to be present in a 2: 1: 1 ratio;
-Glucose- -glucoronic acid- -glucose- -rhamnose-
Gellan: the findings

One of the glucose residues carries substitutions.
Either a glycerate group (occurring every repeat
unit) or an acetate group (occurring once in every 2
repeat units)
Treatment with alkali removes the substitutions
and creates a more brittle gel
Fermentation process is over in ~50 hours, and at
this point the liquor has a viscosity of 4,000-
8,000cP
Gum can withstand several cycles of autoclaving.
Addition of cations produces stronger gels. These
could be mono- or divalent.

Gellan: desirable properties

Taken from Sanderson and Clark (1984). Gellan
gum, a new gelling polysaccharide. In Gums and
Stabilisers for the Food Industry 2.
Can be used at considerably lower levels than
most other gelling polysaccharides
Can be used in the high acyl form to give viscous
solutions and in the presence of salts to give
somewhat elastic thermoreversible gels
Can be cooled in the presence of cations in the
low acetyl form to give brittle gels
Can combine the two forms to modify texture
Gellan: desirable properties
Gellan: desirable properties

Low acetyl gellan can function in many protein-
based foods, including acidified milk products
Can be used in the deacetylated form to solidify
bacteriological media at 25% of the level of agar
used
Has applications in a variety of products
including: confectionery (jellies,fillings), jams,
processed vegetables, dessert gels, instant
puddings, icings, dairy-based desserts and drinks
PETFOOD

Gellan and petfoods

Currently all CIL and CIJ products gelled with
kappa carrageenan in synergy with other gums,
such as LBG, cassia, konjac
Synergists are interchangeable, but there is
nothing to replace carrageenan at present
Carrageenan is a seaweed; its seasonal
availability changes
It is expensive due to an ongoing seaweed
shortage
Real need to find an alternative to carrageenan
Gellan is the alternative.
Gellan and petfoods

Gellan is currently commercially available from
Kelco
Due to its high level of purification, it is costly
Project aims to therefore develop a semi-refined
grade of gellan gum
Idea is to cultivate this material in-house to
maintain control over the gum supply, and not to
depend on buying carrageenan from the Far East.
Making petfood jelly with gellan

Needs to function in a phosphate buffered
system at low pH, and in the presence of meat
Must also be resistant to the sterilisation
process
Must perform better than carrageenan under
similar conditions, in terms of gel texture
Have performed studies using low acetyl gellan
Currently products cannot be made below pH 6.0
because of carrageenan degradation. Will gellan
work at lower pH?
Making petfood jelly with gellan

The best way to measure gel strength is by
texture analysis
Look at the force required to break a gel by
penetrating it with a probe
Plot force applied versus distance of penetration
Usually produces an initial peak of force, which
is the point at which the gel breaks:
Making petfood jelly with gellan
Force/g
Distance/mm
Force at first fracture: force
required to break the gel. The
higher the force, the harder the
gel.
The influence of pH and salt on non-
autoclaved aqueous gellan gels
Making petfood jelly with gellan

The more acid
the environment
in the absence of
added salts, the
stronger the low
acetyl gellan gel
in an
unprocessed gel
Related to how
the glucoronic
acid reacts to the
changes in pH:
The effect of pH on force at first
fracture of 1% gellan gels
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
0.00 5.00 10.00 15.00
pH
f
o
r
c
e

a
t

f
i
r
s
t

f
r
a
c
t
u
r
e
/
g
1% gellan
fit
Making petfood jelly with gellan
The presence
of additional
salts can also
have an impact
on the gel
strength
For example,
increasing
amounts of
NaCl will
increase the
strength of an
unprocessed
1% gellan gel:
The effect of NaCl on gellan gel breakstrength
0
500
1000
1500
2000
2500
0.00 50.00 100.00 150.00 200.00 250.00 300.00
NaCl molarity/mM
f
o
r
c
e

a
t

1
s
t

f
r
a
c
t
u
r
e
/
g
0.5% gellan
1.0% gellan
1.5% gellan
Making petfood jelly with gellan
But in petfood we have:
Harsh process
Complex system containing meats
Buffer system based around phosphates and
containing a mixture of salts
How does gellan behave as compared to carrageenan
in these circumstances?
Making petfood jelly with gellan
Have made gellan and carrageenan gels in a petfood
type buffer (Na phosphate for gellan, K for
carrageenan but containing equal numbers of moles
of salt)
Have processed the gels at 121
O
C for 15 minutes in
cans
Have subjected the gels to texture analysis
Can compare the forces at first fracture at each
concentration of gum
Have studied two pH levels:5.5 and 6.5
Petfood gels at pH5.5
At every concentration, gellan forms a stronger gel than
carrageenan:
Average force at first fracture versus polysaccharide
concentration of gellan and carrageenan gels (made up in
pH5.5 buffer, processed at 121
O
C for 15 mins)
0.00
200.00
400.00
600.00
800.00
1000.00
1200.00
1400.00
gel composition
a
v
e
r
a
g
e

f
o
r
c
e

a
t

f
i
r
s
t

f
r
a
c
t
u
r
e
/
g
0.3% gellan
0.3% carrageenan
0.45% gellan
0.45% carrageenan
0.6% gellan
0.6% carrageenan
Petfood gels at pH6.5
The same is true at pH6.5:
Average force at first fracture of polysaccharide gels in
relation to polysaccharide concentration (made up in pH6.5
buffer, and processed at 121
O
C for 15 minutes)
0.00
100.00
200.00
300.00
400.00
500.00
600.00
700.00
800.00
900.00
gel composition
a
v
e
r
a
g
e

f
o
r
c
e

a
t

f
i
r
s
t

f
r
a
c
t
u
r
e
/
g
0.3% gellan
0.3% carrageenan
0.45% gellan
0.45% carrageenan
0.6% gellan
0.6% carrageenan
Petfood gels :more texture analysis
As well as giving info on gel strength, texture
analysis graphs tell us about whether a gel is brittle or
elastic
If a gel is brittle, it breaks quickly. The initial
force/distance gradient is high
If elastic, it takes a greater penetration distance to
break. The initial slope is much lower:
Force/g
Distance/mm
Brittle
Elastic
Petfood gels :more texture analysis
The data from before can be re-plotted to show the
initial force/distance gradients, which show us that:
Gellan survives processing and can gel in a petfood
buffer system
Gellan gels are much more brittle than carrageenan
gels
At the same concentration, gellan is stronger at the
more acid pH than carrageenan. The difference
between the gels strengths is more pronounced at
pH5.5
Petfood gels :pH5.5
Changes in the average initial force/distance gradient when
gels are made up at different polysaccharide concentrations
in petfood buffer pH5.5 (processed at 121
O
C for 15mins)
0.00
50.00
100.00
150.00
200.00
250.00
300.00
350.00
400.00
450.00
gel composition
a
v
e
r
a
g
e

i
n
i
t
i
a
l

f
o
r
c
e
/
d
i
s
t
a
n
c
e

g
r
a
d
i
e
n
t

(
g
/
m
m
)
0.3%gellan
0.3% carrageenan
0.45% gellan
0.45% carrageenan
0.6% gellan
0.6% carrageenan
Petfood gels :pH6.5
Changes in average initial force/distance gradient when
gels are made up at different polysaccharide concentrations
in petfood buffer pH 6.5
0.00
50.00
100.00
150.00
200.00
250.00
300.00
gel composition
a
v
e
r
a
g
e

i
n
i
t
i
a
l

f
o
r
c
e
/
d
i
s
t
a
n
c
e

g
r
a
d
i
e
n
t

(
g
/
m
m
)
0.3% gellan
0.3% carrageenan
0.45% gellan
0.45% carrageenan
0.6% gellan
0.6% carrageenan
All force data
A comparison of the average forces at first fracture of
polysaccharide gels made up in phosphate petfood buffer
at pH5.5 or 6.5 and processed at 121
O
C for 15 minutes
0
200
400
600
800
1000
1200
1400
gel composition
a
v
e
r
a
g
e

f
o
r
c
e

a
t

f
i
r
s
t

f
r
a
c
t
u
r
e
/
g
0.3% gellan Ph5.5
0.3% gellan Ph6.5
0.3% carrageenan
Ph5.5
0.3% carrageenan
pH6.5
0.45% gellan Ph5.5
0.45% gellan Ph6.5
0.45% carrageenan
Ph5.5
0.45% carrageenan
Ph6.5
0.6% gellan pH5.5
0.6% gellan pH6.5
0.6% carrageenan
pH5.5
0.6% carrageenan
pH6.5
All gradient data
A comparison of the average initial force/distance gradients
of polysaccharide gels made up in phosphate petfood
buffer at pH5.5 and 6.5 and processed at 121
O
C for 15
minutes
0
50
100
150
200
250
300
350
400
450
gel composition
a
v
e
r
a
g
e

i
n
i
t
i
a
l

f
o
r
c
e
/
d
i
s
t
a
n
c
e

g
r
a
d
i
e
n
t

(
g
/
m
m
)
0.3% gellan Ph5.5
0.3% gellan Ph6.5
0.3% carrageenan Ph5.5
0.3% carrageenan Ph6.5
0.45% gellan Ph5.5
0.45% gellan Ph6.5
0.45% carrageenan Ph5.5
0.45% carrageenan Ph6.5
0.6% gellan ph5.5
0.6% gellan Ph6.5
0.6% carrageenan Ph5.5
0.6% carrageenan Ph6.5
Products made up at pH6.5
Chunks in jelly made up in the appropriate pH6.5 buffer
0.45% gum concentration
Gellan is more brittle, carrageenan is more mushy
Brittleness = BETTER FLAVOUR RELEASE.
Products made up at pH6.5
Gellan jelly
Carrageenan
jelly
Product made up at pH5.5
0.3% gellan forms a
very firm gel
Texture comparison, 0.3% gels
Changes in force with distance of compression of product
0
500
1000
1500
2000
2500
3000
0 2 4 6 8 10 12 14 16 18 20
distance/mm
f
o
r
c
e
/
g
carrageenan Ph5.5
carrageenan Ph6.5
gellan ph6.5
gellan ph5.5
Texture comparison, 0.3% gels
Comparison of the forces at first fracture of petfood
products made up in phosphate buffered polysaccharide
gels
0
500
1000
1500
2000
2500
gel composition
f
o
r
c
e

a
t

f
i
r
s
t

f
r
a
c
t
u
r
e
/
g
0.3% carrageenan Ph5.5
0.3% gellan Ph5.5
0.3% carrageenan Ph6.5
0.3% gellan Ph6.5
Conclusions:

Need to replace carrageenan due to shortages and
problems with supply and cost
Gellan is a good candidate to do this
But commercial gellan is very pure and therefore
expensive
Solution is to grow semi-refined material at the plant
and use it as a carrageenan replacement

Conclusions:

Using a semi-refined grade would resolve cost issues

We would have control over the supply of the main
gelling agent, price and availability

Gellan matches or betters the performance of
carrageenan in canned products

Gellan gels are more brittle than carrageenan gels,
resulting in potentially better flavour release.

What is the lowest possible gellan level producing an
acceptable gelled product?