Optimising Beer Stabilisation by the Selective
Removal of Tannoids and Sensitive Proteins
Kenneth A. Leiper 1, Graham G. Stewart 1,3, Ian P. McKeown 2,
Tony Nock2 and Matthew J. Thompson 1
ABSTRACT
J. Inst. Brew. 111(2), 118–127, 2005
Colloidal stabilisation of all malt and adjunct lager beers through
selective removal of haze sensitive glycoproteins using silica gel
and tannoid polyphenols using polyvinylpolypyrrolidone (PVPP)
or a polyvinylpyrrolidone (PVP)-modified silica gel has been
demonstrated during full brewery production. At this scale PVPP
and the PVP-modified silica gel exhibited equivalent binding
capability for tannoid polyphenols although PVPP removed ad-
ditional polyphenolic species. Characterisation of proanthocyani-
dins following treatment at 4°C with PVPP and the PVP-modi-
fied silica gel silica co-product confirmed that PVPP removes a
wider range of polyphenolics. Both products exhibited poorer
polyphenolic binding capability at 4°C as would be expected for
a physical adsorption process.
Key words: PVP-modified silica gel, PVPP, sensitive proteins,
silica gel, stabilisation, tannoids.
INTRODUCTION
Colloidal instability in beer is caused mainly by inter-
actions between polypeptides and polyphenols 17. These
combine to produce visible haze that reduces a product’s
physical shelf life. Reducing the levels of one or both of
the precursors using suitable stabilising treatments will
extend physical stability.
Polypeptides responsible for haze formation originate
mainly from barley, range in size from 10 kD to 30 kD
and are rich in the amino acids proline and glutamic acid 2.
They are heavily glycosylated with glucose and account
for only 3–7% of total beer protein 8. These polypeptides,
known as sensitive proteins, will precipitate with tannic
acid, which provides a means to determine their levels in
beer. Proline sites in these polypeptides bind to silica gel
hydroxyl groups so that haze-forming proteins are selec-
tively adsorbed as foam protein contains little proline and
is thus not affected by silica treatment.
Polyphenols in beer originate from barley and hops.
Their structure is based on phenol (monohydroxylated
1 International
Centre for Brewing and Distilling, Heriot-Watt Uni-
versity, Riccarton, Edinburgh, EH14 4AS, Scotland.
2 Ineos Silicas Ltd, Liverpool Road, Warrington, WA5 1AB, En-
gland.
3 Corresponding author. E-mail: G.G.Stewart@hw.ac.uk
Publication no. G-2005-0718-294
© 2005 The Institute of Brewing & Distilling
118 JOURNAL OF THE INSTITUTE OF BREWING
benzene) and the term “polyphenol” covers all molecules
with two or more phenol rings 3. Beer contains approxi-
mately 100–300 mg/L polyphenol 12 and these can be di-
vided into derivatives of hydrobenzoic and hydroxycin-
namic acids and flavanols and their derivatives 7. The latter
group account for 10% of total beer polyphenols and con-
tain the species related to colloidal instability.
Flavanoids (oligomers of flavanols) all have the same
basic structure of two aromatic rings linked by a three
carbon unit and they are often hydroxylated to varying
degrees and these groups are sometimes glycosylated or
methylated 6. Flavanols found in beer are catechin, epicate-
chin, gallocatechin and epigallocatechin 17 (Fig. 1). These
can exist as monomers but are more commonly joined to
form flavanoids as dimers, trimers or larger polymers.
Polyphenols are lost throughout the brewing process,
particularly during mashing, boiling, wort cooling and
cold conditioning. Flavanoids found in beer consist of
monomers, dimers and a few trimers at a level of approxi-
mately 15 mg/L12. Two dimers have been particularly as-
sociated with haze formation, procyanidin B3 (catechin-
catechin) and prodelphinidin B3 (gallocatechin-catechin),
see Fig. 1. These are known as proanthocyanidins and
come from malt and hops, accounting for only 3.3% of
total beer polyphenols 10. Monomers on their own do not
appear to be involved in haze formation 16.
The exact mechanism by which flavanoids bind to
polypeptides and cause haze is uncertain. It has been pro-
posed that the simple dimeric flavanols are too small to
cause haze on their own and must polymerise into larger
molecules (oligomers) before they are large enough to
cause haze. It is thought that the flavanoids must first be
oxidised before they can form polymers 12. Oxidation can
occur throughout the brewing process, enzymatically dur-
ing mashing or non-enzymatically during boiling.
The number and position of hydroxyl (OH) groups on
the flavanoids’ aromatic rings influence protein binding.
Thus rings with only one OH group are almost inactive
whereas those with two OH groups are more active, espe-
cially when they are adjacent (vicinal), and rings with
three OH groups are even more active 15. Thus prodelphi-
nidin B3 is more haze active than procyanidin B3 as gal-
locatechin has three vicinal OH groups while catechin has
two (Fig. 1).
Chapon 5 refers to haze active polyphenols as “tan-
noids”. These are likely to be similar to the polymeric
proanthocyanidins described above. Tannoids convert to
“tannins” which are able to form haze and these are likely
 Fig. 1. Structures of the main beer flavanol monomers and dimers 17.
Table I. Forced ageing regimes used at the breweries.
Brewery Procedure
A 6 cycles at 60°C for 48 h + 24 h at 0°C
B 6 days at 60°C + 24 h at 0°C
C 2 cycles at 60°C for 48 h + 16 h at 0°C
D 5 days at 60°C + 24 h at 0°C
E 5 days at 57°C + 48 h at 0°C
to include the flavanoid oligomers 9. Chapon 5 defines tan-
noids as polyphenols that precipitate with PVP (polyvinyl-
pyrrolidone). Measurement of the haze resulting from this
interaction is a useful way of measuring the amount of
haze active polyphenol in beer, this is the basis of the tan-
noids assay.
As a beer ages, the first stage of colloidal instability
can be the formation of a chill haze. This forms when beer
is cooled to below 0°C, but will disappear if the beer is
warmed. Chill haze is formed when polypeptides and
polyphenols are bound non-covalently 18. Permanent haze
forms in the same manner initially, but covalent bonds
soon form and insoluble complexes are created which will
not dissolve when heated. Mechanisms of haze formation
have been proposed by Chapon 5, Siebert et al.18 and Reh-
manji et al.14
Removal of haze forming tannoids can be effected us-
ing PVPP. However, recently an alternative product, a
PVP-modified silica gel, has been developed. This con-
sists of amorphous silica coated with PVP which is
strongly attached by hydrogen bonding. Unlike PVPP, it
does not require to be pre-swelled. The surface chemistry
of both these adsorbents and functional groups on the
haze forming tannoids assure selective adsorption of the
haze forming fractions.
PVPP and PVP-modified silica gel adsorption sites
comprise the carbonyl groups of polyvinylpyrrolidone.
These sites interact with hydroxyl groups on the poly-
phenol molecule. The relative number of hydroxyl groups
Desired results
Haze at 0°C must be less than 2.5 EBC for 6 cycles
Haze at 0°C must be less than 2.0 EBC
Haze at 0°C must be less than 2.0 EBC
Haze at 0°C must be less than 3.5 EBC
Haze at 0°C must be less than 2.0 EBC
in the polyphenol molecule and the number of accessible
adsorption sites on PVPP or PVP-modified silica gel de-
termines selectivity by competitive adsorption. Thus poly-
phenols having high numbers of hydroxyls adsorb most
readily and most strongly. Rehmanji et al.14 reported PVPP
is most efficient at lower dosages because at these levels it
preferentially adsorbs haze-active (tannoid) polyphenols.
At higher levels, selectivity is poorer as non-haze active
polyphenols are adsorbed.
The PVP-modified silica gel has fewer adsorption sites
than PVPP making it effective in adsorbing only the most
haze-active polyphenols. Because PVPP and PVP-modi-
fied silica gel use the same polymer type to provide ad-
sorption sites, it should not be surprising that they adsorb
essentially the same haze active polyphenols.
To assure colloidal stability, it is not necessary to re-
move all of the sensitive proteins or tannoids. Identifica-
tion of a tolerable level of these can be used to define a
beer composition at bottling that delivers satisfactory haze
stability 4,11,13. Beers can therefore be high in either tan-
noids or sensitive proteins as long as the antagonist is
low. Consequently stabilisation costs can be balanced with
physical stability by using appropriate combinations of
stabilisers to remove sensitive proteins and tannoids.
This paper presents results demonstrating the effective-
ness of this approach to managing stabilisation. Data are
presented from five breweries (A to E) in Western Europe,
Eastern Europe and Asia from full scale brewing produc-
tion in which a PVP-modified silica was substituted for
VOL. 111, NO. 2, 2005 119
Table II. Treatments used at Brewery A.
Maturation At filtration
(g/hL) (g/hL)
Silica Silica PVP-mod. silica
Beer type semihydrogel hydrogel or PVPP
A 75 30
B 20 0 50
C 25 50
D 50 70
E 25 40
PVPP to stabilise all malt and adjunct lagers. The work is
extended by a laboratory study showing the effects of
PVPP and the PVP-modified silica on specific polyphe-
nols. Results show that PVPP and the PVP-modified silica
are effective in removing haze-causing tannoids under
brewing production conditions. At higher temperature
(4°C), PVP-modified silica removes overall less polyphe-
nolic material than PVPP as it has lower binding capacity
for non-tannoid polyphenolics. Results from this study
also show that measurement of tannoids provides a better
indicator of physical stability than the measurement of
total polyphenols.
MATERIALS AND METHODS
Sensitive proteins, tannoids and Chapon haze
These parameters were measured on a Pfeuffer Tan-
nometer according to the methods of Chapon 4.
Total polyphenols
Polyphenols were measured according to the EBC
method 9.11.1
Accelerated ageing
Temperature regimes used in forced ageing varied be-
tween breweries, these are shown in Table I.
Brewery full scale stabilisation
High gravity all malt and adjunct lagers were stabilised
using silica gel during maturation or filtration and either
PVPP or PVP-modified silica gel at the filter. Details of
the loadings used are given in the text or appropriate tables.
Laboratory scale stabilisation
Sales (1050.2 OG) and high gravity (1082.1 OG) all
malt lagers were brewed in the ICBD’s 2 hL pilot brew-
ery. These were treated with PVPP or PVP-modified silica
gel across a range of concentrations at 4°C (the lowest
temperature at which the cold room employed could be
maintained). The adsorbents were removed by centrifuga-
tion for convenience due to the small sample sizes used
and the beers were analysed for total polyphenols, tan-
20 noids and specific polyphenols.
10 Specific polyphenols by HPLC
20
20 Levels of catechin, epicatechin, gallocatechin, epigal-
locatechin, procyanidin B3 and prodelphinidin B3 were
measured by HPLC. Samples were extracted by being
passed through a column containing Sephadex LH20
which had been equilibrated with water. Recovery was
found to be best at 5% alcohol by volume (abv), therefore
high gravity beer samples were diluted. The column was
washed with 12 mL water and 5 mL methanol (30% v/v).
Polyphenols were eluted from the column with 100 mL
acetone :methanol (1:1). Following concentration by ro-
tary evaporation at 35°C, 10 mL saturated ammonium
sulphate was added to the eluate. This was then extracted
with 2 × 15 mL petroleum ether and 4 × 20 mL ethyl ace-
tate before evaporation and re-suspension in methanol
(20% v/v). Samples were run on a Lichrospher RP18 col-
umn (Phenomenex) with protocatechuic acid as an internal
standard. Detection was by a pulsed electrochemical de-
tector (Dionex) set on amperometry using a glassy carbon
electrode.
Saturation curves
Cumulative saturation curves were produced with
PVPP and PVP-modified silica gel for both pilot brewed
lagers. For each treatment, 100 mg of adsorbent was
placed in a 250 mL centrifuge bottle, 200 mL beer was
added and mixed by being placed on an SO3 Orbital
Shaker (Stuart Scientific) at 200 rpm at 4°C, for 10 min.
The bottles were removed and centrifuged at 13,000 rpm
for 15 min. The liquid was decanted and retained. A fur-
ther 200 mL fresh beer was placed in the bottle contain-
ing the adsorbent and the process repeated. It was found
that 20 cycles were required to achieve saturation of the
adsorbents. Supernatants were analysed for tannoids as
described above. The tannoid value for each supernatant
was subtracted from the value for the untreated beer to
give an amount of tannoid taken up during each cycle.
This amount decreased with each cycle as tannoids pro-
gressively occupied adsorption sites. The amount of tan-
noid removed from the beer in each cycle was added to
that of the previous cycles to produce cumulative satu-
rated curves.

Table III. Brewery A beers before and after stabilisation.

Packaged beer
Tannoids
Maturation tank
(mg/L PVP) Tannoids No. of hot cycles
Sensitive protein Tannoids Sensitive protein with PVP-mod. (mg/L PVP) Chapon to 2 EBC
Beer type (EBC) (mg/L PVP) (EBC) silica with PVPP (EBC) (target 6)
A 5.9 33.0 4.3 7.8 7.9 0.7 6
B 9.6 41.2 8.1 6.9 5.9 0.5 6–7
C 6.6 36.4 8.0 19.0 18.1 2.4 3.4–6
D 6.8 15.4 4.1 7.8 10.8 4.3 2.4–4.5
E 8.7 44.9 5.5 4.8 17.2 0.7 6–7

120 JOURNAL OF THE INSTITUTE OF BREWING

Table IV. Brewery B beer before and after stabilisation.
Sensitive Tannoids
protein (mg/L PVP) Chapon
Beer type (EBC) (EBC)
In maturation tank 5.1 28.9 — —
Packaged beer with
PVP-mod. silica 2.2 15.5 0.9
Packaged beer with
PVPP 4.2 15.8 2.7
RESULTS
Brewery scale trials
In Brewery A, five commercial brands of all malt and
rice adjunct lagers were stabilised according to the scheme
shown in Table II. Different combinations of adsorbents
were used to suit the different levels of tannoids and sen-
sitive proteins present in the different brands at matura-
tion. A minimum of six samples were evaluated for each
treatment regime. The results are shown in Table III.
The use of silica semi-hydrogel in the maturation tank
was effective in reducing sensitive protein levels while
having no effect on tannoids. Tannoid levels varied con-
siderably across the brands due to differences in the rela-
tive proportions of malt and adjunct used. Stabilisation at
the filter with silica hydrogel and either PVPP or PVP-
modified silica gel resulted, mostly, in low Chapon chill
hazes and good forced ageing results. Stability was as-
sured by having sufficiently low concentrations of sensi-
tive proteins and tannoids.
Brands C and D exhibited poor stability because the
haze precursor concentrations were not sufficiently re-
duced. Brand C was too high in tannoids and would benefit
from increased PVP-modified silica gel or PVPP stabili-
sation, or increased silica stabilisation. Also, whichever
option is selected might be influenced by cost. Brand D
was a high alcohol lager and unstable despite the sensitive
protein and tannoids levels being about the same as those
in Brand A. This is because higher alcohol content in final
beer reduces colloidal stability, therefore requiring in-
creased silica and PVP-modified silica gel or PVPP sta-
bilisation.
In Brewery B, a premium all malt lager was stabilised
using silica hydrogel in cold storage at 20 g/hL and PVP-
modified silica gel or PVPP at 20 g/hL at the filter. Sta-
bilisation results are summarised in Table IV. PVP-modi-
fied silica gel and PVPP were effective in lowering the
tannoid concentration although the PVPP-stabilised beer
Forced had poor stability as evidenced by Chapon chill haze and
ageing forced ageing. This instability was due to the beer in ques-
Chapon tion having a higher than expected sensitive protein level
(EBC)
and not due to high tannoids. PVPP was as effective as
PVP-modified silica gel in reducing the concentration of
1.8
the tannoids.
In Brewery C, a premium European lager was stabi-
5.5 lised at the filter with silica xerogel at 40 g/hL and PVP-
modified silica gel or PVPP at 5 g/hL. Results during fil-
tration show the adsorbents’ effectiveness during filtration
(Table V). Silica gel reduced sensitive protein while the
PVP-modified silica or PVPP reduced tannoid levels to
final beer values at between 400 and 700 hL filtered vol-
ume.
Relative to PVPP, the PVP-modified silica gel had little
effect on reducing the concentration of total polyphenols.
As these include both tannoids and non-haze active poly-
phenols, the results suggest that tannoids form a small
fraction of the polyphenols in this beer.
Stability of packaged beers treated with PVP-modified
silica gel taken during the filtration run is shown in Table
VI. The low forced aged haze results show that PVP-
modified silica gel was effective at providing long term
physical stability. PVPP provided equally good physical
stability (data not shown).
In Brewery D, a standard European all malt lager was
stabilised at the filter using silica hydrogel at 35 g/hL and
PVP-modified silica gel or PVPP at 15 g/hL. In cold stor-
age, process differences such as residence time resulted in
differences in sensitive protein and tannoids content be-
tween tanks.
Finished beer stability was assured by reducing sensi-
tive proteins to approximately 5 EBC and tannoids to be-
tween approximately 15 and 27 mg/L PVP (Table VII).
The low Chapon values predict good stability for the beers
stabilised with PVP-modified silica gel and PVPP. The
latter had only a slightly greater impact on total polyphe-
nol levels than PVP-modified silica gel, suggesting a large
proportion of these polyphenols are in the form of tan-
noids.
In Brewery E, an East European lager was stabilised at
the filter with 30 g/hL silica xerogel and 10 g/hL PVP-
modified silica gel or PVPP. Stabilised beer was stored for
six months to provide a measure of real shelf life. Results
show that both PVP-modified silica gel and PVPP gave
good beer physical stability (Table VIII) and that this sta-
bility was predicted and confirmed by both the forced
ageing and Chapon chill haze tests.

Table V. Stabilisation of Brewery C beer during filtration.

Sensitive protein Tannoids Chapon Total polyphenols
(EBC) (mg/L PVP) (EBC) (mg/L)
Volume filtered PVP-mod. PVP-mod. PVP-mod. PVP-mod.
(hL) silica PVPP silica PVPP silica PVPP silica PVPP
200 4.9 10.7 16.1 18.2 0.6 0.8 229 179
400 4.5 7.9 15.7 16.0 0.5 0.1 222 133
700 4.4 5.5 <10 <10 0.2 0.1 225 149
900 5.5 <10 0.1 146
1200 <10 0.1 207

VOL. 111, NO. 2, 2005 121

Table VI. Stability of Brewery C beers taken from various time during tannoids than is PVP-precipitation. Treatment at 50 g/hL
filtration. was required to completely remove catechin, confirming
Sensitive the findings of Siebert 16 that catechin is not particularly
protein Tannoids Chapon Forced ageing haze-active.
Treatment (EBC) (mg/L PVP) (EBC) (EBC)
PVP-modified silica gel had a lower impact than PVPP
1 2.6 <10 0.1 0.7 on polyphenols in the sales gravity beer (Fig. 5) although
2 3.2 <10 0.1 0.6
3 3.0 <10 0.3 0.7
10 g/hL was effective in reducing procyanidin B3 and
4 3.0 <10 0.2 0.7 prodelphinidin B3 levels. As was seen with PVPP, signifi-
5 2.9 <10 0.2 0.6 cant increase in dosing to 40 g/hL was required for further
6 3.3 <10 0.2 0.6 reduction. The findings do not correlate with the tannoid
results (Fig. 2) which showed these were below detection
limits at 30 g/hL. Again, this could be due to these poly-
Laboratory trials phenols not being wholly representative of tannoids.
The effect of PVPP and the PVP-modified silica gel on In the high gravity lager at 10 g/hL, PVPP removed al-
pilot brewed sales gravity (1050.2 OG) all malt beer is most all catechin, epigallocatechin, procyanidin B3 and
shown in Fig. 2. PVPP was more effective in removing prodelphinidin B3 with little additional removal at higher
tannoids than the PVP-modified silica gel, levels being dosing (Fig. 6). PVP-modified silica gel was similarly ef-
below the detection limit in the beers treated at 30 g/hL fective (Fig. 7). As with the sales gravity lager, the find-
or above. Total polyphenols were relatively unaffected by ings do not correspond with the tannoids findings (Fig. 3).
the PVP-modified silica gel but at 30 g/hl or more, PVPP The observed differences between the tannoids mea-
reduced these by approximately 25%. A similar perfor- surements and HPLC analyses might be because the se-
mance was seen in the high gravity (1082.1 OG) beer lected polyphenols do not represent fully “tannoids”, al-
(Fig. 3) but this time the PVP-modified silica was more though Procyanidin B3 and prodelphinidin B3 have been
effective. reported as being actively involved in haze formation 17.
The impact of these stabilisers on specific polyphenols Additionally, the laboratory studies were made at 4°C, a
is shown in Figs. 4 to 7. At sales gravity, 10 g/hL PVPP temperature higher than that used for stabilisation in brew-
removed almost all the epigallocatechin and 30 g/hL sig- eries.
nificantly reduced the levels of procyanidin B3 and pro-
delphinidin B3. This corresponds to the tannoid results of DISCUSSION
Fig. 2, where 30 g/hL reduced tannoids content to below
detectable limits. At up to 50 g/hL polyphenols were still To assure colloidal stability, concentrations of haze
detectable by HPLC. This suggests either that procyanidin forming sensitive proteins and tannoids must be reduced
B3 and prodelphinidin B3 do not wholly represent tan- to levels at which their mutual interactions do not result in
noids, or that HPLC is a more sensitive means to detect precipitation. This can be achieved using appropriate com-

Table VII. Stability of Brewery D beers matured in different vessels.

Maturation Sensitive proteins Tannoids Chapon Total polyphenols
Sample sources vessel no. (EBC) (mg/L PVP) (EBC) (mg/L)
Maturation 85 12.2 237
85 14.0 51.2 >25
109 14.6 68.7 267
90 10.1 48.0 285
90 11.0 50.5 300
92 56.5 258
Packaged after stabilisation with PVP-mod. silica 109 5.5 21.2 0.1 164
109 5.5 22.1 180
90 4.0 19.2 0.1 173
90 4.0 19.2 0.1 173
90 4.0 19.9 0.2 174
Packaged after stabilisation with PVPP 90 5.7 16.2
90 4.9 16.7
94 5.3 27.0 0.6 168
92 6.2 23.5 0.5 168
92 5.4 14.5 0.5 136

Table VIII. Stability, forced ageing and stability after storage of Brewery E beer.
Six month storage
Sensitive protein Tannoids Chapon Forced ageing Chapon
Beer type (EBC) (mg/L PVP) (EBC) (EBC) (EBC)
In maturation tank 11.0 20.8 — — —
Packaged with PVP-mod. silica 5.0 17.0 0.7 0.4 1.1
Packaged with PVPP 5.2 16.9 0.7 0.4 1.0

122 JOURNAL OF THE INSTITUTE OF BREWING

 Fig. 2. Effects of different loadings of PVPP and PVP-Modified Silica on total polyphenols and
tannoids in sales gravity all malt beer at 4°C.

Fig. 3. Effects of different loadings of PVPP and PVP-Modified Silica on total polyphenols and
tannoids in high gravity all malt beer at 4°C.

binations of silica gel, PVP-modified silica gel or PVPP
adsorbents.
Industrial studies demonstrate that both PVPP and
PVP-modified silica gel are effective in reducing the con-
centration of tannoid polyphenols. Measurement of the
concentration of these, together with sensitive protein and
Chapon haze analysis, serves as a good indicator of forced
age stability. Total polyphenol analysis proves a less use-
ful predictor unless tannoid polyphenols form a signifi-
cant proportion of these.
It is well known a number of factors affect adsorption
processes and that temperature is significant, thus:

VOL. 111, NO. 2, 2005 123

 Fig. 4. Effect of PVPP on levels of haze-active polyphenols in sales gravity all malt beer at 4°C.

Fig. 5. Effect of PVP-Modified Silica on levels of haze-active polyphenols in sales gravity all malt beer at 4°C.

C, t, N , M t = contact time of the adsorbent (in tank or at the fil-

Adsorption ∝ ter)
T
Where N = number of accessible adsorption sites at the ad-
C = Concentration of adsorbate (sensitive protein, tan- sorbent surface (silica, PVP-modified silica gel or
noids) PVPP)

124 JOURNAL OF THE INSTITUTE OF BREWING

 Fig. 6. Effect of PVPP on levels of haze-active polyphenols in high gravity all malt beer at 4°C.

Fig. 7. Effect of PVP-Modified Silica on levels of haze-active polyphenols in high gravity all malt beer at 4°C.

M = mass of adsorbent
T = temperature at which the adsorption process takes
place.
High concentrations of sensitive proteins or tannoids,
long contact time, high numbers of accessible adsorption
sites and high mass of adsorbent lead to increased adsorp-
tion. High temperature reduces adsorption.
The PVP-modified silica gel has fewer adsorption sites
than PVPP. This is because less polyvinylpyrrollidone
polymer is used in its production. Industrial studies dem-
onstrate however that the adsorbent carries sufficient sites

VOL. 111, NO. 2, 2005 125

Fig. 8. Cumulative tannoid adsorption from all malt beers at 4°C.
to reduce tannoid concentration to levels that assure sta-
bility at the concentration of sensitive proteins present in
the final beer.
Considering laboratory studies at 4°C, the cumulative
saturation curves shown in Fig. 8 show that adsorption of
tannoids by PVP-modified silica gel and PVPP follows a
type I isotherm. This has also been demonstrated for sen-
sitive protein adsorption by silica gel 8. Initial adsorption is
high, as both the tannoid concentration and number of
adsorption sites are high. As the tannoids concentration is
reduced and adsorption sites filled, the thermodynamic
and statistical drivers to adsorption are reduced and a pla-
teau is reached. The adsorption plateau is generally higher
in the high gravity beers as the higher concentration of
tannoids makes the thermodynamic driver higher than that
at sales gravity.
In general, at 4°C, the carrying capacities of PVP-
modified silica gel and PVPP are the same in high gravity
beers, in agreement with findings from industrial scale
studies at lower temperatures. At sales gravity PVP-modi-
fied silica gel has a lower plateau than PVPP as the high
temperature reduces the tendency for adsorption and high-
lights the difference in the number of adsorption sites be-
tween the adsorbents. Application of PVPP or PVP-modi-
fied silica gel at normal brewery operational conditions
serves to assure stability. If temperature is allowed to rise,
both lose efficiency and physical stability is not assured.
Because the PVP-modified silica gel and PVPP are
based on the same polymer technology (PVP), it should
not be surprising that these remove the same haze-forming
polyphenols. Fewer adsorption sites on the PVP-modified
silica gel means that only the most haze active tannoid
polyphenols are adsorbed. Thus, the product would not be
126 JOURNAL OF THE INSTITUTE OF BREWING
expected to interact strongly with non-haze active poly-
phenols which is the situation being reported here.
CONCLUSIONS
Both brewery-scale and laboratory-scale studies show
that PVPP and PVP-modified silica gel are effective tan-
noid adsorbents that, combined with silica gel stabilisa-
tion, assure long term beer physical stability. Because the
PVP-modified silica gel has fewer (carbonyl) binding sites
than PVPP it generally has little impact on total poly-
phenol levels, interacting only with the most haze active
polyphenols to assure stability.
The studies demonstrate that measurement of tannoid
polyphenols concentration provides a more useful indi-
cator of forced age stability than does measurement of
total polyphenols. Proper selection of stabilizer products,
loading levels, temperature, treatment locations and ap-
propriate laboratory analyses serves to assure the quality
of beer over its desired shelf life.
ACKNOWLEDGEMENTS
The authors would like to thank Graham McKernan for assis-
tance in the pilot brewery and Jim MacKinlay for assistance
with the HPLC analysis.
REFERENCES
1. Analytica EBC, European Brewery Convention, Verlag Hans
Carl Getranke-Fachverlag, 1998.
2. Asano, K., Shinagawa, K. and Hasimoto, N., Characterization
of haze-forming proteins of beer and their roles in chill haze
 formation. Journal of the American Society of Brewing Chem-
ists, 1982, 40, 147–154.
3. Bamforth, C.W., Beer haze. Journal of the American Society of
Brewing Chemists, 1999, 57, 81–90.
4. Chapon, L., Nephelometry as a method for studying the rela-
tions between polyphenols and proteins. Journal of the Institute
of Brewing, 1993, 99, 49–56.
5. Chapon, L., The mechanics of beer stabilization. Brewers’
Guardian, 1994, 123, 46–50.
6. Doner, L.W., Becard, G. and Irwin, P.L., Binding of flavonoids
by polyvinylpolypyrrolidone. Journal of Agricultural and Food
Chemistry, 1993, 41, 753–757.
7. Hough, J.H., Briggs, D.E., Stevens, R. and Young, T.W., Malt-
ing and Brewing Science Vol.2, Hopped Wort and Beer. 2nd Ed.
Chapman and Hall: London, 1982.
8. Leiper, K.A., Stewart, G.G. and McKeown, I.P., Beer polypep-
tides and silica gel. Part I. Polypeptides involved in haze forma-
tion. Journal of the Institute of Brewing, 2003, 109, 57–72.
9. McMurrough, I., Colloidal stabilization of beer. Ferment, 1995,
8, 39–45.
10. McMurrough, I. and Baert, T., Identification of proanthocyani-
dins in beer and their direct measurement with a duel electrode
electrochemical detector. Journal of the Institute of Brewing,
1994, 100, 409–416.
11. McMurrough, I., Madigan, D. and Kelly, R.J., Evaluation of rapid
colloidal stabilization with polyvinylpolypyrrolidone (PVPP).
Journal of the American Society of Brewing Chemists, 1997, 55,
38–43.
12. McMurrough, I. and O’Rourke, T., New insight into the mecha-
nism of achieving colloidal stability. Technical Quarterly of the
Master Brewers Association of the Americas, 1997, 34, 271–277.
13. Moll, M., Colloidal stability of beer. In: Brewing Science,
J.R.A. Pollock, Ed. Academic Press: London, 1987, pp. 1–327.
14. Rehmanji, M., Mola, A., Narayanan, K. and Ianniello, R., Poly-
clar (PVPP) for improving shelf life in laboratory treated lagers.
Technical Quarterly of the Master Brewers Association of the
Americas, 1998, 35, 95–100.
15. Siebert, K.J., Beer clarity stability. Proceedings of the 6th Con-
vention of The Institute of Brewing (Commonwealth & South
Africa Section), Durban, 1997, pp. 67–78.
16. Siebert, K.J., Effects of protein-polyphenol interactions on bev-
erage haze, stabilization, and analysis. Journal of Agricultural
and Food Chemistry, 1999, 47, 353–362.
17. Siebert, K.J. and Lynn, P.Y., Comparison of polyphenol inter-
actions with polyvinylpolypyrrolidone and haze-active protein.
Journal of the American Society of Brewing Chemists, 1998, 56,
24–31.
18. Siebert, K.J., Troukhanova, N.V. and Lynn, P.Y., Nature of poly-
phenol-protein interactions. Journal of Agricultural and Food
Chemistry, 1996, 44, 80–85.
(Manuscript accepted for publication June 2005)
VOL. 111, NO. 2, 2005 127