Journal of the American Society of Brewing Chemists

The Science of Beer

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Beer Haze

Charles W. Bamforth

To cite this article: Charles W. Bamforth (1999) Beer Haze, Journal of the American Society of
Brewing Chemists, 57:3, 81-90

To link to this article: https://doi.org/10.1094/ASBCJ-57-0081

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Beer Haze
Charles W. Bamforth,1 Department of Food Science and Technology, University of California, Davis 95616-8598
ABSTRACT
J. Am. Soc. Brew. Chem. 57(3):81-90, 1999
Several substances can cause haze in beer, but the most frequently en-
countered problem is due to a cross-linking of polyphenol and protein.
These materials probably exist in equilibrium in beer and manifest them-
selves as a haze when the polyphenol polymerizes. The proteins particu-
larly involved in haze are rich in proline. A range of stabilization treat-
ments—of relatively low cost— is available, but the avoidance of haze
problems (which seem to be occurring with increased frequency) de-
mands a holistic approach from the brewer in which all stages from raw
material selection to final processing are geared to achieving prolonged
shelf life.
Keywords: Haze model, Polyphenol, Polypeptide, Prediction, Stabi-
lizer
RESUMEN
Existen diversas substancias capaces de enturbiar la cerveza, pero el
problema que se encuentra más frecuentemente se debe a un entre-
cruzamiento de polifenoles y proteínas. Probablemente estos consti-
tuyentes se encuentran en equilibrio en la cerveza y se manifiestan en
forma de turbiedad cuando los polifenoles polimerizan. Las proteínas
específicamente implicadas en la formación del turbio son ricas en
prolina. Se dispone de una gama de tratamientos para la estabilización de
la cerveza, todos ellos de un costo relativamente pequeño, pero el
soslayar los problemas de turbiedad (que parecen presentarse cada vez de
forma más frecuente) exige que el cervecero aborde el problema
globalmente, de forma que todas las etapas, desde la selección de
materias primas hasta las fases finales del proceso, estén encaminadas a
conseguir la mayor vida útil del producto en el mercado.
The great unsolved mystery in the world of brewing is, surely,
the cause of (and solution to) flavor instability. Most other aspects
of beer quality, including foam stability, color, and initial beer
flavor are, at least for the most part, under control. For many
brewers, haze problems, too, are a thing of the past. Remarkably,
though, some brewers have encountered difficulties in recent
years, despite the proven worth of several palliative treatments
allied to good brewing practice.
There are at least three possible explanations for this situation.
The first is that some companies are forgetting the basics. The
second is that they are trying to take short cuts. The third is that
colloidal instability problems of a different type are being en-
countered.
Types of Haze
In connection with the third explanation, one very real change
in recent years has been the distances over which beers are trans-
ported. Walters et al (102) described the formation of “bits” in
beers which had been subjected to a degree of agitation mimick-
ing that which a beer will encounter when it is shipped and han-
dled. These bits, which contain protein and perhaps pentosans, are
thought to arise as the skins around foam generated within the
package.
1 Corresponding author. Tel: 530 752-1467; Fax: 530 752-4759;
E-mail: cwbamforthgucdavis.edu
Publication no. J-1999-0608-01R.
© 1999 American Society of Brewing Chemists, Inc.
81
These authors are not the first to describe bits in beer (103), and
it is certainly known that unsightly particles may arise through the
interaction of different stabilizing agents in beer, such as a cross-
linking of papain with propylene glycol alginate (PGA) occurring
during pasteurization (52). Indeed, PGA can cross-link with other
proteins in beer, including residual isinglass finings, to throw ge-
latinous precipitates when beer encounters high temperatures.
These precipitates break up into a snowstorm of bits when the
beer is poured.
At the other end of the particle size range are the so-called
“invisible” hazes, which are more accurately (if rather less fre-
quently) called “pseudo-hazes.” These are caused by very small
particles (<0.1 µm) which cause high levels of light scatter when
measured at 90° to incident. At least one cause was found to be
unmodified regions of the starchy endosperm of barley (42), per-
haps manifesting themselves in the form of retrograded α-glucan
(103).
From time to time, visible hazes in beer have been reported as
being due to residual starch (50), pentosans from wheat-derived
adjunct (17), oxalate from calcium-deficient worts (34), β-glucan
from inadequately modified malt (30), carbohydrate and protein
from damaged yeast (51), lubricants from can lids (88), and dead
bacteria from malt (4,99). For the purposes of this article, the
author is not considering the risk of biological hazes arising from
living microbes.
Articles by Glenister (31,32) on how to identify hazes have long
since become bibles for haze classifiers. Buckee (7) has also pub-
lished a description of haze identification procedures, including a
comprehensive listing of the materials that may cause hazes in
beer. Being able to establish the composition of a haze
(remembering that the underlying cause of a haze may be at the
nucleus of the particle rather than in the material which resides on
the surface) is key to rectifying the problem.
However, by far and away the largest clarity risk in beer is the
haze produced from protein and polyphenol. The vast majority of
publications on haze center on this problem and it is likely that a
great many of the recent haze difficulties have been caused by it,
despite this extensive study. This article will focus primarily on
this type of haze.
Protein-Polyphenol Hazes
When a low molecular weight polyphenol cross-links with a
protein through weak interactions such as hydrogen bonds, a “chill
haze” (a haze which forms when beer is chilled to 0°C, but which
returns to solution when the beer is returned to 20°C) is produced.
Particle sizes range from 0.1 to 1.0 µm. Polyphenols, however, are
prone to polymerization and, when they interact with protein after
this process, they form a “permanent haze” (a haze which is present
in beer even at 20°C), with particles between 1 and 10 µm. Both are
obviously a concern; however, in reality, it is chill haze which the
brewer must counter, because it is this which will arise first and
which will go on to develop into permanent haze.
Polymerization of polyphenols is promoted by oxidation. In
part, this may be catalyzed by enzymes such as polyphenol oxi-
dase, sometimes known as laccase, (44) and peroxidase (15), but
polyphenol can react extensively with oxygen during wort boiling,
presumably during the heat-up phase as oxygen concentration at
boiling point will be sensibly zero (76), during which no enzyme
activity can occur. Furthermore, malt enzymes do not survive into
82 / Bamforth, C. W.
finished beer, in which the majority of the take-up of any oxygen
is into polyphenols (76). Kaneda et al (45) remind us that ground-
state oxygen is comparatively unreactive and they invoke reduced
radical forms of oxygen, notably hydroxyl, as being responsible
for haze formation owing to the efficiency with which it oxidizes
polyphenols in beer.
Delcour et al (20) observe that most beers today are packaged
with very low levels of oxygen, yet nonetheless can throw a haze.
They suggest that aldehydes, including acetaldehyde (in their
model studies, they used atypically high concentrations ranging
from 25 to 400 mg/L), can react with polyphenols to form species
which cross-link with proteins.
Clearly, any strategy for dealing with this type of haze must ad-
dress the elimination of haze-active polyphenol or haze-active
protein during the brewing process, or a proportion of both, be-
cause there is a school of thought that maintains that classes of the
polyphenols are beneficial for mouthfeel (48), as antioxidants
countering staling (100), or for their nutritional value (33). Fur-
thermore, as long as there is doubt about whether the haze-form-
ing and foam-forming proteins are different, there will be concern
about the removal of too much protein.
Haze-Active Proteins
As little as 2 mg/L of protein is sufficient to induce a haze of 1
EBC unit (12). Haze intensity is defined by an EBC method (1)
which involves the measurement of light scattering at an angle of
90° to the incident beam, calibrated with a formazin standard. On
the EBC scale, a value of <0.5 is “brilliant,” 0.5–1 is “almost
brilliant,” 1–2 is “very slightly hazy,” 2–4 is “slightly hazy,” and
≥4 is “hazy.” In view of the fact that most beers contain in excess
of 2 g/L of protein, it is apparent that there is vastly more protein
in beer than is needed to form a haze.
Asano and colleagues (2,3) have made the most detailed study
of haze-active proteins. They isolated a series of polypeptide frac-
tions from beer with haze-forming tendencies and concluded that
they were for the most part derived from hordeins and were rela-
tively rich in proline. However, there was not an absolute distinc-
tion. Albumin- and globulin-derived polypeptides also came out
of solution as chill haze, but only after the hordein-derived spe-
cies. Indeed, foam-forming polypeptides progressively came out
of solution as haze, with a commensurate decay in foaming ability
of beer with time. This observation flies in the face of theories
that predict a clear separation between haze-forming and foaming
polypeptides. Adherents to the dogma that haze-active proteins
originate in hordein and foam-active polypeptides in albumins
should also note recent observations that antibodies raised to hor-
deins will cross-react with foaming polypeptides (68).
McMurrough et al (58) isolated four high molecular weight
polypeptide fractions on DEAE-cellulose and found that they dif-
fered greatly in their response to different polyphenols. Generally
speaking, the polyphenols derived from hops caused more pre-
cipitation than did those from malt.
Matsuzawa (67) claims that polypeptides with an isoelectric
point between 3 and 5 are particularly haze-active, and Mussche,
too, claims that haze-potentiating proteins can be clearly differen-
tiated from foaming proteins on the basis of isoelectric point, with
the acid proteins being haze formers and the foaming polypeptides
being basic (70). He furthermore claims that the higher molecular
weight proteins are more prone to throwing hazes.
Outtrup (83,84) cites the high level of proline residues in haze-
forming protein, accepting that it is not simply the amount of
proline in a protein that matters, but also its distribution. He notes
the similarity of the polypeptide polyproline to the stabilizer poly-
vinylpolypyrrolidone (PVPP), which makes it unsurprising that
polyphenols recognize both PVPP and proteins containing rela-
tively high levels of exposed proline. Furthermore, Outtrup notes
the significance of hydrophobic amino acid residues; he believes
that haze particles grow through interactions between these resi-
dues. Hydrophobic character is also key to the foaming properties
of beer polypeptides (94), which might argue for a crossover be-
tween haze- and foam-forming materials. In addition, isinglass
finings (gelatin) contain high proportions of proline residues;
normally, finings are considered to be protein precipitants, but it is
very likely that they also adsorb polyphenols.
Recently, Ishibashi (40) raised antibodies to both foaming
polypeptides and haze. Whereas the antibody raised against
foaming polypeptide was specific to that type of material, the an-
tibody raised against haze cross-reacted both with haze and
foaming polypeptide, suggesting that a broad span of polypeptides
can enter into haze. Ishibashi used the antibodies to show that
both foam and haze polypeptides were lost throughout the brew-
ing process but preferentially during boiling, fermentation, and
filtration. This would not augur well for the prospects of being
able to preferentially eliminate haze proteins. Furthermore, he
claimed a good correlation between the shelf life of a beer and the
level of haze protein measured by an enzyme-linked immunosorb-
ent assay test incorporating the anti-haze antibody.
In summary, at this time there must be some doubt about there
being a clear differentiation between haze- and foam-potentiating
polypeptides in beer. Indeed, it has been claimed that polyphenols
can cross-react with foaming polypeptide to improve head reten-
tion (18), and this would support cross-functionality in the
polypeptide species.
When considering haze, however, it should be reiterated that
materials may accumulate adventitiously on the surfaces of parti-
cles, without in themselves being causative agents of haze forma-
tion.
Haze-Active Polyphenols
There are few more intimidating topics in brewing science than
that of polyphenols; the complexity is immense. Even leaving to
one side the myriad of formulae, we are confronted with a con-
fusing plethora of terminology. Phenolics, as the name indicates,
are based on a backbone of phenol (monohydroxylated benzene).
Phenolic acid includes a carboxyl group (e.g., ferulic acid).
“Polyphenol” includes all molecules containing two or more phe-
nol rings. Thus, the following are all examples of polyphenols:
flavanol, a monomeric species with structures of the type dis-
played by catechin; flavonol, monomeric species with structures
of the type displayed by quercetin, but usually present in hops as
glycosides (i.e., joined to sugar); flavanoid, oligomers of flavanols
(e.g., prodelphinidin B3 and procyanidin B3); proanthocyanidin,
molecules cleavable by acid to form substances which polymerize
in the presence of oxygen to pigments called anthocyanidin
(examples include the flavanoids mentioned above); anthocyano-
gen, an outmoded terminology for proanthocyanidin; tannoid,
polymers of flavanoids which are intermediates on the “growth
route” to tannins; and tannin, polymers of flavanoids of a size
sufficient to precipitate proteins. An illustrative set of formulae
for the various classes is shown in Figure 1.
Bright beer is usually devoid of tannins, but does contain tan-
noids (12). These species, of relatively low molecular weight, co-
exist in beer alongside protein, and Chapon claims that there is a
readily reversible equilibrium between the polyphenols and the
proteins in their free and soluble but bound forms. He observes
that proanthocyanidins are the most active low molecular weight
polyphenols.
The ability of catechin to form a haze is enhanced by its oxida-
tion (82). McMurrough and O’Rourke (65) demonstrated that the
level of flavanoids declines during beer storage, through conver-
sion to tannoids. McMurrough et al (63) showed that monomeric
polyphenols potentiate haze once they have been oxidatively poly-
 Beer Haze / 83

merized. This occurs readily if beer is “punished” by heat (e.g., in of polyphenol extraction during wort separation is a reflection of
a forced-aging regime), even in the absence of oxygen. the varying extents to which oxidation has taken place in mashing
McMurrough concludes that 75% of the haze in untreated beer is and lautering.
formed from already complexed polyphenols, which surely should The polyphenols precipitated during wort boiling are believed
focus more concern on what happens during the brewing process to find their way into hot break by way of adventitious association
than on whether or not excessive levels of monomeric polyphe- with coagulated protein rather than by taking part in the insolubi-
nols survive into beer. lization process (56). In large part, this conclusion hangs on the
McManus (55) claims that, for a polyphenol to participate in the observation that hot break production is unaffected by the mode of
reactions leading to haze formation, at least two hydroxyl groups “hopping” (e.g., tannin-free kettle extracts give the same hot break
on an aromatic ring are required. Flavanoids are readily oxidized formation as “standard” extracts) (23). By contrast, polyphenols
through dihydroxy and trihydroxy aromatic rings to form tanning do have a role to play (probably via their oxidation) in the forma-
complexes (21,29).
Polyphenols in beer arise from both malt and hops. Some
authors have claimed that those from hops have an insignificant
role in protein precipitation (95). Chapon (12) says that this is true
in the context of the quantitative removal of total nitrogen from
beer, but he maintains that the contribution of hop polyphenols is
substantial when judged in protein-sensitivity terms. Delcour et al
(22) claim that malt and hop polyphenols are identical in their
haze potentiating capability. Srogl et al (95) state that hop
polyphenols have little influence during wort boiling as regards
the precipitation of proteins, but rather remain into beer, where
presumably they potentiate haze formation. They observe that
aroma hops deliver more polyphenols pro rata than do bitter hops.
Between 2 and 4% of the dry weight of hops is accounted for by
polyphenols (98). Srogl et al (95) claim that barley polyphenols
are much less extractable into buffer of pH 5.5 than are the hop
polyphenols. As for the barley-derived polyphenols, Bellmer et al
(5) confirm that winter varieties have higher levels than do spring
cultivars.
Hops contain flavonols (57), usually in the form of glycosides,
and they survive into beer (59). McMurrough and Delcour say that
there is no convincing evidence that they have any effect on beer
quality (56). Rather, they observe that it is the monomeric and
oligomeric flavanols that impact quality. Among these are cate-
chin and epicatechin, which exist as monomers and in polymer-
ized forms known as proanthocyanidins. In acidic conditions in
the presence of oxygen, these materials yield anthocyanidins, with
their strong red coloration. These tannin polymers also cross-react
with proteins to form haze.
McMurrough and Delcour (56) briefly summarize the literature
concerning the levels and types of the monomeric and polymeric
flavanols in barley and malt, and conclude that catechin, two
dimers, and four trimers are present. Monomers and dimers, at
least, survive into beer.
Malting probably has an insignificant effect on the levels of the
flavanols. Catechin is more readily extracted into mashes than are
the dimers (56). McMurrough claims that extraction of mono-
meric, dimeric, and trimeric flavanols is greater from single tem-
perature infusion mashes than from programmed mashes (56).
During mashing, too, heat can promote the co-precipitation of
proteins and polyphenols and, at least as importantly, any oxygen
present in the mash can be involved directly (13,15) or indirectly
(69) in the oxidation of polyphenols, primarily through the inter-
mediacy of peroxidases from malt. The effect is an increase in the
polymerization index of the polyphenols, an attendant develop-
ment of red color, and an increased precipitation (16) due to the
conversion of flavanol monomers and dimers to tannins.
McMurrough and Delcour (56) have amply described how the
extraction of monomeric and polymeric flavanols during wort
separation is complex and variable. It appears that total polyphe-
nol extraction mirrors that of other wort constituents (43).
McMurrough et al (60) observed that the highest concentrations of
all flavanols are to be found in the first runnings from a mash.
Conversely, it has been found that tannins are eluted maximally at Fig. 1. A series of phenolics of increasing complexity found in wort and
the end of runoff (47). Perhaps the variation observed in the extent beer.
84 / Bamforth, C. W.
tion of cold break (18). McMurrough et al found that 70% of malt
polyphenols survive boiling and remain in solution, whereas only
20% of hop-derived polyphenols avoid precipitation as break (58).
McMurrough’s lab has been instrumental in identifying the
types of flavanol found in wort and beer (60). In sweet wort, there
is a preponderance of dimers, and some trimers, from malt. After
boiling, there is proportionately more catechin and epicatechin
(which is extracted from hops and by transformation of catechin)
and also of complexed flavanols. Very little change to this distri-
bution occurs during fermentation, though the more polymerized
materials do seem to be lost on cold conditioning (56). The com-
plexed flavanols formed the bulk of the polyphenols in beer, but
did not automatically correlate with haze formation. McMurrough
concludes that it is the low levels of such materials as dimeric
flavanols that are the problem regarding haze (56).
Model for Protein-Polyphenol Interactions
Siebert’s team (92,93) has described a model for protein-
polyphenol interactions (Fig. 2). The model assumes that it is only
proline-containing proteins that interact to form chill haze, with a
fixed number of polyphenol binding sites in toto. Furthermore, it
is assumed that a polyphenol has two (or more) “ends” which can
specifically interact with these binding sites on proteins, thereby
allowing a single polyphenol molecule to bridge between protein
molecules. If there is an excess of haze-active protein over haze-
active polyphenol—as Siebert claims for beer (89)—then most
polyphenols are involved in bridging two proteins together, with
insufficient polyphenol to bridge dimers and form larger particles.
If the haze-active polyphenol is in excess of protein (as, for in-
stance, occurs in ciders), then there will be a shortage of free
proline sites able to enter into cross-linking of protein molecules.
The conditions exist for the formation of large networks that will
Fig. 2. Siebert’s model for protein-polyphenol interaction in beer.
especially manifest themselves as visible particles when there are
roughly equal quantities of haze-active protein and haze-active
polyphenol. Naturally, the levels of both will need to be suffi-
ciently high to manifest a visible haze when they associate. Light
scattering is less intense when the levels of protein and polyphe-
nol are disproportionate.
Such a model has major implications for the stabilization of
beer. For instance, “single ended” polyphenols would be expected
to block haze formation by competing for proline residues in pro-
teins and preventing cross-linking. Indeed, an excess of either
haze-active protein or haze-active polyphenol would be expected
to counter haze development, suggesting that a beer should be
“over-dosed” on one or other, but certainly not both. Also relevant
is Chapon’s model (12), which states that the following equilibria
exist in beer: P + T ←→ P – T (soluble) → P–T (insoluble), where
P = haze-active protein and T = tannoid.
This model implies that protein-tannoid complexes exist in beer
in equilibrium with the monomeric species and that this equilib-
rium can be shifted towards the monomers by removing either
protein or tannoid.
Stabilization Treatments
It is clear that both raw materials and process have a major
bearing on the level of haze precursors entering into beer, sug-
gesting that good practice can be recommended in respect to col-
loidal stabilization of beer. However, when considering how to
lengthen the shelf life of a product, most people automatically
gravitate to considerations of stabilizer treatments. Stabilizers can
undoubtedly have a major role to play, but should only be applied
as part of a more holistic approach to the achievement of colloidal
robustness. Furthermore, some caution needs to be applied when
surveying the literature discussing these agents, because much of
it has been generated by suppliers of one or the other of the stabi-
lizing treatments, who are obviously going to stress the merits of
their own type of product.
Essentially, there are three potential strategies: remove protein,
remove polyphenol, or remove a proportion of each. Many would
argue, in the context of uncertainties concerning the value of some
polyphenol and some protein in benefiting other aspects of prod-
uct quality, that the third of these strategies is the most valuable.
Whichever is applied, it must be borne in mind that the binding
forces involved in holding polymeric materials to adsorbents are
relatively weak; therefore, low temperatures are a pre-requisite for
colloidal stabilization.
One other key factor, which is sometimes neglected in descrip-
tions of beer stabilization, is beer clarity. Quite apart from the
influence which clarity may have on the efficiency of processes
involving PVPP and silica hydrogels, for instance, less-than-bright
beer will have a greater tendency to develop a haze through parti-
cle growth. If there are many small particles in beer (perhaps
those which are responsible for invisible or pseudo-hazes), they
can form nucleation sites for haze development. The first priority
must be to ensure that brewery operations are configured to mini-
mize the load on the filter (e.g., possible use of kettle, isinglass,
and auxiliary finings; efficient particle settling regimes in cold
conditioning; and so on) and that the filtration regime is properly
set up in respect of filter aid selection, dosing rate, lowest possible
temperature, minimum oxygen pick-up, and other procedures, not
forgetting that filter aid will itself adsorb haze materials. Only
then is it appropriate to establish the appropriate stabilization
treatment for the product in question.
Polyinylpolypyrrolidone
Polyinylpolypyrrolidone (PVPP) adsorbs both flavanoids and
tannins (82). Some people consider it an inappropriate treatment
because of its removal of potential antioxidants such as catechin.

However, as Walters et al have demonstrated (101), catechin and,
by inference, other flavanols surviving into beer have a value only
as protectants against new oxidation in beer and not the inherent
staling potential built in during the process. Therefore, the litera-
ture from suppliers of PVPP claims that beers treated with this
agent are of identical flavor stability to other beers. It has even
been claimed (78)—but disputed by McMurrough (64)—that
PVPP preferentially adsorbs highly hydroxylated flavanoids that
promote staling by stimulating the production of oxygen free radi-
cals (i.e., PVPP is beneficial to all types of shelf life). Further-
more, O’Rourke (82) and others have inverted the arguments that
polyphenols are needed for beer body with their claims that PVPP
improves taste quality by removing harsh and astringent con-
tributors. This whole issue of the contribution of polyphenols to
taste and mouth feel needs urgent rationalization. At this point in
time, the conclusion seems to be that the levels of polyphenols
present in most beers are too low to make a material contribution
(6).
Two types of PVPP are presently in use (78). The first, single-
use PVPP, comprises a micronized white powder of high sur-
face/weight ratio. This type of material readily adsorbs polyphe-
nols on its surface and can therefore be incorporated into a filter
aid bodyfeed dosing regime. The second type, regenerable PVPP,
can either be impregnated into sheets or used within devoted hori-
zontal leaf pressure vessels. These are regenerated by 1–2% caus-
tic with subsequent rinsing with hot and cold water and neu-
tralization by CO2 or 0.3% nitric acid. These materials are only
used after powder-based filtration (35), and a trap filter of cotton
or cellulose candles may be necessary after a powder-based sys-
tem in order to retain any very fine PVPP.
Chapon (12) reminds us that treatment of beer with PVPP must
be homogeneous; otherwise, there may be substantial differences
between the level of polyphenols in different packages.
The rate of usage of PVPP differs between beers (e.g., in par-
ticular, depending on the level of polyphenols emerging from raw
materials) and the level required needs to be identified empirically
for each beer (78). O’Reilly claims that reduction of a typical
flavanoid level of 30–40 mg/hL in a 20% adjunct lager by 25–
30% will allow a 12-month shelf life. To achieve this would de-
mand a dose rate of 15–20 g/hL for single-use PVPP and 35–
40g/hL for the regenerable grades, which have lower surface area.
These low doses of PVPP preferentially remove flavanoid dimers
and greater, with doses as high as 100g/L needed to remove large
quantities of the monomers such as catechin (66), which should
reassure those who worry about the removal of a strong antioxi-
dant from beer.
McMurrough (61) cites a binding capacity of PVPP for
polyphenols of ≈90 mg of polyphenol per 1 g of PVPP. O’Reilly
(78) acknowledges the role of haze-sensitive protein and points
out that the majority of single-pass PVPP is used alongside silica
hydrogel or xerogel, whereas the regenerable material is fre-
quently used alone.
McMurrough et al (61) demonstrated a convincing relationship
between haze development and the product (sensitive proteins ×
proanthocyanidins), with the proteins measured by tannic acid
precipitation and the latter as the sum of the dimeric flavanoids
prodelphinidin B3 and procyanidin B3 measured by HPLC. A
much poorer correlation was demonstrated when the proanthocya-
nidin measurement was replaced by total or oxidizable polyphe-
nols. Therefore, models were developed which calculate how
much a given beer needs to be treated with PVPP, silica hydrogel,
or both to achieve a given shelf life. McMurrough is adamant that
the dimeric species should be of particular concern to the brewer
and should be measured with a view to eradication. He accepts
that they need to be oxidized into a polymerized form before they
acquire a tanning capability.
Beer Haze / 85
An additional claim is that PVPP is beneficial to foam stability,
perhaps by taking out polyphenol that would otherwise remove
foaming polypeptide (78).
Silica Hydrogels and Xerogels
The manufacturing process for silica hydrogels and xerogels
has been described by Fernyhough et al (27). Xerogels are pro-
duced from hydrogels by drying before the milling stage that is
used to derive the preferred particle sizes. The critical features
include the pore size of the particles and the surface area pre-
sented by them. McKeown and Nock (54) say that the most effec-
tive pore size for a hydrogel is 3–12 nm and that to use anything
larger is to risk head retention. A reduction in particle size (giving
an increase in surface area) increases the adsorption rate. This is
of particular significance for the mode of use of hydrogels. If they
are dosed into the storage tank, then time will allow equilibrium to
be established. Conversely, if they are to be dosed in-line, then
adsorption rate is an especially important parameter. The latter
approach has been increasingly used, with 50 g/hL of an appropri-
ate grade having been successfully substituted for kieselguhr body
feed, allowing savings on the latter and longer filter runs (27).
Silica hydrogels with low permeability (filterability) afford
better stability (54). To achieve beers of prolonged shelf life, the
brewer should employ either low-permeability gels in storage
tanks, with a commensurate decrease in throughput and increased
filter aid usage, or else use larger quantities of high-permeability
gels. Newer generations of silica hydrogels have been developed
with very high stabilization efficiency (36) and it is claimed that
such preparations allow shelf lives as long as two years (27). They
have reduced permeability and should be added to the storage
tank. Guzman and Nock (37) describe the use of combined filtra-
tion and stabilization with silica hydrogel, describing savings in
raw materials, waste disposal costs, total process costs, filter life,
and reduced risk of iron pick-up. Fernyhough et al (27) say that
the extent of silica hydrogel usage depends on the intrinsic stabil-
ity of the beer being treated, the shelf life required, and the extent
to which other stabilizers are being used. They report the devel-
opment of models for individual beers. For one product, hydrogel
at 75 g/hL increased shelf life by 3–6 months, whereas doubling
this rate also doubled colloidal lifetime. O’Rourke cites an
equivalence of 1 g/hL PVPP to 7 g/hL silica hydrogel (79).
The earth bentonite (which is now rarely, if ever, used in the
brewing industry) is non-specific in its protein binding, removing
both haze and foaming polypeptide; in contrast, silica hydrogel
removes haze-forming protein preferentially (91). This is because
silica hydrogel recognizes and interacts with the same sites on
haze-active polypeptides, as do the polyphenols. A question still
not wholly answered is whether a competition can exist in beer, in
which polyphenols and hydrogels vie for the polypeptides. If this
is the state of affairs, then it may be that high levels of polyphe-
nols interfere with stabilization efficiency by silicas (as is cer-
tainly the case with ciders, possessed of far higher polyphenol
levels than beers) and that a co-treatment of beer with PVPP and
silica hydrogel would be best. Narziss mentions a pairing of 20–
50 g/hL of PVPP with a similar quantity of silica hydrogel incor-
porated into the body feed (73).
Tannic Acid
Tannic acid possesses a molecular structure closely similar to
that of other polyphenolic species; therefore, it is hardly surprising
that tannic acid is claimed to be a relatively specific precipitant of
haze-active proteins in beer (72). Just as the co-use of PVPP and
silica hydrogel has been advocated, so too did Mussche (72) ex-
plain the benefits of joint use of tannic acid and PVPP, in order
that both haze-active proteins and haze-active polyphenols should
be removed.
86 / Bamforth, C. W.
Tannic acid is a precipitant, as opposed to an adsorbent like
PVPP or silica hydrogel; therefore, it throws a sizeable precipitate
when added to a cold conditioning tank. This necessitates either
cautious transfer of beer from sedimented material in the tank or
the use of a polisher centrifuge followed by membrane filtration
(71). Alternatively, because the reaction time of the new genera-
tion of gallotannins is so rapid, they can be dosed on-line to the
powder filter.
Tannic acid is normally added from a 1–5% solution made up in
deaerated water at room temperature in the brewery. Sedimenta-
tion time following dosing on transfer from fermenter to storage
tank is at least one day, depending on temperature, yeast count,
vessel geometry, and related factors. When tank bottoms are in-
creased, the claim is for 25% longer filter runs.
If the gallotannin is dosed as beer flows to filter, then 5–10 min
of contact time at 0 to –1°C is necessary and the filter aid must be
adjusted to a much coarser grade of kieselguhr or a blend with a
high (90%+) proportion of perlite.
Mussche claims that tannic acid is not detrimental to foam
when used at recommended dose rates, but that it can remove
foaming polypeptides when used at levels as high as 200 mg/L
(72). Ishibashi, however, using antibodies, detected a loss of
foaming polypeptides caused by tannic acid (40).
Papain
Papain (26), from Carica papaya (paw paw), was the first haze-
preventative employed in the brewing industry. It retains some
usage, particularly by brewers taking a “belt and braces” approach
for beers destined for particularly challenging conditions. How-
ever, few brewers would deny the disadvantage of proteolytic
enzymes as stabilizing agents, because of their tendency to lessen
foam quality. Papain has a preference for peptide bonds formed
from hydrophobic amino acids; therefore, it is perhaps no surprise
that it hydrolyses foaming polypeptides, which are those with a
high hydrophobic character. Should foam quality be a secondary
consideration in a given marketplace, then papain is a perfectly
acceptable stabilizer, one which has the particular attraction of not
requiring any special equipment to enable its use.
Papain is added on transfer to maturation or during maturation
itself. It progressively loses its activity during storage and especially
during pasteurization. Notwithstanding, it will continue to act for a
limited time in a tunnel pasteurizer, and for a short period will effect
proteolysis approximately 100-fold more rapidly than during cold
conditioning. In sterile-filtered beers, any papain would survive into
the package to progressively lower foam stability.
Some argue that the mode of action of papain has as much to do
with a clotting effect as one of hydrolysis. Militating against this
is the observation by Fukal and Kas (28) that the action of papain
is blocked by a combination of ascorbic acid, copper, and oxygen.
Such a mixture generates hydroxyl radicals which inactivate the
enzymatic activity. This observation has practical implications in
that some brewers are less than circumspect about the manner by
Comparison of Stabilizer Costs
Point of Addition
Process Aid To Kettle
PVPP single usea 20 g/hL* b
Tannic acid 5 g/hL
Silica hydrogel 30 g/hL*
Proteolytic enzyme nil
PVPP regeneration c 15 g/hL*
a PVPP = polyvinylpolypyrrolidone.
b * = not usual point of application but has been or is being tried.
c The regeneration grade price is based on material costs with 1% loss and takes no account of capital or running cost of the filter.
which they make process additions. If papain (as haze stabilizer)
is added as a solution with ascorbic acid (antioxidant) and copper
sulfate (sulfur scavenger), then at least one of those agents won't
be functional.
Future Possibility
Katzke et al (46) described the development of regenerable ion
exchangers for removing haze-forming proteins from beer, materi-
als which are at the trial stage.
Relative Cost of Stabilizing Treatments
A recent comparison of stabilizer costs (80) is given in Table I.
Predictive Methods
There is great interest in the availability of reliable methods that
will enable the brewer to predict how long a beer will last in the
trade before it throws a haze. The very fact that a number of
methods exist is a sure sign that none of them is perfect. It is es-
sential for any of these tests that the brewer convinces himself or
herself that there is an unalterable relationship between actual
performance of a beer in trade and the results of one or a combi-
nation of tests.
O’Neill (77) defines colloidal shelf life as the length of time be-
fore beer displays a haze value of 2.5 EBC at 0°C. For many
brewers, this (or a similar figure) would be the yardstick against
which they would judge breakdown in a predictive test. There are
two main types of predictive tests: hot-cold cycling tests and pre-
cipitation tests.
Hot-Cold Cycling
There seem to be almost as many variants of this test as there
are brewers. Some tests don’t even consider the cold stage. For
instance, in the Guinness test (61), beer is held at 37°C; years of
experience with their products convince them that one week at
this temperature is the equivalent of one month of “normal” stor-
age (18°C). O’Neill (77) cites a few examples, illustrating the
length of time needed for a result on a beer by focussing on a
variant calling for 60°C for 2 days followed by –2°C for one day,
in which one complete cycle is said to be the equivalent of six
weeks of normal storage. A four-week test is needed to fully pre-
dict whether a beer will last a full year in the trade. Few brewers
have the luxury of being able to hold packaged beer for long
enough to allow such a test and, once the beer has left for the
marketplace, there is very little value in going through with such a
test, other than as a warning that there may be some beer to re-
cover from trade in a few months’ time.
Such tests are useful in the study of trial brews; for example,
the evaluation of new palliative procedures.
Precipitation Tests
The most famous such procedure—one which has almost be-
come an industry norm—is the alcohol-chilling test of Chapon
TABLE I
To Maturation To Filter Cost Treated ($/hL)
12–20 g/hL 15–20 g/hL 0.40 at 20 g/hL
5–7 g/hL 2–5 g/hL 0.32 at 6 g/hL
50–100 g/hL 30–80 g/hL 0.16 at 80 g/hL
2–5 mls/hL 2–5 mls/hL 0.14 at 5 mls/hL
nil 20–30 g/hL 0.05 at 1% loss

(11). Alcohol is added in the lowering of the temperature of a beer
to –8°C and chill haze is forced out within a total test time of 40
min. McKeown and Nock (54) observe that the method is depend-
ent on the starting alcohol content of a beer (i.e., it is “beer de-
pendent”), but they report a good correlation between the values
obtained and the product of sensitive protein and tannoid which,
as we have seen earlier, McMurrough has shown to relate closely
to shelf life. Chapon himself, however, accepts that the test pre-
dicts only chill haze. Although this is the main problem in the
lifetime of most beers, it is not the only potential colloidal prob-
lem in beer.
A further test—one of those incorporated into the Tannometer
(a commercial instrument which combines several predictive tests
for haze life) (8,86)—involves the precipitation of haze-active
proteins by tannic acid, the “protein-sensitivity” of a beer. In a
comparable test, the saturated ammonium sulfate precipitation
limit (SASPL) test, gallotannin is replaced by a solution of satu-
rated ammonium sulfate. In the former, the amount of light scatter
caused by a standard addition of tannic acid is measured. In the
latter, the number of milliliters of (NH4)2SO4 which need to be
added to cause a measurable increase in turbidity is recorded, on
the basis that the more salt is needed to bring out protein, the less
such precipitable protein is in solution. This method is useful for
comparing samples of a single brand of beer, but not for compar-
ing performance across brands. Tannoids can be quantified in a
method analogous to the sensitive-protein test by using poly-
vinylpyrrolidone monomer (PVP) as precipitant.
Finally, there are several procedures available for measuring the
redox state of beer, either reducing power (14) or redox coefficient
per se (9). Although it is unequivocally the case that oxidation is
an integral aspect of haze production, this type of measurement is
no better an indicator of colloidal stability than of flavor stability.
In each case, the chemistry is complicated.
In one of the few authoritative comparisons of predictive tests,
McMurrough et al (62) used a selection of procedures to evaluate
PVPP treatments of beers. Clearly, values of simple flavanoids
(rather than those which had polymerized into tannoids) and the
cooling test are the best predictors of instability.
Holistic Approach to Achieving Haze-Stable Beer
No brewer should expect to deal simply and efficiently with
colloidal stability by the application of one or a couple of down-
stream stabilization techniques. As much as any other aspect of
beer quality, the achievement of a colloidally robust beer depends
on attention to detail from selection of raw materials all the way
through to packaging, storage, and distribution. In this section, I
summarize the relevance of raw materials and the various process
stages for haze stability, and address preventative measures rele-
vant to hazes additional to protein-polyphenol hazes.
Raw Materials
The author is unaware of any claim that a given barley variety
is particularly low (or high) in its level of haze-active protein. It is
to be expected that there will be a pro rata higher level of poten-
tially troublesome material in high-nitrogen batches. However, it
would be wise to be dubious about any claims regarding nitrogen
modification of malt in respect to colloidal stability of proteins
until there is a clear demonstration that high molecular weight
polypeptides have a greater propensity to haze formation than do
low molecular weight ones. Based on Siebert’s model, it could be
argued that relatively low molecular weight polypeptides with
proline residues would enter into a more convoluted (and pre-
sumably larger-sized) network than a few very high molecular
weight proteins. On the other hand, the proven ability of papain to
enhance colloidal stability is accepted, although its efficacy
against polypeptides of different sizes is not fully appreciated. The
Beer Haze / 87
importance of homogeneous modification to the elimination of
troublesome β-glucans and, indeed, to the subsequent efficient
release and degradation of starch in mashing is significant. Re-
placement of barley malt with syrup adjuncts, or with rice and
maize grits or flakes, will dilute all types of haze precursor.
Barley- and wheat-based adjuncts, however, will increase risks
from haze-forming proteins, polyphenols, glucans, and, in the case
of wheat at least, pentosans.
Barley varieties vary considerably in their content of polyphe-
nols; for example, winter varieties having relatively high levels
(49). This is not an argument against the use of such varieties,
because it has been shown that the behavior of specific flavanoids
is important, rather than the absolute level of polyphenol. The
majority of the polyphenols are located in the husk. Alkaline
steeping of barley removes polyphenol from the husk (19). How-
ever, in order to lower the total polyphenol contribution from any
variety, it is possible (if perhaps tedious) to remove the husk from
malt prior to brewing (41). The first low-anthocyanogen barley
was bred several years ago (25) and varieties with improved agro-
nomic qualities have been developed since then (85). These varie-
ties are not yet in widespread use, apparently because of short-
comings other than in the brewery; however, their efficacy in
terms of providing colloidally stable beer is unquestioned. The
brewer should never lose sight of the fact that hops also provide
polyphenols; therefore, a stabilizer-free brewing regime must in-
volve polyphenol-free hop preparations as well as proanthocya-
nidin-free barley.
Aroma varieties of hops tend to contain higher levels of
polyphenols; however, it is the nature of these substances which
matters, not the absolute level. Various polyphenol-free bitterness
preparations are available (39). The major concern for the brewer
should be to use good-quality hops with the appropriate α-acid
content for the purpose in question. The author is aware of one
instance in which a brewery was left with a substantial quanity of
relatively low-α hops that had deteriorated so badly on storage
that the residual α-acid was extremely low. Undaunted, the brewer
simply increased the hop charge in the kettle, without dealing with
the substantially higher levels of polyphenol that this practice
unavoidably introduced into the process. A severe haze problem
ensued.
In summary, concerning raw materials (apart from the low-
polyphenol barleys and hop preparations), we might conclude that,
without knowledge of the varietal contribution to specifically
troublesome flavanoids or a proven link between use of a given
variety and haze problems, there is little potential for doing more
than specifying a maximum nitrogen content in malt (or consid-
ering dilution of the malt charge with low nitrogen adjuncts) and a
minimum α-acid content for hops.
Brewhouse
Sweet wort production is best viewed as a protein
“precipitation” rather than a protein “hydrolysis” stage because of
claims that proteolysis during mashing is limited (53). However,
the limitations of the Coomassie Blue method used by Lewis et al
have been highlighted (38,90). Low-temperature mashing-in, often
called a “proteolytic stand,” could be re-named a “β-glucanolytic
stand.” It will certainly be necessary to deal with high-glucan
grists, unless exogenous β-glucanases are used. Concerning the
polyphenols, it is generally accepted that lower pHs are commen-
surate with polyphenol precipitation and that prolonged run-off to
extract weaker worts will deliver proportionately more polyphenol
into the wort if pH is allowed to drift too high (water pH of 6.5–
7.0). The application of weak wort recycling can hardly be in
keeping with attempts to maximize shelf life. Furthermore, any
brewhouse technique which promotes wort turbidity (e.g., exces-
sive use of rakes in lautering) will be disadvantageous in this re-
88 / Bamforth, C. W.
gard, unless the high-particle charge is dealt with in some other
way. It is important that there is sufficient calcium in the grist to
ensure precipitation of oxalate (10).
Of particular significance for colloidal stability is the kettle
boil, with a well-formed hot break readily removed in hop back or
whirlpool representing nothing less than precipitable material that
would otherwise survive the process to destabilize beer. Apart
from the levels in sweet wort of polyphenols and proteins and the
extent to which polyphenolics are extracted from the preferred
hopping material, factors influencing the formation and removal
of hot break include the extent of agitation and turbulence (a
“rolling” boil affords enhanced opportunity for precipitation of
materials at localized surfaces) and the use of coagulants. O’Neill
(77) points out that proteins barely in solution at 101°C will be-
come insoluble as very fine particles (diameter <2 µm) as wort is
cooled to pitching temperature. These are the materials removed
by agents such as carrageenan, the use of which (as is true for any
fining agent) needs to be evaluated empirically by site trials.
It is not known whether a recurrence of colloidal stability
problems in recent years has mirrored the development of
brewhouse operations in which much more attention is paid to
minimizing oxygen ingress. It is claimed that wort oxidation is
substantially to the detriment of flavor stability (75) and that, as a
consequence, every attempt should be taken to minimize the con-
tact of wort with air (apart from that required to support fermenta-
tion). However scrutiny of a series of papers (74,76,81,82,87,96)
reveals that the benefits are by no means dramatic. In contrast,
long-established observation reveals that oxidation of polyphenols
during wort production is demonstrably to the benefit of haze life
because polymerization to tannins and their removal as trub is
promoted. It is only downstream that oxidation is to be avoided, if
the polymerization of monomeric flavanoids is promoted, with
such materials passing into beer as a destabilizing influence.
There seems to be an involvement of oxygen in the formation of
cold break (18), although it is felt by some that gas injection has a
physical effect on wort cooling and that nitrogen serves perfectly
well as a replacement for oxygen to promote trub formation in
systems where yeast rather than wort is oxygenated.
Fermentation and Maturation
Other than consideration of cold-break removal (24), there are
few adjustables in fermentation associated with colloidal stability.
It is likely that polyphenols are removed by adsorption onto the
yeast cell surface and that the extent of this removal will depend
on the freshness of the yeast and the extent of the growth. It also
appears that yeast in poor condition (large number of generations,
physical abuse such as centrifugation, and adverse storage condi-
tions, among other factors) will release polysaccharide materials
from within and from its surface which can cause clarity prob-
lems. However, the cold-conditioning stage is particularly critical.
Beer should be chilled to as low a temperature as possible without
freezing (high-gravity beers will stand lower temperatures; there-
fore, beers produced using high-gravity brewing are potentially
more stable than those brewed at sales gravity). The target for a
beer of 5% (v/v) alcohol should be –1°C. Three days at this tem-
perature is rather more effective than three weeks at 0°C. Ac-
cording to O’Neill (77), “a filter room should show evidence of
frosted mains.”
Judicious use of finings will help sedimentation of particles at
this stage. For many loss-conscious brewers, a primary considera-
tion is the maximal recovery of beer from cold storage. Some will
blend back sediments on run-off from cold tank, removing them
by centrifugation. Others will recover beer from tank bottoms in
various ways, including by cross-flow filtration. Although the
economic desirability of these processes is accepted, there is an
unavoidable problem of recovered beer presenting a stability risk
when blended back to the mainstream. Temperature and oxygen
control are critical; otherwise, the dangers of returning haze pre-
cursors to beer are huge.
Brewers employing PGA as a foam-stabilizer should do so
strictly according to manufacturers’ instructions. Experience
shows that it is worth paying slightly more for PGA already made
into solution rather than trying to produce PGA solutions from
scratch.
Filtration and Packaging
Beer should be kept as cold as possible en route to and through
the filter; otherwise, material precipitated in cold storage will tend
to return to solution and pass through into bright beer. Rigorous
minimization of oxygen ingress is essential, as is the avoidance of
any opportunity for heavy metal ions, such as iron and copper, to
enter the beer, because they will activate oxygen to the radical
forms in which it is active. Precautions here include the use only
of additions with low metal loadings, avoidance of recycling on
filters, especially during filter loading when high iron charges can
be leached off filter aid and, of course, use of water supplies with
low metal content, perhaps achieved by treatment. Filter aid se-
lection is also critical if there is to be efficient removal of the dead
bacteria that originate in malt, survive the brewing process, and
enter into beer where they cause dullness.
Attention should be paid to getting the gas contents correctly
within specification the first time, in order to avoid the need for
gas washing with its risks of foaming and “skin” formation.
Cans should be properly screened to ensure the absence of lu-
bricant residues capable of generating haze.
ADDENDUM
Since preparation of this manuscript, a further relevant review paper
has been published by K. J. Siebert: Effect of protein-polyphenol inter-
actions on beverage haze, stabilization and analysis. J. Agric. Food
Chem. 47:353-362, 1999.
ACKNOWLEDGMENTS
I thank G. Stewart and Graphics Services at Heriot-Watt University for
the artwork.
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[Received March 26, 1999. Accepted April 26, 1999.]