Degradation of Iso--Acids During Wort Boiling

S. Kappler1,*, M. Krahl1,2, C. Geissinger1, T. Becker1 and M. Krottenthaler1

ABSTRACT

J. Inst. Brew. 116(4), 332338, 2010

A detailed study on the degradation of iso--acids was conducted. Because of the complexity of the wort matrix and interfering interactions during real wort boiling, the investigation of
degradation kinetics was performed in an aqueous solution. Degradation was investigated as a function of time (090 min), temperature (80110C), pH value (47), original gravity (1018P)
and ion content of the water (0500 ppm Ca2+ and Mg2+). After
90 min of boiling, over 20% of the dosed iso--acids could no
longer be detected. A strong dependence of degradation could be
shown due to high temperature, low pH, high original gravity
and a high Mg2+ content. The cis:trans ratio and co-iso--acid
content did not change significantly. Losses of isohumulones
could be lowered by reducing the temperature and original gravity, as well as by heightening the pH value. High amounts of
Ca2+ and Mg2+ salts also led to an increase in degradation products. Solutions to decrease degradation and thereby possible
improvements in sensory bitter quality are discussed.
Key words: Hops, iso-alpha acids, wort boiling, utilisation rate.

INTRODUCTION
Hops, used in brewing, are the dried cones of the female plant Humulus lupulus sp. Other than in some specialized beers, only unfertilized cones are used. The
beginning of the use of hops in brewing is believed to date
back to the 11th or 12th century. It probably took place in
different regions of Belgium and Germany. The growing
popularity of hops is believed to be due to the bacteriostatic properties of the - and iso--acids16,26. Thus beers
brewed with hops were more stable against infections and
negative health effects occurred less often when hops
were used. The lower amount of infected beers was surely
one of the reasons why hops were the only allowed spicy
adjunct in the brewing process4. The most popular declaration regarding brewing is the Bavarian Purity Law, enforced in 1516, which defined hops as the only spicy adjunct allowed in beer. Nowadays, in over 99% of all
brews, hops are the only spice used43.
1 Technische

Universitt Mnchen, Lehrstuhl fr Brau- und

Getrnketechnologie, Weihenstephaner Steig 20, 85354 FreisingWeihenstephan, Germany.
2 MEG, Langendorfer Strae 23, 06667 Weienfels, Germany.
* Corresponding author. E-mail: Sebastian.Kappler@wzw.tum.de
Parts of this paper were presented at the 2nd International Symposium for Young Scientists and Technologists in Malting, Brewing
and Distilling, May 1921, 2010 in Freising Weihenstephan, Germany.
Publication no. G-2010-1206-117
2010 The Institute of Brewing & Distilling

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JOURNAL OF THE INSTITUTE OF BREWING

Hop bitter acids are the main bitter compounds in beer.

They contribute to more than 85% of the overall bitterness35. Humulones, also called -acids, which are present
in hops undergo an isomerisation reaction to isohumulones, also known as iso--acids, after thermal treatment2.
At least five homologues of humulones exist and these
only differ in one side chain at the C2-position51.
The percentage of the three main homologues, co-, nand ad-humulone, is around 90%. During the isomerisation reaction, two stereoisomers, cis- and trans-isohumulone are formed from each of the homologues50 and these
differ in their properties. It is known that cis-isohumulone
is more stable against ageing, but has weaker foam stabilising properties20. Previously published work shows that
a mixture of cis- and trans-isohumulones is more bitter in
beer than trans-isohumulones alone1. It is also known that
pure cis-isohumulones are more bitter than trans-isohumulones21. Just recently, purified cis-isohumulones were
isolated for the first time28. Losses during the fermentation
and storage of beer were shown to be higher for transisohumulones than for cis-isohumulones8, although there
is little difference in polarity between the cis- and transisohumulones20. Jaskula et al.25 found that iso- acid formation followed first-order kinetics and Arrhenius behaviour. Differences in activation energy for the formation of
trans- and cis-isomers were measured. The activation energy for the formation of trans-iso- acids was approximately 9 kJmol1 lower. Usually the yield of iso- acids
derived from the dosed hops is not more than around
30%38. This low yield is affected by numerous factors.
One of the main reasons is the poor solubility of the unisomerised humulones, as determined by Kolbach29 and
Spetsig49. Solubility of -acids can be improved by using
an increased pH value, which may result in an accelerated
isomerisation reaction, although the isomerisation reaction itself is not affected by changes in pH33. Additionally,
boiling time, boiling temperature, original gravity, type of
hop product and hop variety used are all factors that influence the yield of iso- acids13,3334,41. Prolonged boiling
time, a higher temperature and a higher concentration of
-acids in the dosed product have all shown a positive
effect11,17,18. Higher extract levels and higher concentrations of -acids in wort have resulted in lower yields34.
Another factor is the content of divalent cations and their
salts in the reaction medium. Some of these, for example
calcium and magnesium salts, were found to promote the
isomerisation of -acids into iso- acids in higher
amounts31. The use of pre-isomerised hop products such
as isomerised kettle extract or iso-pellets is a possible
approach to achieve higher yields in the cooled wort.
However, losses during fermentation and filtration are
reasons for a poor recovery rate of isohumulones in the
finished beers19,32,36. These losses are due to adhesion onto

yeast cells and filter aids. Carbon dioxide as the primary

yeast metabolite, in addition to ethanol, removes hop
derived compounds from the fermenting medium32. A
further approach to reduce losses is the use of downstream
products. Besides the traditionally used iso-extract, which
is added just before filtration, the use of reduced isohumulones such as rho-, tetrahydro- or hexahydro-isohumulones can reduce the risk of production of a skunky lightstruck flavour in bottled beer and also improve foam
stability27.
Some knowledge exists about the degradation kinetics
of humulones during hop storage7,42. Many substances are
formed from -acids by various chemical reactions51.
These substances are known to partly survive the brewing
process or are converted during wort boiling to compounds which impart a bitter flavour to beer44. Several
papers have been published regarding the factors that influence the stability of -acids during storage and the influence of the degradation products on the brewing quality
of the hops7,9,10,40,54. The Hop Storage Index (HSI) is
used as an indicator of hop freshness42,52. It has been
reported that a small amount of degradation products can
improve the quality of the bitterness in beer15. In larger
amounts, possibly resulting from the alkaline isomerisation of -acids, the sensory impression can be negatively
influenced due to the formation of humulinic acid14.
Recent research has also shown that there are some degradation reactions which are specific for trans-isohumulones22,23. These reactions form substances with a lingering and a harsh bitter taste33.
The role of iso-co-humulones has been controversial in
the past. Schnberger47 summarised as follows: By increasing pH value, more of the isohumulones are dissociated. This can lead to an unpleasant and harsh bitterness
in beer6,37. Rigby45, who compared beers with different
amounts of isohumulones, stated that iso-co-humulones
create a harsher and more intense bitterness. Newer research has contradicted this finding and could not find a
negative effect of iso-co-humulone to bitter quality30,39,48,53. Furthermore, there was a higher yield due to
the higher polarity and thus better solubility47. Nevertheless, many brewers still favour a low iso-co-humulone
content in the finished beer.
Recent research has shown that nearly 25% of the
dosed -acids cannot be found in the trub or hot wort,
either as -acids or as iso- acids12. Little knowledge exists about their fate. The aim of this study was to gain an
insight into the degradation process of the isohumulones
during thermal treatment. Changes in iso--acids were
monitored in a model solution during a simulated wort
boiling process.

MATERIALS AND METHODS

Samples and experimental setup
Pre-isomerised pure iso-alpha acids (Barth-Haas
Group, Nrnberg, Germany) were diluted in distilled water, lauter wort or diluted unhopped malt extract (Weyermann, Bamberg, Germany) respectively. The concentration of the isohumulones was 100 ppm in all trials. In
order to simulate wort boiling, the samples were heated in
an oil bath (Memmert, Schwabach, Germany) filled with

polyethylene glycol (BASF, Ludwigshafen, Germany)

using an inert reflux condenser. The parameters of time,
original gravity, pH, and temperature were varied. Boiling
time was set between 15 and 90 min with intervals of 15
min. Original gravity was between 10 and 18P with steps
of 1P. Temperature was set to 80C, 90C, 100C and
110C respectively. The pH value was adjusted before
boiling to 4.0, 5.0, 6.0 and 8.0 using phosphoric acid
(Baker, Deventer, The Netherlands) or sodium hydroxide
(Baker, Deventer, The Netherlands). Unless indicated otherwise, boiling time was set to 60 min. The effect of water
hardness was investigated using calcium sulphate (SigmaAldrich, Schnelldorf, Germany), magnesium sulphate
(Sigma-Aldrich, Schnelldorf, Germany) and calcium chloride (Sigma-Aldrich, Schnelldorf, Germany) in concentrations of 200 and 500 ppm and referred to Ca2+ and Mg2+.
The influence of different lauter fractions was determined
in separate boiling trials according to Yamashita et al.55
Iso--acids levels were measured before and after the
boiling process. All trials were carried out in duplicate.
All measurements were checked for suitability with the
coefficient of variation.
Determination of iso--acids
Iso--acids were measured after extraction with iso-octane (Baker, Deventer, The Netherlands) according to the
method presented by Jaskula et al.24 with some minor
modifications. Separation of the homologues and stereoisomers was performed using an Alltech Alltima C18, 5
m, 150 4.6 mm column (Grace, Columbia, MD, USA).
The liquid chromatographic system consisted of an
Agilent 1100 series system with autosampler, quaternary
pump, thermostat and an Agilent 1200 series diode array
detector (DAD). Isocratic elution was conducted with
52% acetonitrile, HPLC gradient-grade (Baker, Deventer,
The Netherlands) and 48% of bi-distilled water (Millipore, Billerica, MA, USA) adjusted to a pH of 2.8, with
phosphoric acid (Baker, Deventer, The Netherlands). Injection volume was 25 L and time of analyses was set to
70 min. The thermostat was set to 30C. Because brown
vials had shown lower retrieval rates in previous trials due
to iron traces in the glass5, clear vials were used. Detection wavelength was set to 270 nm. Prior to analysis, the
samples were filtered through a 0.45 m membrane filter.
Calibration was conducted using ICS-I2 (Labor Veritas, Zrich, Switzerland) as the external standard. The
coefficient of variation for this analysis was below 2%
(data not shown).

RESULTS AND DISCUSSION

During wort boiling at atmospheric conditions, a constant decrease of isohumulones was observed (Fig. 1).
After 30 min of boiling, the recovery of isohumulones
was about 90%. Subsequently a linear drop to a recovery
rate of 77% after 90 min was measured. The cis-trans
ratio showed a slight increase from 4.5 to 4.7 in this trial
(data not shown). Regarding the amount of co-isohumulones, no significant effect of boiling time was seen.
Figure 2 shows the effect of different temperature treatments over 60 min on the recovery rate of the isohumulones. At 80 and 90C, isohumulone losses of 5 and 9%
VOL. 116, NO. 4, 2010

333

Fig. 1. Recovery rate of dosed isohumulones during 90 min of atmospheric boiling.

Fig. 2. Recovery rate of dosed isohumulones after treatment with different temperatures.

Fig. 3. Recovery rate of dosed isohumulones after atmospheric boiling with different pH values.

were measured. During atmospheric boiling, losses were

more pronounced and only 84% of the dosed isohumulones were recovered. A further increase in temperature
led to a recovery rate of only 81%. The cis-trans ratio
changed from 4.5 to 4.8 (data not shown). No changes
were seen regarding the iso-co-humulone fraction.
Figure 3 shows the effect of pH changes on the recovery rate of isohumulones after boiling. At a pH of 4.0,
only 58% of the initially dosed isohumulones were found.
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Detection rate was 80% at a pH of 5.0, 86% at a pH of 6.0

and 95% at a pH of 8.0. No changes were seen in the cistrans ratio, while the co-isohumulone fraction decreased
slightly from 48% at a pH of 4.0, to 45% at a pH of 5.0, to
44% at a pH of 6.0 and to 41% at a pH of 8.0.
Figure 4 shows the effect of varying the original gravity on the recovery rate of isohumulones after wort boiling. The recovery rate dropped linearly from 90% at 10P
to 52% at 18P. No changes were observed in the cis-trans

Fig. 4. Recovery rate of dosed isohumulones after atmospheric boiling with varying original
gravity.

Fig. 5. Relative co-isohumulone content after atmospheric boiling with varying original gravity.

Fig. 6. Recovery rate of dosed isohumulones after atmospheric boiling with varying ion content.

ratio. The relative amount of iso-co-humulones increased

with increasing original gravity from 38% at 10P to 45%
at 18P (Fig. 5).
These results were confirmed by using different lauter
fractions during the boiling trial. In the first wort, only
48% of the isohumulones initially present were detected.
Boiling of the isohumulones with the last running resulted
in an 83% recovery. Iso-co-humulone levels were 45% in

the first wort, and decreased to 38% in the last runnings.

Addition of mineral salts resulted in lower recovery
rates. Compared to a recovery of 83% after boiling with
distilled water, values were 38% lower after the addition
of 200 ppm CaCl2 and 48% lower after the addition of
500 ppm CaCl2. Addition of 200 ppm MgCl2 resulted in a
decrease of 52%. Boiling with 500 ppm MgCl2, resulted
in a 54% lower recovery rate. Boiling with CaSO4 reVOL. 116, NO. 4, 2010

335

Fig. 7. The cis:trans ratio after atmospheric boiling with varying ion content.

sulted in 10% lower isohumulone levels at 200 ppm and

25% lower levels at 500 ppm (Fig. 6). The cis-trans ratio
decreased in all trials (Fig. 7).
However, this decrease was only significant after the
addition of MgCl2. In this particular case, the ratio decreased from 4.7 to 3.8 after the addition of 200 ppm and
to 3.6 after the addition of 500 ppm. Addition of chloride
containing salts did not significantly change the percentage of the iso-co-humulones. Levels increased from 38%
to 39% with a dosage of 200 ppm, and to 41% with 500
ppm CaCl2. In the boiling trial with MgCl2, 41% of the
iso-co-humulones could be measured after an addition of
200 ppm and 43% after an addition of 500 ppm. No effect
was seen after dosage with CaSO4.
The results obtained in these trials demonstrated that
prolonged wort boiling, as well as higher original gravity,
led to lower final concentrations of isohumulones. The
higher temperatures and lower pH values, as well as the
dosed mineral salts, also lowered the recovery rate. In the
practical brewing process, lower temperatures during wort
boiling and treatment (e.g. temperatures in the heat exchanger) will reduce the losses of the isohumulones and
lead to a lower amount of undesired degradation products
in the cooled wort. Regarding the degradation of isohumulones, whirlpool temperature should not exceed 90C.
Simultaneously, lower temperatures offer further advantages such as lower total DMS levels, as DMS-P cleavage
is reduced3. If iso-kettle-extract is being used during wort
boiling, a short boiling time after dosage should be chosen
to guarantee an optimum isohumulone yield. Late addition of iso kettle extract, is not a problem regarding the
yield of isohumulones, as no further isomerisation reaction is needed. However, although isomerisation is already
completed, the evaporation of undesired aroma components is needed. Consequently, at least a short boil is recommended. Additional wort acidification should be performed just before the end of the wort boil to reduce
degradation of the isohumulones. This beneficial effect of
late acidification is independent of the hop product used.
Regarding water treatment, the usage of calcium sulphate
is beneficial towards a higher yield of isohumulones, in
comparison to calcium and magnesium chloride. In the
brewing process, calcium sulphate and calcium chloride,
as well as magnesium chloride lead to a lower pH during
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JOURNAL OF THE INSTITUTE OF BREWING

mashing and are thus beneficial for the desired enzymatic

activities and can reduce undesired enzymatic activities46.
Consequently, brewers need to compromise between
beneficial effects during mashing, and the degradation of
isohumulones during the wort boil, if chloride containing
salts are used. Regarding high-gravity brewing, the results
indicated that higher losses are to be expected during the
wort boil. A possible approach to reduce such losses, especially if iso kettle products are being used, might be a
separate boiling of the hops with the last runnings. This
would limit losses and optimize recovery rates. However
if traditional hop products are used another problem has
to be taken into account. On the one hand, the unisomerised -acids from hops, pellets or hop extract have to be
dissolved and subsequently isomerised. On the other
hand, degradation of the isohumulones is not desirable
and should be limited to a minimum. Equilibrium between isomerisation and degradation must be found to
guarantee optimum yields. If hops are added at the beginning of wort boiling, the degradation reaction could lead
to an increase in less favourable flavour impressions under unfavourable conditions.

CONCLUSIONS
In this work, boiling trials were performed to evaluate
the degradation kinetics of isohumulones, the main bittering substance in beer. Isohumulones, which are formed
from hop-derived humulones, are not stable under thermal
treatment. Various degradation products form and these
can create a harsh bitterness and lingering aftertaste. Today many of these substances have been identified, but the
kinetics of their formation is still unknown. The aim of
this study was to evaluate the factors affecting the degradation of the isohumulones. Boiling trials on a lab-scale
with purified iso--acids, at a concentration of 100 ppm,
were conducted. Temperature, pH value, original gravity,
lauter fraction and ion content were varied. Before and
after the thermal treatment, the content of the isohumulones was measured. The recovery rates of the isohumulones, as well as the cis:trans ratio and the relative
amount of iso-co-humulone were calculated.
By varying the wort composition and the boiling parameters, losses of isohumulones during wort boiling and

wort treatment could be reduced. Boiling at atmospheric

pressure for 90 min, comparable to a standard boil and hot
wort treatment, led to losses of nearly 25% within 90 min.
These losses could be minimized by lowering the temperature. High losses were also found when isohumulones
were boiled at a low pH value, high original gravity and
high water hardness. By optimizing these parameters,
losses of isohumulones and thereby a decrease in less
favourable bitter impressions can be attained.
ACKNOWLEDGEMENTS

This work was supported by the Barth-Haas Group.

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(Manuscript accepted for publication August 2010)