INTERNATIONAL
TECHNICAL FEATURE
Calcium – oxalic acid – technological
importance
F. Jacob, Munich-Weihenstephan
alcium has a special significance
when it occurs together with oxalic
acid and can form with the latter
calcium precipitates (Ca-oxalate) in beer.
In addition to the accepted factors such a
fusaria infestation of barley or malt, also re-
ferred to as “malt-based” gushing, or exces-
sive iron concentrations in bottled beer,
these Ca-oxalate precipitates are regarded
increasingly as possible contributors to
gushing. Data collected by the State Testing
and Experimental Institute for Brewing Tech-
nology Weihenstephan points to the fact
that Ca-oxalate may have played a signifi-
cant role in the problem of gushing experi-
enced by many breweries as of the beginning
of March 1998. But further, hitherto un-
known factors cannot be excluded.
■ Evidencing presence of Ca-oxalate
crystals
These Ca-oxalate precipitates involve fine
particles which may arise in a number of
forms. On the one hand, they can be octahe-
dron-shaped crystals (Fig. 1), on the other
hand, they can be amorphous bodies (Fig. 2)
which are regarded as particularly danger-
ous as a cause of gushing. Ca-oxalate precip-
itates can be identified with a microscope
when 96% H2SO4 is added, whereby crystals
resembling gypsum needles are formed
(Fig. 3).
■ Introduction of Ca and oxalic acid
The Ca-content of beer ranges from 10 to
50 mg/l and is determined by the liquor qual-
ity – malt contributes only small quantities
of calcium. Liquor quality can be altered by
additives such a Ca-chloride or Ca-sulphate
(brewing gypsum) already in the brew-
Assessment of tendency of beer to form calcium oxalate precipitates (2)
Group Q:CaS04/CaC204) Ca-oxalate (mg/l)
(1) < 0.25 < 50
2 0.25 – 5 > 20
3 5 – 13 15 – 20
4 > 13 < 15
58 BRAUWELT INTERNATIONAL 2000/I
It is well known that Ca-
oxalate precipitates act as
crystallisation nuclei.
Carbon dioxide is set free
at these nuclei, this may
contribute to gushing of
beer and may also Fig. 1 Calcium oxalate crystals shaped
as octahedrons
reinforce this
phenomenon. This article
describes factors
promoting formation of Ca-
oxalate crystals and the
possibilities of taking
preventative measures.
Fig. 2 Unusual calcium oxalate forms
house. The major part of the calcium con-
tributed by malt and brewing liquor goes
with the spent grains. Overall balances of
calcium from brewing liquor, malt and CaCl2/
CaSO4 additives showed a “Ca-yield” in wort
of only about almost 30% and of about 20%
in beer (1).
Oxalic acid gets into wort primarily via
malt and to a lesser degree via hops. En-
riched hop products introduce only low
oxalic acid levels into wort (2). In recent
years, the trend of oxalic acid concentra-
tions found in malting barleys and wheats
analysed in Weihenstephan has been rising. Fig. 3 Formation of unusual gypsum
Values up to 60 mg of oxalic acid/l in wort are needle shape after addition of H2SO4 to
no longer a rare occurrence. calcium oxalate
oxalic acid levels than barley malts. A multi-
The oxalic acid content in malt is a func-
plicity of investigations carried out at the
tion of variety, year and growing conditions.
State Testing and Experimental Institute for
Wheat malts contain significantly higher
Brewing Technology Weihenstephan has
shown that oxalic acid concentrations in
barley malt range from 10 to 20 mg/100 g of
State dry matter, even values up to 40 mg of oxalic
acid/100 g of dry matter were found.
relatively stable (as long as no Ca gets into the beer)
unstable Author: Dr. Fritz Jacob, State Testing and
stable Experimental Institute for Brewing
Technology, Technical University Munich-
very stable Weihenstephan

Oxalic acid concentrations in wheat malts
fluctuate between 30 and 60 mg/100 g of dry
matter. An overall rising tendency has been
observed, particular in last year’s harvest.
■ “Factor Q” – tendency to form Ca-
oxalate
Determination of the “free Ca-ratio” Q ac-
cording to Schur et al. (2) has proven suc-
cessful in order to provide a better assess-
ment of the tendency of a beer to form Ca-
oxalate precipitates and adopt suitable and
timely measures for preventing same. It
gives the quotient from the fraction of Ca++
ions (calculated as Ca-sulphate) and the
oxalate value (expressed as Ca-oxalate)
(Fig. 3).
A stable state is reached when Ca-oxalate
concentration is below the solubility limit Lp
( Ca++ . C2O4- - ) in beer. In finished beer, Ca-
oxalate precipitates occur when the quo-
tient Q has been unfavourable from the very
start, or when the equilibrium is shifted due
to subsequent introduction of calcium ions
during filtration. Calcium reacts with oxalic
acid and precipitates in the form of Ca-
oxalate.
In the course of beer production, the solu-
bility limit of Ca-oxalate is lowered: While 60
mg/l of Ca-oxalate are soluble in wort, the
INTERNATIONAL
TECHNICAL FEATURE
figure goes down to about 20 – 30 mg/l in
beer (3, 4).
The objective is to eliminate or separate
out as much of the oxalic acid as possible,
with an excess of calcium ions, even before
filtration, in order to prevent any subse-
quent reaction between an excessive quan-
tity of free oxalic acid in filtered beer and
calciumP.
In order to predict the tendency of a beer
to form Ca-oxalate precipitates, it is best to
determine the Ca-oxalate ratio in the storage
tank prior to filtration. A Q factor >10 is most
advantageous, with the oxalate value (ex-
pressed as Ca-oxalate) being less than 15
mg/l.
■ Preventative measures
These include: Addition of an excess of
calcium in the form of Ca-chloride and/or Ca-
sulphate in the brewhouse to induce precip-
itation of the largest possible quantity of
oxalic acid in the form of Ca-oxalate, even
before filtration; or preventing subsequent
introduction of calcium into the finished
beer e.g. through filter aids, water.
As far as filter aids are concerned, a beer
soluble Ca-portion in kieselguhr and also in
stabilising agents of <1000 ppm should
be regarded as an upper limit value (5).
Beer soluble Ca in filter aids can be meas-
ured according to MEBAK.
Ca-chloride and/or Ca-sulphate should be
added both to the mashing-in liquor and to
the spargings. When calculating additions, it
must be borne in mind that 1 kg of CaCl2
solution (34%) contains 123 g of calcium
and 1 kg of CaSO4.2H2O (gypsum) 223 g of
calcium.
Calcium chloride imparts a smooth full fla-
vour although larger additions will cause a
“salty” tang. On the other hand, gypsum in-
troduces a somewhat drier character, beers
might tend to have a hop blossom flavour (6).
■ References
1. Schröder, C., Semester paper, TU Munich
Weihenstephan 1993.
2. Schur, F., Anderegg, P., Senften, H., Pfen-
ninger, H., Schweiz. Br. Rdschau 91 (1980)
201.
3. Burger, M., Becker, K., Proc. Amer. Soc.
Brew. Chem. 7 (1949) 102.
4. Brenner, M. W., Proc. EBC Congr., Copen-
hagen, (1957) 349.
5. Jacob, F., Getränkeherstellung Deutsch-
land. Handbuch Getränkeproduzierende
Industrie (97) 22.
6. Narziss, L. “Technologie der Würzeberei-
tung”, Enke Verlag Stuttgart 1992, 43. ■
2000/I BRAUWELT INTERNATIONAL 59