Stability of Glutamic Acid and Monosodium Glutamate
Under Model System Conditions:
Influence of Physical and Technological Factors
A. GAYTE-SORBIER,
ABSTRACT
The stability of glutamic acid and monosodium glutamate as regards
pH, temperature and oxygen was studied during storage and two
thermal processings, the residual products and those which ap-
peared being determined. The initial molecules only change into
pyrrolidonecarboxylic acid, never into glutamine nor y-aminobuty-
ric acid. Preservation is good in all cases at pH 0 and pH 14, but
glutamic acid is converted to pyrrolidonecarboxylic acid at inter-
mediate pH values. The change is favored by pH values ranging from
2 - 3, by temperature increase and by oxygen.
INTRODUCTION
FREE GLUTAMIC ACID in sodium salt form is added as
a taste-active ingredient to many industrially prepared food
products. It exists naturally, however, in varying concen-
tration in free form, in several foods such as chicken, shell-
fish, crustacea, different vegetables and fruit. In combined
form, glutamic acid is also a native constituent of food pro-
teins. This amino acid on the other hand plays an important
role at several levels of nitrogen metabolism.
This double aspect of glutamic acid, sometimes as an
additive, sometimes as a normal constituent of foods,
and its metabolic importance have been reviewed in a book
recently published (Filer et al., 1979). They induced us
to study the fate of glutamic acid under different storage
conditions and during several technological procedures.
Wilson and Cannan (1937) observed that glutamic acid was
converted to pyroglutamic acid at some pH values, but
their work was almost exclusively theoretical. Later, Olcott
(1944) showed that autoclaving a protein hydrolyzate
changed glutamic acid almost entirely into pyroglutamic
acid under certain conditions. Goodban et al. (1953)
established that this derivative was produced from gluta-
mine during beet juice processing. It has long been known
that vegetables lose free glutamic acid during cooking, as
well as during the first 24 hr of refrigerator storage (Hat
et al., 1949). It is now recognized in the food processing
industry that thermal processing reduces the taste-active
effect of added monosodium glutamate if processing takes
place after addition. Rice and Pederson (1954), and El
MiIadi et al. (1959) stressed the pyroglutamic concentra-
tion increase in heated and/or stored tomato juices. The
same phenomenon was observed in cherries and in some
vegetables which had been heated, then stored for 2 yr
(Mahdi et al., 1959), in spinach (Lin et al., 1970, 1971),
and in carrots (Bibeau and Clydesdale, 1975) after differ-
ent treatments. The pyroglutamic acid concentration in-
crease was attributed in several of these cases to glutamine
conversion, since glutamine concentration decreased ac-
cordingly.
It was assumed that the more marked flavor of freshly
gathered vegetables might be due to their higher concen-
tration of glutamic acid (Hat et al., 1949) and that the
The authors are affiliated with the Laboratoire de Bromatologie,
0itWtiqu.s et Analyse appliquhe a /‘Expertise, Facult6 de Pharma-
tie, 27 boulevard Jean Moulin, 13385 Marseille Cedex 5, France.
350-JOURNAL OF FOOD SCIENCE-Volume 50 (7985)
Ch. B. AIRAUDO, and P. ARMAND
appearance of off-flavors was probably related to the in-
crease in pyroglutamic acid concentration (Rice and Peder-
son, 1954). Subsequent investigations (Shallenberger and
Moyer, 1958; Shallenberger et al., 1959) corroborated that
ammonium pyroglutamate added to beet purees gave them
bitter, medicinal, or phenolic flavors, similar to those of
heated beets. Mahdi et al. (196 1) concluded that pyrroglu-
tamic acid changed the flavor of various foods when its
concentration reached a given level, which varied with the
food in question.
The objective of the present work has been to study the
different factors influencing the conversion of glutamic
acid during its storage and processing, and to identify the
conversion products.
MATERIALS& METHODS
SOLUTIONS at 1 g/L and 5 g/L of L-glutamic acid (Merck, ref.
291) and monosodium L-glutamate (Merck, ref. 6445) were pre-
pared in acid and alkaline aqueous dilutions, obtained from normal
solutions of hydrochloric acid and sodium hydroxide so as to cover
the whole range of pH values from 0 - 14 steps of 1 pH unit.
This range is considerably larger than the normal range of food pH
values and allowed us to study the stability of glutamic acid in all
possible situations, thus extending the practical range into the realm
of theory. The solutions were sterilized by filtration through mem-
brane (Millipore, MiIlex type, ref. SLKA 02505, 25 mm diameter,
0.45 @rn porosity) as soon as they were prepared. The effect of
the different storage and processing procedures described below
was evaluated on each of the solutions.
Storage and processing conditions
In all storage studies, the solutions were stored for 50 days in
the dark in sterilized ground-glass stoppered bottles. In order to
study the preservation of glutamic acid and monosodium glutamate
protected from the air, the solutions were stored at room tempera-
ture (20°C) and in a refrigerator (4°C) in completely filled and
stoppered bottles. Each determination of residual concentration
after a given time necessitated an individual bottle to avoid the
entry of air resulting from sampling. The solutions were therefore
not entirely oxygen-free, but the influence of air was limited to that
of the air dissolved in them. This storage was termed, for con-
venience sake, “without atmospheric contact? For the study of
preservation at room temperature under nitrogen, the dissolved air
was eliminated by bubbling nitrogen through the solutions. A
nitrogen atmosphere was maintained on the liquid surface before
the bottles were stoppered and reconstituted after each sampling.
To study the effect of oxygen, storage was similar to that above,
except that nitrogen was replaced by oxygen. Finally, to study the
effect of air, the solutions were stored in stoppered (in order to
avoid microbial contamination) but half-full bottles and with resid-
ual air on the liquid surfaces. In each experiment, the time depen-
dent residual glutamic acid or monosodium glutamate concentra-
tions were determined after 1, 2, 3, 5, 10, 15, 20, 30 and 50 days,
as were the conversion product concentrations.
Boiling under reflux was done for 15, 30, 60 and 120 min and
residual glutamic acid was determined as soon as the solutions had
cooled. The conversion products were determined, however, only
after 60 mm boiling, based on information from the study on the
disappearance of glutamic acid. In the autoclaving processing, the
solutions were heated to 135°C under 2.7 kg/cm2 pressure in
screw-top glassbottles with bakelite capsand Teflon@ seals(“SVL”@,
France). Conversion products were determined only after 30 min
processing.
 Analytical methods and 5 days. In alkaline media, the glutamic acid concen-
Glutamic acid and monosodium glutamate were determined by tration remained unchanged for at least 10 days. The ex-
oxidative deamination with L-glutamate dehydrogenase (Bernt cellent preservation of glutamic acid in very acid (pH 0)
and Bergmeyer, 1974). We have reported a critical study of this and very alkaline (pH 14) media should be particularly
method (Armand et al., 1976). y-Arninobutyric acid was separated emphasized. The smallest residual concentrations of glu-
by ion exchange liquid chromatography according to the Moore and tamic acid were observed after 50 days at pH close to 3
Stein method (Spackman et al., 1958), using ninhydrin. Glutamine (Table 2). The glutamic acid which disappeared seemed to
was also determined by the same method. Pyroglutamic acid was be almost completely converted into pyroglutamic acid
determined after reaction with hydroxylamine and iron (III) chlor-
(Table 2).
ide. These methods have been reported elsewhere (Airaudo et al.,
1984). When glutamic acid was stored at room temperature
under nitrogen, its behavior after 50 days was quite similar
RESULTS to that observed in the previous case (Table 2). The preser-
vation was excellent in very acid and very alkaline media.
THE RESULTS are summarized in Tables 1 to 3, in which When degradation was observed, glutamic acid was once
the value 1.00 is arbitrarily attributed to the initial concen- again converted to pyroglutamic acid.
tration and the other values quoted are the stoichiometric On the contrary, the conversion at room temperature
relations of residual glutamic acid (or monosodium gluta- under oxygen was larger and faster as early as the first days,
mate) and of pyroglutamic acid formed. except in very acid and very alkaline media (Tables 1 and
Glutamic acid without atmospheric contact did not 2). The greatest conversion was observed between pH 2 and
show any conversion at room temperature for 24 hr, what- pH 3. Another less marked conversion was also observed
ever the pH (Table 1). A small change began to occur in between pH 6.5 and pH 8.5. The conversion resulted again
acid media after 3 storage days and increased between 3 in the formation of pyroglutamic acid. Very alkaline and

Table I-Degradation of glutamic acid /initial concentration I g/L represented as 1.00) under different storage conditions at room temperature
over 30 days

Residual glutamic acid without atmospheric contact Residual giutamic acid under oxygen
Number of storage days Number of storage days
PH 1 3 5 10 15 20 30 2 5 10 15 20 30

0.0 1.oo 1 .oo 0.99 0.99 0.99 0.99 0.98 0.99 0.99 0.99 0.95 0.90 0.90
1.0 1 .oo 1 .oo 0.99 0.99 0.97 0.95 0.92 0.99 0.98 0.96 0.91 0.88 0.85
2.0 1 .oo 1.00 0.98 0.97 0.96 0.94 0.87 1 .oo 0.98 0.95 0.84 0.65 0.54
3.0 1 .oo 1.00 0.98 0.97 0.95 0.92 0.85 1.oo 0.98 0.98 0.78 0.62 0.51
4.0 1 .oo 1 .oo 0.98 0.97 0.95 0.92 0.86 1.oo 0.98 0.97 0.84 0.69 0.62
5.0 1 .oo 0.99 0.98 0.98 0.95 0.93 0.88 0.98 0.98 0.96 0.88 0.68 0.65
6.0 1 .oo 0.99 0.98 0.98 0.95 0.94 0.89 0.98 0.98 0.95 0.88 0.66 0.62
7.0 1 .oo 1.00 0.99 0.99 0.96 0.95 0.90 0.98 0.98 0.95 0.82 0.64 0.59
8.0 1 .oo 1.00 1 .oo 0.99 0.97 0.95 0.91 0.98 0.98 0.96 0.76 0.66 0.59
9.0 1 .oo 1 .oo 1.00 1 .oo 0.98 0.96 0.93 0.99 0.98 0.96 0.78 0.73 0.65
10.0 1.oo 1.00 1.00 1.00 0.99 0.97 0.94 0.99 0.98 0.96 0.85 0.82 0.77
11.0 1 .oo 1.00 1 .oo 1 .oo 0.99 0.98 0.97 1 .oo 0.98 0.97 0.92 0.90 0.86
12.0 1.00 1.00 1.00 1.00 0.99 0.99 0.98 1 .oo 0.98 0.98 0.94 0.92 0.88
13.0 1 .oo 1.00 1 .oo 1.00 1 .oo 0.99 0.98 0.99 1 .oo 0.98 0.96 0.94 0.92
14.0 1.00 1 .oo 0.99 1 .oo 1.00 0.99 0.98 0.99 0.99 0.99 0.98 0.95 0.95

Table Z-Conversion of glutamic acid and monosodium glutamate (initial concentrations 5 g/L, represented as 1.00) under different storage con-
ditions after 50 daysa

At room temperature At 4’C

Under Under With atmos-
Without atmospheric contact nitrogen oxygen pheric contact Without atmospheric contact

PH a a’ b b’ a a’ a a’ a a’ a a’ b b’

0.0 0.99 0.00 1 .oo 0.00 1 .oo 0.00 0.95 0.02 0.98 0.00 1 .oo 0.00 1 .oo 0.00
1 .o 0.93 0.05 0.93 0.07 0.94 0.07 0.80 0.20 0.85 0.15 0.97 0.00 0.98 0.00
2.0 0.88 0.10 0.88 0.11 0.90 0.09 0.47 0.53 0.50 0.47 0.95 0.04 0.95 0.05
3.0 086 0.10 0.87 0.10 0.90 0.10 0.47 0.54 0.53 0.47 0.95 0.05 0.95 0.05
4.0 0.87
L -0.88
0.10 0.11 0.90 0.10 0.56 -0.43 -0.56 -0.45 0.95 0.05 0.95 0.05
5.0 0.88 0.10 0.87 0.10 0.90 0.10 0.60 0.40 0.55 0.45 0.95 0.05 0.95 0.05
6.0 0.88 0.10 0.88 0.10 0.90 0.10 0.57 0.43 0.55 0.45 0.95 0.05 0.95 0.05
7.0 0.88 0.09 0.88 0.10 0.91 0.09 0.54 0.42 0.55 0.45 0.95 0.05 0.95 0.05
8.0 0.91 0.08 0.91 0.08 0.93 0.07 0.54 0.43 0.55 0.45 0.95 0.05 0.95 0.05
9.0 0.93 0.07 0.94 0.06 0.95 0.04 0.60 0.41 0.60 0.41 0.95 0.04 0.95 0.05
10.0 0.97 0.04 0.97 0.05 0.99 0.02 0.78 0.24 0.77 0.25 0.96 0.03 0.97 0.04
11.0 0.98 0.02 0.98 0.00 0.99 0.00 0.86 0.12 0.85 0.13 0.98 0.00 0.98 0.00
12.0 0.99 0.00 0.99 0.00 1 .oo 0.00 0.89 0.10 0.89 0.10 0.99 0.00 1 .oo 0.00
13.0 1 .oo 0.00 1 .oo 0.00 1 .oo 0.00 0.91 0.08 0.92 0.08 1 .oo 0.00 1 .oo 0.00
14.0 1 .oo 0.00 0.99 0.00 1 .oo 0.00 0.95 0.01 0.98 0.01 1.00 0.00 1.00 0.00

a a - residual glutamic acid; a’ - pyroglutamic acid formed from glutamic acid; b - residual monosodium glutamate: b’ - Pyroglutamic acid
formed from monosodium glutamate.

Volume 50 (798514OURNAL OF FOOD SCIENCE-351

 STABILITY OF GLUTAMIC ACID. . .

Table 3-Conversion of glutamic acid and monosodium glutamate (initial concentrations 5g/L, represented as 1.00) during thermal processingsa

Boiling processing Autoclaving processing at 135’C

Number of processing minutes Number of processing minutes

PH - 15 - 30 60 120
-__ 15 30 - 60 - 120
a a a a’ b b’ a a a a’ b b’ a a

0.0 1.oo 1 .oo 0.99 0.00 1.00 0.00 0.98 0.98 0.96 0.02 0.98 0.02 0.96 0.95
1.0 Q.&L Q&7- 0.88 0.12 0.90 0.10 0.78 0.75 0.69 0.22 0.72 0.24 0.68 0.65
2.0 0.94 0.92 0.83 0.18 0.85 0.15 0.71 0.57 0.39 0.64 0.35 0.70 0.31 0.30
3.0 0.97 0.95 0.87 0.15 0.88 0.13 0.77 0.55 0.35 0.69 0.27 0.75 0.22 0.17
4.0 0.99 0.98 0.94 0.07 0.94 0.06 0.89 0.73 0.5 1 0.53 0.45 0.55 0.35 0.30
5.0 0.99 0.99 0.99 0.00 1.00 0.00 0.97 0.86 0.74 0.25 0.65 0.28 0.59 0.54
6.0 0.99 0.99 0.99 0.00 1 .oo 0.00 0.98 0.90 0.84 0.10 0.90 0.10 0.8 1 0.80
7.0 0.99 0.99 0.99 0.00 1 .oo 0.00 0.99 0.92 0.88 0.04 0.94 0.06 0.86 0.85
8.0 0.99 0.99 0.98 0.01 1.00 0.00 0.97 0.94 0.90 0.05 0.94 0.07 0.85 0.75
9.0 0.99 0.99 0.98 0.01 1 .oo 0.00 0.96 0.94 0.88 0.12 0.88 0.11 0.72 0.55
10.0 0.99 0.99 0.96 0.03 0.97 0.02 0.95 0.88 0.80 0.17 0.84 0.15 0.58 0.40
11.0 0.99 0.99 0.96 0.03 0.96 0.05 0.94 0.80 0.75 0.17 0.84 0.15 0.60 0.42
12.0 0.99 0.99 0.96 0.02 0.97 0.03 0.95 0.85 0.80 0.13 0.86 0.12 0.70 0.60
13.0 1 .oo 1 .oo 0.97 0.01 0.98 0.02 0.97 0.92 0.87 0.07 0.93 0.05 0.84 0.79
14.0 1 .oo 1 .oo 0.99 0.00 1 .oo 0.00 0.99 0.98 0.99 0.00 1 .oo 0.00 0.98 0.98

a a: residual qlutamic acid; a’: pyroqlutamic acid formed from glutamic acid; b: residual monosodium glutamate; b’: pyroglutamic acid formed
from monosodium glutamate.
very acid media preserved glutamic acid over the 50 days, not form because there was no ammonia source in the
but less efficiently than when it was stored without atmos- media studied. It seems more interesting to have shown that
pheric contact. The same phenomena occured at room tem- glutamic acid does not decarboxylate into y-aminobutyric
perature in the presence of air, but were a little less marked acid under any of the conditions tested. The similar be-
I
than in the presence of oxygen (Table 2). havior of glutamic acid and monosodium glutamate were
Glutamic acid stored at 4’C without atmospheric con- also expected. In alkaline media, the acid forms the salt
tact was better preserved than at room temperature under (more or less completely in the solutions considered, de-
the same conditions, or under nitrogen (Table 2). It was pending on the alkali concentration), and when mono-
completely converted to pyroglutamic acid in this case sodium glutamate is in acid mediaj glutamic acid is dis-
also, when degradation was observed. placed from its salt by hydrochloric acid (also according to
Glutamic acid submitted to boiling under reflux re- the concentration), because it is weaker (pK, : 2.19, pKz :
mained stable over 60 min in very acid, in almost neutral 4.25).
and in very alkaline media (Table 3). On the contrary, two The study has shown that glutamic acid was converted
lability maxima were observed close to pH 11 and pH 2. to pyroglutamic acid as soon as it was no longer under
The conversion resulted only in pyroglutamic acid. extreme pH conditions (pH 0 or pH 14). Given that the
When glutamic acid was autoclaved, it showed a good majority of food products fall into the pH range 4 - 6, a
degree of stability in very acid and very alkaline media. large part of native glutamic acid or monosodium glutamate
It was a little more stable in the latter case (Table 3). The added as a taste-active ingredient may be converted into
greatest lability was observed at pH ranging from 2 to about pyroglutamic acid when the products are either stored
3.5. Another, less marked, lability range occurred between under normal conditions, or boiled, or canned.
pH 8 and pH 13. The conversion was greater and faster than
that observed in boiling, and the two pH ranges correspond- CONCLUSION
ing to the greatest lability shifted a little towards neutrality. THE STUDY we conducted allowed us to underline some
All the glutamic acid degraded was converted to pyroglu- factors such as the influence of pH and temperature on the
tamic acid only. glutamic acid and monosodium glutamate stability, or the
Under all conditions, the results obtained with mono- identity of the conversion product obtained. It should be
sodium glutamate were similar to those obtained with glu-
borne in mind that the conversion to pyroglutamic acid is
tamic acid under corresponding conditions (Tables 2 and important in the slightly acid pH range, which corresponds
3), as would be expected a priori. from a practical point of view to the majority of food prod-
ucts.
DISCUSSION
THE STUDY was performed on aqueous solutions to deter- REFERENCES
mine the individual effect of each factor influencing the Airaudo, Ch.B., Gayte-Sorbier, A., and Armand. P. 1984. Stability
degradation of glutamic acid. Foods were considered to be of pyroglutamic acid. Influence of physical and technological
factors. J. Food Sci. (submitted for publication).
too complex, because several factors may play a role simul- Armand, P., Abello, G., and Gayte-Sorb&. A. 1976. M&thodes de
taneously and their influences may be complementary or dosage? du glutamate de sodium. II. Potages en bolte, sauces, plats
cuisines, assalsonnements et aromes divers. Ann. Fals. EXP. Chim.
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permitted a generalization; the eventual discordances which Bern& E., and Bergmeyer, H.U. 1974. L-Glutamate. Determination
might be subsequently observed in foods could be attributed with glutamate deshydrogenase. diaphorase and tetrazolium salts.
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other phenomena. Bibeau. T.C. and Clydesdale, F.M. 1975. Organic acid profiles of
thermally processed carrot puree. J. Milk Food Technol. 38: 518.
Whatever the storage conditions, the applied processing El Miladi. S.S.. Gould, W.A., and Clements, R.L. 1959. Heat proc-
and the pH values, glutamic acid and monosodium gluta- essing effect on starch, sugars, proteins, amino acids, and organic
acids of tomato juice. Food Technol. 23: 93.
mate were only converted to pyroglutamic acid. Conver- Filer, L.J. Jr.. Garattini, S., Kare, M.K., Reynolds, W.A. , and Wurt-
sion to glutamine or to y-aminobutyric acid was never man. R.J. 1979. “Glutamic Acid: Advances in Biochemistry and
observed. We could assume a priori that glutamine would Physiology.” Raven Press. New York. NY.
-Continued on page 360

I 352-JOURNAL OF FOOD SCIENCE-Volume 50 (1985)