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Food Quality and Preference 14 (2003) 319–325

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The taste of calcium and magnesium salts and anionic modifications


Harry T. Lawless*, Frank Rapacki, John Horne, April Hayes
Department of Food Science, Stocking Hall, Cornell University, Ithaca, NY 14853, USA

Abstract
Taste properties of divalent salts are complex. The first study examined the taste profiles of calcium chloride, magnesium chloride
and magnesium sulfate. These divalent cation salts were characterized primarily by bitter taste, with additional sensations described
as salty, metallic, astringent, sour and sweet, generally in decreasing order of intensity. A second study examined the taste proper-
ties of calcium salts other than chloride. Calcium gluconate, calcium glycerophosphate and calcium lactate had lower salty and
bitter responses than equimolar concentrations of calcium chloride, an effect suggesting anionic inhibition.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Calcium; Magnesium; Taste; Bitterness; Inhibition

1. Introduction Halpern, and Desimone (1999) pointed out that


MgSO4, which has been used at times as a bitter taste
Calcium fortification is an increasingly common stimulus, has bitter, salty and sour tastes. Schiffman and
practice that is used to add nutritive value to many Erickson (1971) classified calcium and magnesium chlo-
foods and beverages. Insufficient consumption of diet- ride as bitter-salty based upon their position in multi-
ary calcium can contribute to risks for calcium defi- dimensional scaling space. Monovalent halides also
ciency and osteoporosis, a condition affecting 20–30 stimulate multiple taste qualities and the general pat-
million Americans and a major cause of bone fractures terns are much better understood. In 1981, Murphy,
among the elderly (Williams, 1999). Calcium addition Cardello, and Brand published a landmark study that
has provided a market niche for food and beverage systematically examined the two important columns of
products in keeping with the recent trend to produce the periodic table for monovalent salts. The taste prop-
multi-functional and nutritionally fortified food (Sloan erties of 15 monovalent halides, including the chloride,
& Stiedman, 1996). According to FDA regulations, a bromide and iodide salts of lithium, sodium, potassium,
fortifying agent can be added to foods if it is used to rubidium and cesium were profiled. As the atomic
correct a dietary insufficiency recognized by the scien- weight of the anion or cation increased, bitter and sour
tific community that results in a nutritional deficiency tastes increased and came to predominate over saltiness
disease. Based on that interpretation, the food industry (only sodium chloride and lithium chloride were
is producing breakfast cereals, powered drink mixes and primarily salty).
waters fortified with calcium to help the consumer A similar systematic evaluation of the tastes of multi-
achieve intakes consistent with recognized nutritional valent salts is lacking, although they have been used
requirements and aimed at preventing osteoporosis sporadically in taste research including studies of the
(Weaver, 1998). In spite of these widespread applica- metallic taste of iron sulfate (e.g. Hettinger, Myers, &
tions, little has been published in the psychophysical Frank, 1990) and the use of magnesium sulfate (Del-
literature on the taste properties of calcium salts or wiche, Butelic, & Breslin, 2000; Keast & Breslin, 2002;
other multivalent ionic compounds in simple aqueous McBurney, Smith, & Shick, 1972; Yokomukai, Cowart,
solutions (Tordoff, 1996). & Beauchamp, 1993) and magnesium chloride (Schiff-
The general consensus about the tastes of divalent man & Erickson, 1971) as bitter taste stimuli . Recently,
salts is that they are complex. For example, Delwiche, psychophysical characterization of calcium salts was
carried out by Tordoff (1996). He found thresholds for
* Corresponding author. Tel.: +1-607-255-7363; fax: +1-607-254-
chloride, lactate, hydroxide, phosphate and gluconate
4868. salts to be in the range of 8–50 mM. Calcium chloride
E-mail address: htl1@cornell.edu (H.T. Lawless). was characterized as bitter, sour and sweet at 1 mM but
0950-3293/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
PII: S0950-3293(02)00128-3
320 H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325

bitter, salty and sour at 100 mM. The purpose of weak on the labeled magnitude scale. Concentrations
Experiment 1 was to extend those results to include were raised for this study to provide a clearer sensory
additional concentrations, to report intensity scaling of impressions. However, calcium sulfate was not soluble
all sensory attributes (not just the four classical taste above the second concentration step and was therefore
qualities), and to provide a comparison of magnesium omitted.
and calcium salts. Calcium was of interest because of its
use in nutritional fortification. Unfortunately, a direct 2.1. Methods
comparison of the taste properties of magnesium sulfate
to calcium sulfate proved difficult due to the solubility Twenty-eight healthy subjects (11 female) with no
limitations of calcium sulfate (Rapacki, 2001). There- reported taste or smell problems from the Cornell Uni-
fore, calcium chloride was examined, as well as versity community in Ithaca, NY volunteered to parti-
magnesium chloride. cipate and completed this study. Informed consent was
As shown by Murphy et al. (1981), the anion has an given. Subjects were paid at the conclusion.
effect on the taste properties of a salt. If it did not, During orientation, panelists were given reference
sodium chloride, bromide and iodide would all taste the samples of 0.15 M sucrose for sweetness, 0.32 M NaCl
same, but they are perceptually different. Calcium is for saltiness, 0.19 M citric acid for sourness, 0.00009 M
added to foods as the cation in divalent salts with var- quinine HCl for bitterness, 0.009 M monosodium glu-
ious anions. The idea that anions play an important role tamate for umami, and 0.002 M aluminum ammonium
in the perception of salts has been supported by studies sulfate for astringency. A sanitized copper penny was
that show large organic anions prevent calcium from used as a metallic reference. Panelists were instructed
acting on receptor sites in rats (Nakamura & Kurihara, that the ‘other’ category was to be used for oral sensa-
1991). Recent work from Desimone and colleagues in tions that did not fit into any of the other categories, for
physiological recordings from rat chorda tympani and example ‘irritation’. The experimental samples consisted
voltage clamping studies have helped explain decre- of calcium chloride, magnesium chloride, and magne-
ments in saltiness when anions other than chloride are sium sulfate, each prepared at concentrations of 0.01,
present (Ye, Heck, & Desimone, 1991, 1993). The dif- 0.018, 0.032, 0.056, and 0.1M in deionized water (15 ml,
fusion of larger anions across tight junctions and into 22 C) and labeled with three-digit random codes.
basolateral areas of taste receptor cell channels is lim- Panelists were required to complete a training session
ited, therefore salts with larger anions are less effective and two experimental sessions. Vocabulary was based
stimuli. Delwiche et al. (1999) provided psychophysical on preliminary work with lower concentrations of cal-
parallels in humans to these observations. Even when cium and magnesium salts (Rapacki, 2001). Sensations
the anions are not present in the stimulated area, they of sweetness, saltiness, sourness, bitterness, metallic
may exert an inhibitory effect. Miller (1971) showed a taste, umami, astringency and ‘other’ tastes were
dramatic inhibition of response of a single fungiform described to panelists using examples as follows: sugar
papilla to NaCl when the surrounding area was stimu- for sweetness, table salt for saltiness, lemons for sour-
lated with potassium benzoate. This converged with ness, black coffee for bitterness, placing a penny in the
earlier observations by Beidler that benzoate was largely mouth for metallic, red wine for astringent, and irrita-
inhibitory. Tordoff (1996) also reported that calcium tion from hot salsa as an example of ‘other’. Panelists
lactate solutions were rated less bitter than equimolar were then given the reference samples in random order
calcium chloride solutions. The purpose of Experiment (15 ml at 22  C). Panelists rinsed with each solution for
2 was to examine the taste properties of calcium salts 5 s, expectorated, and described the oral sensation.
with different anions that are used in food products Panelists then placed a sanitized copper penny into their
(lactate, gluconate and gylcerophosphate). mouth to familiarize themselves with metallic taste.
Panelists were allowed to rinse with Chemung Spring
water between all training samples. Finally, panelists
2. Perception of calcium chloride, magnesium chloride were asked to verbally describe ‘irritation’ in the mouth
and magnesium sulfate and instructed that any sensations detected in the
experimental samples that cannot be sufficiently descri-
The purpose of Experiment 1 was to provide infor- bed by one of the seven defined categories, should be
mation on the taste properties of salts of two common rated in the category labeled ‘other’.
and physiologically important elements, calcium and Magnesium salt samples (12 total) were examined in
magnesium. We had initially intended to complete a first experimental session and were balanced so half of
factorial design of the chloride and sulfate salts of both the panelists tested the magnesium sulfate set first, and
calcium and magnesium. A preliminary study used these half the magnesium chloride set first. Calcium salt sam-
stimuli (Rapacki, 2001) but sensations in the con- ples (6 total) were tasted in the second experimental
centration ranges selected (0.01 M or less) were only session. Panelists were instructed to swish each of the
H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325 321

samples in the mouth for 15 s, expectorate, and then [F(2,54)=11.2]; magnesium chloride and calcium
rate the sample on eight attributes—sweetness, saltiness, chloride were more bitter than magnesium sulfate
sourness, bitterness, metallic, astringent, umami, and (Duncan tests).
other—using a horizontal labeled magnitude scale The less salient taste properties are shown in
(Green, Shaffer, & Gilmore, 1993). Between each sam- Fig. 2. Sweetness decreased with concentration
ple panelists were required to rinse with deionized [F(4,108)=3.95] possibly due to intramolecular ‘mixture
water, and eat a cracker if desired. All panelists received suppression’ as the bitter tastes became more promi-
15 ml of each sample and all samples were served at nent. Murphy et al. (1981) were able to show mixture
room temperature, approximately 22  C. Sessions took suppression by various taste qualities of monovalent
place on separate days. Data were collected using halide salts, and demonstrate release of mixture sup-
Compusense 5 (Guelph, Ontario, Canada) along with pression through cross adaptation for ionic salts. For
information regarding gender and age. Descriptive sta- example, an increase in sweetness for sodium chloride,
tistics were collected and a three-way repeated measures potassium chloride, rubidium chloride, cesium chloride,
ANOVA was performed with chemical and concentra- potassium bromide, and rubidium bromide occurred
tion as within subject factors using Statistica v.5.1 after exposure to sodium chloride. The other more
(Statsoft, Inc. Tulsa, OK). Statistics reported below are intense tastes of these divalent salts may be suppressing
significant at P < 0.05 unless stated otherwise. a low level intrinsic sweet taste (Bartoshuk, Murphy, &
Cleveland, 1978). Umami ratings increased with con-
2.2. Results and discussion centration but appeared to plateau [F(4,108)=3.73] and
there were slight differences among compounds
The predominant taste sensations were saltiness and [F(2,54)=6.51] with calcium chloride being the most
bitterness and both increased with concentration umami at these concentrations. No differences among
[F(4,108)=10.2 for salty and 40.5 for bitter] as shown in the compounds or concentrations were noted for the
Fig. 1. Saltiness showed a concentration by substance other taste qualities (sour, metallic, other).
interaction as calcium chloride increased, while the
magnesium salts remained at a low but perceivable
intensity [interaction F(8, 216)=8.2]. Bitterness differed 3. Effects of organic anions on the taste of calcium
salts

In examining the calcium content of various fortified


foods, we determined that calcium was often added to
foods as the salt of organic anions such as lactate or
gluconate. Given the predominance of bitter taste of
CaCl2 noted in Experiment 1 and the tendency of some
anions to inhibit tastes associated with chloride salts,
Experiment 2 was conducted to examine anion effects.
Tordoff (1996) had noted lower bitterness of calcium
lactate solutions compared with equivalent levels of
calcium chloride. Concentrations were raised to exam-
ine a wider range of calcium tastes. Magnesium salts
were not included in this study due to an overall focus
of the experimental program on the properties of calcium.

3.1. Methods

Two groups were tested. In Group 1, 25 healthy adult


subjects (eight male) with no self-reported problems in
taste or smell from the Cornell University community in
Ithaca, NY volunteered to participate. In Group 2, 17
healthy adult subjects (eight female) were tested.
Informed consent was given. Subjects were paid a token
incentive at the conclusion of the study.
Panelists were given solutions of reference samples to
taste as described in Experiment 1. A sanitized copper
Fig. 1. Taste intensity of calcium and magnesium chloride and mag- penny was used as a metallic reference. Panelists were
nesium sulfate across concentrations for bitter and salty qualities. instructed that irritation meant sensations similar to hot
322 H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325

Fig. 2. Taste intensity of calcium and magnesium chloride and magnesium sulfate across concentrations for sour, metallic, sweet and umami qualities.

salsa, hot peppers or Tabasco. Group 1 panelists tasted In the first experimental session, panelists were pre-
calcium chloride and calcium lactate solutions at 0.01, sented with eight samples (15 ml, 22  C) labelled with
0.03, 0.1 and 0.3 M. Group 2 panelists tasted 0.03 and three digit blinding codes. Presentation order was ran-
0.06 M solutions of calcium gluconate, calcium glycer- domized. Panelists were instructed to swish each of the
ophosphate, and calcium chloride. Concentrations were samples in the mouth for 15 s, expectorate, and then
chosen to produce a perceivable taste of intermediate rate each sample using a horizontal labeled magnitude
intensity and be within solubility limitations. Solutions scale (Green et al., 1993). Between each sample panelists
were prepared using deionized water as the diluent. were required to rinse with deionized water for 30 s, and
Attributes were determined by benchtop screening eat a cracker if desired. The second experimental session
and in reference to previous work (Rapacki, 2001). replicated the first on a separate day.
Group 1 used the attribute ‘astringency’ to refer to oral Data were collected using Compusense 5 (Guelph,
tactile sensations. After further data were gathered in Ontario, Canada). Descriptive statistics were collected
other mixture studies (Rapacki, 2001), panelist con- and repeated measures ANOVAs were performed with
sensus indicated that the tactile sensation from CaCl2 replicates, type of anion, and concentration as within
was better described as slightly irritative rather than subject factors (Statistica v.5.1, Statsoft, Inc. Tulsa,
astringent (drying) and so irritation replaced the astrin- OK). All statistics reported below were significant at
gent scale for Group 2. Oral sensations of saltiness, bit- P < 0.05 unless stated otherwise.
terness, metallic taste, sourness, and irritation were
described to panelists using examples as follows: lemons 3.2. Results and discussion
for sourness, table salt for saltiness, black coffee for
bitterness, placing a penny in your mouth for metallic, Calcium lactate solutions were less intense than cal-
and hot salsa as an example of irritation. Panelists were cium chloride across all attributes but sweetness. Fig. 3
then given reference samples, 15 ml at 22  C, in random shows the mean intensity ratings for calcium chloride
order. Panelists were asked to rinse with all 15 ml of the and lactate across concentrations. Calcium chloride
reference solution for 5 s, expectorate, and verbally samples were judged more metallic, sour and astringent
describe the oral sensation. Panelists placed a sanitized than calcium lactate across concentrations
copper penny in the mouth to familiarize themselves [F(1,24)=4.64, 4.72 and 3.56 (P < 0.07)]. Decrements for
with metallic taste. Panelists were allowed to rinse with the more salient characteristics of bitterness and salti-
Chemung Spring water between all training samples. ness were even more pronounced and the size of the
Finally, panelists were asked to verbally describe ‘irri- difference increased with concentration as shown by a
tation’ in the mouth to insure that they understood the concentration by anion interaction, F(3,72)=5.84 for
concept. bitter and 17.29 for salty. Calcium lactate was judged
H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325 323

slightly sweeter than calcium chloride across concentra- 4. General discussion


tions [F(1,24=6.32)], but intensities were very low, less
than five (data not shown). Calcium is a physiologically critical nutrient for
Calcium glycerophosphate and gluconate were less humans. Calcium is consumed through food, beverages,
intense than calcium chloride across all attributes but or supplements, and is lost in urine, sweat, feces and
metallic. Fig. 4 shows the mean intensity ratings for milk. Approximately 99% of calcium is stored in the
calcium chloride, glycerophosphate and gluconate at skeleton, but it is also important in nerve and muscle
0.03 and 0.06 M. Calcium chloride was judged more contraction, blood clotting and membrane permeability.
bitter, salty, sour and irritative than the other two cal- Calcium is absorbed in the bones until approximately
cium salts [F(2,32)=20.71, 55.84, 7.57 and 19.95, the mid-30s and the highest levels of calcium absorption
respectively]. For saltiness and irritation, the differences occur during adolescence and pregnancy (Whitney &
among salts were greater at the 0.06 M concentration Rolfes, 1999). Levels of calcium in the blood are tightly
than the 0.03M concentration [interaction regulated in humans. When blood calcium levels fall,
F(2,32)=26.07 and 8.47, respectively]. calcium is taken from bone and reabsorbed into the
In comparison to the first experiment, these higher bloodstream. Calcium balance can be affected by a
concentrations of calcium chloride appeared to have a variety of factors including growth, pregnancy, age,
tactile component, labeled as astringent by Group 1 but lactation, menopause, vitamin D status, dietary protein,
reclassified as a kind of irritation by Group 2. In general dietary sodium, exercise and smoking (Insel, Turner, &
the sensations from these salts are complex and some- Ross, 2001). Understanding the taste properties of cal-
what difficult to characterize. Further work needs to cium salts may aid in the development of fortified foods
address the qualitative aspects divalent salts and whe- with greater consumer acceptance. That idea prompted
ther they possess unique sensation qualities that were our study insofar as the literature on taste properties of
not well-captured by the vocabulary imposed here. calcium and other divalent salts was sparse, with the
exceptions of MgSO4 (used as a bitter tastant) and the
psychophysical characterization of calcium salts by
Tordoff (1996). Our findings are largely consistent with
those of Tordoff regarding the taste qualities of calcium
salts and the observation of anionic inhibition.
Although calcium salts may have unpleasant taste
properties in solution, it is difficult to predict their

Fig. 3. Bitter and sour taste intensity ratings of calcium chloride and
calcium lactate (upper panel). Metallic astringent and salty ratings Fig. 4. Tastes of calcium chloride, calcium glycerophosphate and
(lower panel). Filled symbols: chlorides. Open symbols: lactates. calcium gluconate.
324 H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325

contribution to the overall flavor of foods. Mixture correlation between PROP ratings and MgSO4.
suppression (Bartoshuk, 1975; Lawless, 1986) from the McBurney et al. (1972) found cross adaptation of urea
other tastes present in a food is likely to decrease or and MgSO4, consistent with ratings differences for urea-
partially mask the tastes contributed by calcium salts sensitive (vs. quinine sensitive) individuals for MgSO4
added to a food. Previous studies on bitterness masking (Yokomukai et al. 1993). However, Keast and Breslin
by sodium chloride and sodium gluconate show little (2002) concluded that MgSO4 was an outlier in their
masking of MgSO4 bitterness by sodium salts, in con- study that included urea, i.e. that urea and MgSO4 had
trast to other bitter tastants which are effectively sup- unrelated patterns of sensitivity across persons. The
pressed by sodium ions (Breslin & Beauchamp, 1995; nature and relationships among bitter mechanisms and
Keast & Breslin, 2002). Whether these patterns of sup- overlapping patterns of responsiveness and sensitivity to
pression are also true of calcium chloride are unknown. divalent cation salts are worthy of further study.
Studies of mixture effects in simple systems with mono- One quality reported for these salts is metallic taste.
gustatory tastants such as sucrose, NaCl and citric acid Metallic taste is generally associated with stimulation by
added to calcium chloride would be informative (Law- ferrous sulfate (FeSO4). Hettinger et al. (1990) showed
less, Rapacki, Horne, Hayes, & Wang, submitted for that qualitative reports of metallic taste decreased when
publication). the sample was tasted with the nose occluded, indicating
Evidence in the present study for suppression of tastes that the metallic taste was primarily a retronasal smell.
by the anion is consistent with the previous observations Recent work in our laboratory confirms this observa-
of Tordoff (1996). The suppression of bitterness has tion for ferrous sulfate (Lawless, Schlake, & Smythe,
potential functional value since bitterness is usually 2002), but not for copper sulfate in which a residual
(although not universally) objectionable in foods. The metallic taste was reported even with nasal occlusion.
mechanisms for the anion effects are not clear at this The potential effects of retronasal smell sensations and
time. Relevant observations include the effect of large their confusion with true taste sensations indicates that
organic anions preventing calcium from acting on future evaluations should be conducted with the nose
receptor sites (Nakamura & Kurihara, 1991). The closed to eliminate or minimize such influences. It is
inability of larger anions to diffuse across paracellular unclear whether metallic tastes associated with all mul-
junctions and into basolateral areas of taste receptor cell tivalent salts are olfactory sensations. Metals such as
causes decrements in salt response (Delwiche et al., iron and copper are strong catalysts for oxidation a give
1999; Ye et al., 1991, 1993). Whether a similar mechan- rise to a number of organic products with olfactory
ism could affect bitter taste is unclear. A mechanism for potency, a well-known quality problem in food proces-
bitterness suppression was noted by Ming, Ninomiya, sing (Bodyfelt, Tobias, & Trout, 1988). Whether cal-
and Margolskee (1999) who found AMP and some clo- cium or magnesium is acting in a similar way is not
sely related analogues to block the taste receptor acti- clear. Another question concerning metallic taste is
vation of gustducin. Given the rather narrow range of whether this is an appropriate and accurate word to
AMP analogues that showed such activity, the exten- describe these sensations. Schlake (2001) found that
sion of this finding to the range chemically diverse only 7 of 25 subjects used the word ‘metallic’ to describe
organic anions used in the present study would make the taste of ferrous sulfate when given an open ended
that an unlikely mechanism. question. However, about 70% of subjects rated FeSO4
The influence of genetic mechanisms on bitter taste is as metallic when provided a rating scale with that label.
well known. The dimorphism associated with phe- Further work is needed concerning the semantic aspects
nylthiocarbamide (PTC) and propylthiouracil (PROP, a of these complex tastes. Potential methods include qua-
thyroid medication) predicts to a greater or lesser degree litative group interviews (Lawless & Corrigan, 1994)
responses to many other bitter substances. That is, per- and multivariate statistical approaches such as multi-
sons sensitive to the bitterness of PROP, and especially dimensional scaling (Schiffman, 1974; Schiffman &
those with very high sensitivity—the so-called ‘super- Erickson, 1971).
tasters’—are more likely to be responsive to the bitter-
ness of other chemically unrelated substances such as
caffeine and saccharin (Bartoshuk, 2000). They also 5. Conclusions
may be more responsive to some sweeteners (Gent &
Bartoshuk, 1983). However, Delwiche et al. (2000) have The salts of divalent cations such as calcium and
argued that this is a general sensitivity difference, per- magnesium are characterized primarily by bitter and
haps due to the larger number of taste buds present in salty tastes, and to a lesser extent by other basic tastes
PROP supertasters (Bartoshuk, Duffy, & Miller, 1994). and metallic, astringent and irritative sensations. The
At this time it is unclear as to whether the PROP taster tastes associated with calcium chloride are largely sup-
effect also predicts the bitterness of divalent cation salts. pressed when calcium is combined with larger organic
Delwiche et al. (2000) reported only a weak positive ions such as lactate, gluconate or glycerophosphate.
H.T. Lawless et al. / Food Quality and Preference 14 (2003) 319–325 325

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