Research Paper
Research Paper
Research Paper
Sweet cherries and other fruits are preserved in sul- control are given in papers by Waiters et al. (1963) and
fur dioxide solutions for manufacture into maraschino, Yang et al. (1966).
cocktail, and glace fruit. The sulfur dioxide solution, Sulfur dioxide and calcium are directly related to
commonly called brine, may be prepared from liquid brined cherry quality. Improper use of these chemicals
sulfur dioxide, sodium bisulfite, or sodium metabisulfite may result in cherries that are soft, poorly bleached, or
using alkali or acid to control pH. Calcium salts such as spoiled due to fermentation. It is the purpose of this
calcium hydroxide, calcium carbonate, and calcium chlo- circular to show how the basic chemical and preservative
ride are added to the brine to prevent cracking and pro- components of brine solutions are afifected during prep-
mote firming of the fruit tissue through interaction with aration, storage, and use.
pectic materials. Directions for brine preparation and
When sulfur dioxide or materials containing sulfur range of sulfur dioxide concentrations, the relative dis-
dioxide (bisulfite or metabisulfite) are dissolved in tribution of the sulfur dioxide ionic forms is constant.
water, three types of chemical substances are formed: Within the initial pH range used for brining cher-
sulfurous acid (H2SO3),1 bisulfite (HSO3"), and sulfite ries, there is a predominance of calcium bisulfite
(SO~). The amount of each substance formed depends (Ca(HS03)2) and sulfurous acid (HjSOs), both
upon the pH (hydrogen ion concentration) of the solu- forms being water soluble. However, calcium sulfite
tion, which is regulated by the amount of sulfur dioxide (CaSOs), which is highly insoluble, precipitates as the
present and/or by addition of acid or alkali. The effect pH of the brine is adjusted upward, giving the brine a
of pH upon the ionic forms of sulfur dioxide is shown milky-white appearance. This usually occurs within a
in Figure 1. Brine solutions containing sulfur dioxide range of pH 2.8-3.2, varying with the sulfur dioxide
exhibit the same general equilibrium characteristics; concentration and temperature of the sulfur dioxide so-
their chemical properties are somewhat dififerent, how- lution. For example, lower sulfur dioxide concentrations
ever, since brine solutions form insoluble calcium sulfite. and/or cool brine temperatures shift the precipitation
The chemical reaction for sulfur dioxide-calcium brine point of calcium sulfite and permit adjustment of brine
is given below. to higher pH values. Formation of white calcium su'fite
precipitate indicates excessive use of alkali and should be
Ca(OH), Ca(OH)2
avoided. Cherries placed in brine solutions containing
S02 + H20^±H2SOs^± Ca (HSCM^CaSOjJH-H.O
calcium sulfite or solutions with an initial pH above 3.2
Addition of alkali raises the pH and shifts the reac- may be inadequately bleached and are subject to crack-
tion to the right, while lowering the pH with acid forces ing and spoilage. Brines prepared with insufficient alkali
a shift to the left. An increase or decrease in tempera- (pH below 2.5) lose excessive amounts of sulfur dioxide
ture will bring about a left or right shift respectively. to the atmosphere during brining and this may cause
For any given pH and temperature within a limited cracking and softening of the fruit. The alkali/acid ad-
justment of brines should be such that the sulfurous
1
Experiments in recent years have tended to disprove the ex- acid portion is approximately half neutralized to give a
istence of HvSO:. molecules, or at least show they are present in
infinitcsimally small concentrations in aqueous sulfur dioxide
theoretically complete conversion of sulfurous acid
solutions. The term sulfurous acid (H-SO.-t) as it is used in this (H2SO.,) to calcium bisulfite (Ca(HSO:,)2). In reality,
paper descrihes undissociated sulfur dioxide in aqueous solutions. complete conversion to calcium bisulfite is never at-
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tained since the three forms overlap (Figure 1) to give condition is upset, calcium sulfite begins to precipitate
some sulfurous acid and calcium sulfite. However, half- and continues to do so until equilibrium is restored.
neutralization of the brine solution gives an optimal sul- Onset of precipitation may be detected by monitoring
furous acid-calcium bisulfite ratio by minimizing cal- levels of sulfur dioxide, calcium, and pH. Appreciable
cium sulfite formation and sulfur dioxide volatilization. changes in one or more of these factors will affect
Adjusting the pH to give a clear brine does not pre- brined fruit quality.
vent precipitation of calcium sulfite indefinitely. Small Variation in initial pH of brine solution within the
amounts of calcium sulfite are formed in all brine solu- range of 2.5 to 3.3 and sulfur dioxide concentration
tions^ but they remain temporarily soluble in a super- within 0.75 to 1.50% has little effect on retention of cal-
saturated condition. Supersaturated solutions are un- cium and sulfur dioxide. There is a gradual decrease in
stable and susceptible to temperature changes, seeding, concentration at all levels, with brine containing higher
and nucleation of the precipitate by foreign solid mate- initial calcium and sulfur levels maintaining slightly
rial introduced into the brine. Once the super.saturated higher levels throughout storage.
Elevated temperatures are the primary cause of brine mental brine containing sodium bisulfite and calcium
instability during storage, drastically reducing the level chloride was acidified to pH 3.0 with citric acid and held
of calcium ions (Figure 2) and sulfur dioxide (Figure eight weeks at 70° F. It retained essentially all of its
3). High temperatures also lower the pH. Low pH calcium and twice as much sulfur dioxide as a control
coupled with reduced calcium levels may cause cracking sodium bisulfite brine acidified with hydrochloric acid.
and softening of brined fresh fruit. Brines prepared Brines often are prepared in advance and held for
and stored at cooler temperature (40° F) are more re- extended periods of time prior to use. This appears to
sistant to deterioration. Calcium and sulfur dioxide be an undesirable practice due to brine instability. In
losses incurred during storage should be corrected be- view of the changes occurring in brines during storage,
fore fresh fruit is brined to assure high quality brined it is recommended that brines be used within 48 hours
cherries. following preparation. If this is not convenient and ex-
Brines should be prepared and used fresh to provide tended brine storage is necessary, calcium and sulfur
maximum firming, bleaching, and preservation. A rapid dioxide losses should be determined and the brine re-
method of preparation was given by Weast (1940). It adjusted to desired concentrations before brining fresh
provides rapid preparation of brine by introducing fruit.
liquid sulfur dioxide into a lime suspension. Using this Recommended levels of calcium ion in fresh brines
procedure, brine can be prepared much faster than by range from 3,000 to 5,000 ppm, depending upon the va-
the method of adding alkali slurry to sulfur dioxide riety and maturity of fruit. Additional calcium in the
solutions. Both methods of preparation have essentially form of calcium chloride may be added to assist in firm-
the same storage characteristics in terms of stability. ing the cherry. Brekke et al. (1966) suggest that calcium
In laboratory brining trials at Oregon State Univer- also serves to inhibit enzymatic softening. They report
sity, improved storage of brines has been achieved that addition of 2% calcium chloride by weight of fruit
through use of chemicals which prevent precipitation of above the usual amount of calcium salts prevents enzy-
calcium sulfite. Citric acid and citrate salts improve brine matic and non-enzymatic softening in brined cherries.
stability by sequestering calcium ions and thus prevent- A rapid method for determination of calcium in brines
ing formation of insoluble calcium sulfite. An experi- and brine adjustment is given later in this publication.
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DAYS
Preservation of cherries and other brined fruit is more effective than bisulfite in controlling yeasts and
made possible through the use of sulfur dioxide. The molds (Rehm and Wittmann, 1962). In fact, many in-
preservative effect of sulfur dioxide is not permanent vestigators believe that the bisulfite and sulfite forms
and is reduced or lost when the sulfur dioxide content is have little or no preservative properties. Rehm and Witt-
lowered due to volatilization, oxidation to the sulfate ion, mann (1962) mentioned that the most common orga-
precipitation as calcium sulfite, or combination with nisms are inhibited by 200 to 300 ppm sulfite, but with
fruit_constituents as orgariic-bisulfite compounds. The notable exceptions. It is the more resistant microbial
pH of sulfur dioxide solutions is perhaps the most im- strains that cause difficulty in commercial practice. Cruess
portant single factor affecting preservation. (1932) found that at pH 3.5, two to four times as much
Sulfur dioxide solutions are effective preservatives sulfur dioxide was required to inhibit microbial growth
only at relatively low pH values (high hydrogen ion as at pH 2.5. At pH 7.0, sulfur dioxide was ineffectual
concentration). This may be due to an extensive pene- on mold and yeast, while 1,000 ppm was required to
tration of microbial cell walls by un-ionized sulfur diox- inhibit bacteria. Rahn and Conn (1944) suggest that at
ide where it acts to reduce essential enzyme disulfide high pH values the bisulfite ion functions to inhibit bac-
linkages (Wyss, 1948). The most effective agents are teria but is not effective against yeasts.
molecular sulfur dioxide gas (SO2) and sulfurous acid Yeasts which have been subjected to high concen-
(H2SO3), both of which are present at low pH. Care- trations of sulfur dioxide for a period of time develop
ful attention must be given to control of brine pH since a tolerance for SO2 and are able to grow and ferment
shifts in pH profoundly affect the relative proportions under what would otherwise be abnormal conditions. The
of the sulfur dioxide forms. For example, the concen- authors have observed yeast growth in brined cherries
tration of sulfurous acid (HzSO.,) in a 0.5% sulfur with a pH of 3.3 and 3,200 ppm free sulfur dioxide
dioxide solution at pH 3.0 is 5.91% or 295 ppm H2SO3. (98 ppm HoSOs). The fermentation was quite active
At pH 4.0, the concentration of sulfurous acid de- and evolved copious amounts of carbon dioxide, causing
creases to 0.6% or 31 ppm HjSOs (Figure 4). gas pocketing and softening of the fruit. Yeasts are
Sulfurous acid (H2SO.-,) inhibits yeasts, molds, and particularly resistant to sulfur dioxide once they have
bacteria, but not with equal effectiveness since yeasts are attained a full fermentation rate. Amerine (1967) sug-
the most resistant. Surfurous acid is 100 to 1,000 times gests this is due to fixation of sulfur dioxide by the
PERCENT OF TOTAL FREE S02
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metabolite, acetaldehyde. Consequently, the arrest of ranging from 4 to 80 ppm. In commercial practice, fer-
fermentation is often difficult, requiring unusually high mentation may occur in cherry brines containing as high
levels of sulfur dioxide. as 98 ppm sulfurous acid. Observation and analysis of
During curing and storage of brined cherries, the commercial samples of cherry brine over a wide range
concentration of sulfur dioxide is reduced continually of pH and sulfur dioxide levels indicate 100 to 125 ppm
through volatilization and combination with fruit sugars sulfurous acid sufficient to provide preservation.
and other- organic materials forming sugar-bisulfite Large tanks and tote bins of fruit are particularly
compounds. Joslyn and Braverman (1954) noted that vulnerable to microbial attack because of their large sur-
the rate of sugar-bisulfite formation is influenced by pH, face area. This is especially true during warm weather
temperature, ahd sugar content of the sulfur dioxide so- when sulfur dioxide losses are at a maximum and tem-
lution. Although sugar-bisulfite compounds remain in peratures are optimum for microbial growth. Storage
solution, they no longer have preservative properties. tanks are also susceptible to stratification; if tanks
Yang et al. (1966) recommend a free sulfur dioxide are not sealed properly, dilution by rain water will raise
content of 7,500 ppm to be maintained during storage the pH and reduce the sulfurous acid content. Stratifica-
and shipping of brined cherries. This level of sulfur di- tion can be avoided by periodic circulation, which will
oxide provides preservation and allows for some loss help to maintain uniform conditions throughout the tank.
prior to finishing. Free sulfur dioxide, pH, and sulfurous acid values
It would be convenient for all concerned if it were should be determined at regular intervals as a quality
possible to specify a minimum concentration of sul- control measure. If the sulfurous acid concentration
furous acid above which complete preservation could drops below the critical level, adjustment should be
be maintained. However, establishment of such a stand- made. This may be accomplished by careful addition of
ard is prohibited by variations caused by storage tem- sulfur dioxide or acid in amounts sufficient to increase
peratures, brining techniques, quality of fruit, and mi- the sulfurous acid concentration to a safe level. Soften-
crobial load, and particularly those caused by microor- ing of the fruits may occur if the brine pH is reduced
ganisms resistant to sulfur dioxide. Amerine (1967), below 3.0 for extended periods. A record of this infor-
Joslyn and Braverman (1954), and Rahn and Conn mation for each tank would be helpful in maintaining an
(1944) indicate inhibition of most common yeast and adequate concentration of sulfurous acid and avoiding
bacteria is achieved bv concentrations of sulfurous acid fermentation and spoilage of the fruit.
Methods of Analysis
Pipette 5 ml of the brine solution into a 250 ml 2. Determine parts per million (ppm) free sulfur
Erlenmeyer flask containing approximately 100 ml dis- dioxide by direct iodine titration.
tilled water. Add 1 ml of starch solution and five drops 3. Refer to Figure 4 and obtain the percentage sul-
of 20% sulfuric-acid. Titrate with standardized 0.156 N furous acid corresponding to the pH of the sample solu-
iodine solution until a blue color persists for 30 seconds. tion.
Multiply the ml iodine required by 1,000 to obtain parts 4. Multiply ppm free sulfur dioxide by the percent-
per million free sulfur dioxide, or by 0.1 to give percent age of sulfurous acid to obtain parts per million sulfu-
free sulfur dioxide. rous acid.
Example 1:
Sulfurous Acid pH = 3.0
Utilization of free sulfur dioxide as a means of esti- SO, (ppm) = 5,000 (iodine titration)
mating the effective preservation of brine is misleading % H2S03= 5.91% (from Figure 4)
since the iodine titration does not distinguish between H2S03 (ppm) =0.0591 x 5,000
the three forms of sulfur dioxide in solution. Therefore = 295.0
it becomes necessary to use the pH in conjunction with
the free sulfur dioxide concentration to determine if Example 2:
sufficient sulfurous acid is present to insure preserva- pH = 3.7
tion. The sulfurous acid content of a sample solution SOo (ppm) = 5,000 (iodine titration)
may be closely approximated in the following manner: % H2SO.H= 1.21% (from Figure 4)
1. Measure the pH of the brine sample with a prop- H...S03 (ppm) =0.0121 x 5,000
erly standardized pH meter. = 60.5 ppm
From these examples it is apparent that effective Determination of calcium in cherry brine.
preservation of sulfur dioxide solution, expressed in Transfer 1.0 ml of well-mixed brine sample into a 500
parts per million sulfurous acid (H2SO3), is appreci- ml flask containing 200 ml distilled water. Add 5 ml am-
ably reduced by shifts in pH, even though the iodine monium hydroxide buffer, six drops indicator, and ti-
titration for free sulfur dioxide remains constant. trate immediately to the blue endpoint.
ppm Ca++ =
Calcium (ml EDTA used) (mg calcium/ml EDTA) (1,000)
Literature Cited
Amerine, M. A., H. W. Berg, and W. V. Cruess. 1967. The Rahn, O., and J. E. Conn. 1944. Effect of Increase in Acidity on
Technology of Wine Making, 2nd ed. VVestport, Conn.: Antiseptic Efficiency. Ind. Eng. Chem., 36:185-187.
AVI Publishing Co., Inc., 188-192. Rehm, H. J., and H. Wittmann. 1962. Z. Lebensm, Untersuch-
AOAC. 1965. Official Methods of Analysis, 10th ed. Washing- Forsch, Ji5:413-429.
ton, D. C.: Association of Official Agricultural Chemists. Walters, G. G., J. E. Brekke, M. J. Powers, and H. Y. Yang,
Brekke, J. E., G. G. Walters, R. Jackson, and M. J. Powers. (rev. 1963). Brined Cherries: Analytical and Quality Con-
1966. Texture of Brined Cherries. U.S. Dept. of Agric, trol Methods. U.S. Dept. of Agric. ARS 74-23.
ARS 74-34. Weast, C. A. 1940. Preparation of Solution to be Used in Brin-
Cruess, W. V. 1932. Hydrogen-Ion Concentration in Preserva- ing Cherries. Western Canner and Packer, 32(6) :26-27.
tive Action. Ind. Eng. Chem., 24:648-649. Wyss, A. 1948. Microbial Inhibition by Food Preservatives.
Joslyn, M. A., and J. B. S. Braverman. 19S4. Chemistry of Sul- Adv. Food Res., 2:373-393.
fur Dioxide, Sulfites, and Their Organic Compounds. Adv. Yang, H. Y., E. Ross, and J. E. Brekke. 1966. Cherry Brining
Food Res., 5:97-160. and Finishing. Ore. Agric. Expt. Sta. Cir. of Inform. 624.