THE UNIVERSITY OF ILLINOIS LIBRARY G3CX7 I-f-Cab F" , OP . 'Tn RE LTBRAITY CIRCULATING CHECK FOR UNBOUND CIRCULATING COPY A Study of the Causes of a Stale Metallic Flavor in Strawberry Ice Cream Together With Tests of Methods of Packing Berries By P. H. TRACY, R. J. RAMSEY, and H. A. RUEHE UNIVERSITY OF ILLINOIS AGRICULTURAL EXPERIMENT STATION Bulletin 407 CONTENTS PAGE SIX VARIETIES TESTED FOR USE IN ICE CREAM 411 PACKING BERRIES FOR STORAGE AT LOW TEMPERATURES.. 413 COPPER SALT PROVES BASIC CAUSE OF METALLIC FLAVOR. . 415 STUDY OF FACTORS CONTRIBUTING TO DEVELOPMENT OF METALLIC FLAVOR 417 Commercial Packs Differed in Tendency to Cause Off-Flavor 417 Heating of Fruit Retarded Off-Flavor 419 Amount of Fruit Added Is Important 420 Juice of Berry Contains Factor Causing Off- Flavor 420 Flavor Defect Associated With Presence of Butterfat 421 Citric Acid Content of Strawberries Is Not Important 422 Homogenization of Mix Retarded Off-Flavor 424 Other Fruits Than Strawberries May Cause Off-Flavor 425 OXIDATION THEORY TESTED BY OXIDATION-REDUCTION POTENTIAL MEASUREMENTS 425 Eh Measurements Show Off-Flavor Is Due to Fat Oxidation 425 Different Amounts and Different Parts of Berries Cause Varying De- grees of Oxidation 427 SUMMARY AND CONCLUSIONS 429 LITERATURE CITED.. 430 Urbana, Illinois November, 1934 Publications in the Bulletin series report the results of investigations made by or sponsored by the Experiment Station. A Study of the Causes of a Stale Metallic Flavor in Strawberry Ice Cream Together With Tests of Methods of Packing Berries By P. H. TRACY, R. J. RAMSEY, AND H. A. RUEHE* iTRAWBERRY ICE CREAM is one of the most popular varie- ties of ice cream manufactured in the United States, representing '8.27 percent of the total ice-cream production in 1931. 4 * This flavor ordinarily is exceeded in sales only by vanilla and chocolate. Altho alcoholic extracts of strawberries are available for use in manu- facturing ice cream, the entire berry is more commonly used because of the superior flavor imparted by the fruit constituents and the fact that consumers like to see the fruit in the ice cream. Tho strawberries can be preserved in various ways, the frozen- pack method, because of its reduced cost and the resulting superior flavor of the berries, is being used by many ice-cream manufacturers. Investigators who have studied this method have reported results of variety tests, methods of packing, types of sugars used, storage tem- peratures, and in some cases flavor defects. 1 3> * 5 ' 6> * 8 " 10 * The main purpose of this study was to determine the cause of the stale metallic, or tallowy, flavor that is common in strawberry ice cream. Incidentally certain facts concerning the frozen-pack method of preserving berries were secured. The study extended over a period of four years (1930-1933) and covers so many different experimental runs that the method of procedure is best presented with the data. SIX VARIETIES TESTED FOR USE IN ICE CREAM Six common varieties of strawberries marketed in southern Illinois were tested to determine their relative merits as a source of flavor in ice cream. The average number of berries per quart, the average loss in stemming, and the rating on a flavor basis of the ice cream to which the fruit was added (15 percent by weight) are given in Table 1. Losses were due to the presence of stems, small, hard, and green berries, and overripe berries. As a rule the riper the fruit the greater By P. H. TRACY, Associate Chief in Dairy Manufactures, R. J. RAMSEY, Assistant, and H. A. RUEHE, Chief. *These numbers refer to literature citations on page 430. 411 412 BULLETIN No. 407 [November, was the shrinkage in stemming. The smaller berries often were of superior flavor but required more hours of labor in stemming. The Dunlap berry, which produced the finest flavored ice cream, is not nearly so popular a market variety as the Aroma. This is prob- ably due to the fact that altho the flavor and texture of the Dunlap is TABLE 1. COMPARISON OF STRAWBERRY VARIETIES FOR USE IN ICE CREAM Varieties in order of flavor rating in ice cream Average number berries per quart Average loss in stemming 1 . Dunlap 101 perct. 10.5 2. Parson Beauty 280 7.5 3. Gandy 110 4.9 4. Premier 180 6.5 5. Gibson 102 5.5 6. Aroma 82 5.5 superior, the Aroma is a larger and more attractive berry and ships to better advantage. Parson Beauty was a very close second to the Dun- lap in quality of flavor. The more highly flavored strawberry varieties such as the Dunlap, when available, should be used for flavoring ice cream. The labor involved in preparing Dunlap berries for packing and the yield of packed strawberries is given in Table 2. These data are on the 1931 crop. The average net weight of berries per crate was 24.5 pounds, the average shrinkage being 2.5 pounds. TABLE 2. PREPARATION OF DUNLAP STRAWBERRIES FOR STORAGE AT Low TEMPERATURE Crates Weight of Man labor to Loss in Net yield' k Shipment (24-quart) berries wash stemming 2:1 3:1 4:1 1. . 5 Ibi. 127 hrs. 13 perct. 7.1 gals. 11 gals. 9 gals. 2 5 137 13.5 8 16 6 3 5 128 11.5 9.0 11 5 5 4 5 b 117 11.2 8.5 8 4 4 5 5 141 12.5 8.8 22 5 Average per crate 27 2.5 2.5 4.20 3.85 3.70 2:1 pack berries weighed 8.7 pounds per gallon; 3:1 pack berries weighed 8.50 pounds per gallon; 4:1 pack berries weighed 8.25 pounds per gallon. The proportions refer to parts of berries and sugar by weight. b LeM 16 quarts. 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 413 On the basis of the results obtained in these tests the approximate cost per gallon of berries ready for storage can be calculated by using the following formulas: cost of berries per crate -f (12.25 X cost of sugar per - . , pound) -f- 2.5 X cost of labor per hour 4.20 cost of berries per crate + (8.17 X cost of sugar per pound) + 2.5 X cost of labor per hour - . , P " 3.85 cost of berries per crate + (6. 1 X cost of sugar per pound) + 2.5 X cost of labor per hour 4:1 pack = - For example, if the cost of berries is $2 a crate, sugar 5 cents a pound and labor 40 cents an hour, the cost per gallon of each of the three packs would be calculated as follows: 2:1 pack = * + 02.25 XJ.05) + (2.5X1.40) 4.20 3:1 pack = * 2 + (8-"X*.05) + (2.5 X *.4Q) 3.85 4:1 pack = *2 + (6.1 X J.05) + (2.5 X *.4Q) O* I\J These cost figures do not represent total costs; such items as con- tainers, refrigeration, and storage must be added. Variations from these figures will result with variations in amount of shrinkage and hours of labor. PACKING BERRIES FOR STORAGE AT LOW TEMPERATURES Addition of Sugar. When strawberries are to be stored at low temperatures, the addition of sugar reduces the danger of fermenta- tion before freezing and after thawing. The sugar also preserves the color and, to some extent, the natural flavor and aroma of the fruit, and keeps the berries from becoming too hard in the frozen ice cream. The addition of sugar, however, causes the fruit juice to be withdrawn 414 BULLETIN No. 407 [November, from the berry tissue-by osmotic action. The greater the concentration of sugar on the outside of the berry the more complete will be the removal of fruit juice from the fruit tissue and the more shriveled will the fruit become. If, however, the berries are surrounded with an isotonic aqueous solution of cane or beet sugar, there will be little loss of juice by the fruit tissues and the fruit will retain its original shape. Use of a Sugar Sirup. In preserving peaches by freezing the use of a sugar sirup has many advantages over the use of sugar, according to Woodroof. 9 * His claims are as follows: (1) There is little or no change in fruit volume or in the juice volume when a sugar sirup is used. (2) The osmotic pressure of the sirup is near that of the peach juice. (3) The freezing point of the sirup is near that of the peach tissue. (4) The sirup is a better aid than sugar in preserving the color and texture on freezing and defrosting. (5) It is easier to get a uni- form distribution and coverage of sirup than of sugar. (6) The use of prechilled sirup assures a more rapid cooling of the fruit than occurs in the sugar pack. Many of these advantages in the use of a sirup in preserving peaches would very likely apply to the frozen-pack method of preserv- ing strawberries. Study of Different Methods. In order to study the importance of the method of packing strawberries, three varieties Howard 17, Bur- TABLE 3. COMPARISON OF STRAWBERRIES FROZEN-PACKED IN VARIOUS WAYS Pack Flavor Appearance Color Plain Tasteless Cell walls ruptured Water Tasteless and collapsed Slightly better than Lacking Sirup 20 percent sirup Somewhat tasteless plain pack 40 percent sirup Fairly good Normal Good 60 percent sirup Good Shrunken and mushy Good Sugar 2:1 sugar Good Similar to 60 per- Good 3:1 sugar Good cent sirup Good 4:1 sugar Good Good rill, and Dunlap were packed without the addition of sugar, sirup, or water; with water; in three different concentrations of sirup; and with three different proportions of sugar (Table 3). After seven months of storage at F., the berries were removed to room tempera- ture and allowed to thaw gradually before being examined. 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 415 The larger proportions of sugar, whether added dry or in the form of a sirup, improved the palatability of the berries but detracted from their appearance when too great a concentration was used. If berries are to be used only in ice cream, their shape after storage is not of great importance. If, however, part of the pack is to be marketed for household use, such as for making strawberry cakes or pies, the melted berries should look as nearly normal as possible, in which case either the 3:1 or 4:1 sugar pack or the 40-percent sirup pack is recommended. Additional sugar may be needed either in the mix or in the berries when the light sugar pack (4:1) is used, if the finished ice cream is to be as sweet as is usually desired. The best type. and size of container to use for storing the berries depends upon the extent of the freezing operations in the plant. It has been the practice in the creamery at the University of Illinois to use gallon paper containers. This size of package is particularly conveni- ent in small plant operations because the portions of the pack left un- used are small. In large plants 50-gallon fir barrels paraffined on the inside may be practical. In smaller plants 30-gallon barrels or 10- and 5-gallon kegs may be more suitable, tho tinned containers, such as cream storage cans, are sometimes used. COPPER SALT PROVES BASIC CAUSE OF METALLIC FLAVOR The main object of this study, as previously stated, was to de- termine the cause of a peculiar off-flavor that sometimes develops in strawberry ice cream. The defect seems to be more common in winter than in summer, and some manufacturers are more troubled with the off-flavor than are others. The ice cream at the freezer has a normal flavor but upon storage, either in the hardening room or in the dealer's cabinet, changes sometimes occur that bring about a stale metallic-like flavor. In preliminary studies attempts were made to ascertain whether the off-flavor might be caused by the variety of strawberries used, by the method of packing the berries, by aeration of the fruit, by yeast and mold contamination of the berries, by the presence of copper salts in the fruit, or by the source of the butterfat used in the mix. Eight different varieties of Illinois grown berries packed in both sugar (4:1, 3:1, and 2:1 packs) and sirup (40 percent cane sugar) were used to flavor ice cream, but none of the experimental ice creams developed the flavor defect. 416 BULLETIN No. 407 [November, The effect of aeration was tested in a series of experiments in which ice cream* was used that was made with 15 percent strawberries that had been packed in 40 percent sugar sirup and aerated by per- mitting compressed air to bubble thru them for as long as 24 hours, a glass diffuser being used. While aeration of the fruit did cause a slight off-flavor in some of the ice creams, especially those containing TABLE 4. RELATION OF SOURCE OF BUTTERFAT TO THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM Description of sample Flavor of ice cream after 24 hours 2 weeks 94-score butter, no berries. . Good Good High butter flavor High butter flavor Slight tallowy Strong metallic and tallowy Good Slight stale High butter flavor Stale Tallowy Very tallowy and stale 94-score butter, 15 percent 2 89-score butter, no berries . 1 frozen-pack berries 89-score butter. 15 percent 2 88-score butter, no berries. . 1 frozen-pack berries 88-score butter, 15 percent 2 1 frozen-pack berries berries to which a copper-sulfate solution had been added, it did not seem to be of any great significance. The presence of the copper salt was of much greater importance than aeration. To determine whether the growth of yeast and mold in the berries had any connection with the flavor defect, three lots of berries were inoculated with different cultures of pure yeast and three with different cultures of molds. After incubating the berries at room temperature for 24 hours, they were held at 40 F. for 24 hours and then added to ice cream at the rate of 15 percent. Duplicate sets were prepared, a small amount of a copper sulfate solution being added to one set. An uninoculated control incubated sample and one held at 40 F. were used in each test. After four months in storage the samples containing no copper were all of fairly good quality, none having the stale metallic flavor. The samples containing copper, on the other hand, were all off- flavor. The sample with the greatest degree of off-flavor was the one containing the uninoculated berries stored at 40 F. ; the ice creams containing the berries inoculated with yeast had the most pronounced and most desirable strawberry flavor. In a series of experiments in which the source of butterfat in the mix was varied, it was found that the stale metallic flavor was much 'Unless otherwise specified all experimental batches were frozen in a 40- quart direct expansion freezer. 1934} STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 417 more likely to develop in ice cream containing an 88- or 89-score butter than in that containing a 94-score butter (Table 4). The butter used in these mixes was melted and washed with water to remove the salt. The source of the serum solids was skim-milk powder. The mixes were pasteurized and homogenized after being standardized to contain 13 percent fat, 10.5 percent serum solids, 14 percent sugar, and .3 percent gelatin. As a result of these preliminary tests it was concluded that a stale metallic -like flavor not unlike talloiviness will develop in ic,e cream containing a copper salt, and that the defect is greater when jrozcn- pack strawberries have been added to the ice cream. The fact that the flavor defect developed more rapidly in ice creams made from butter of relatively low score and in the presence of a copper salt suggested that the problem was one of buttcrfat oxidation. STUDY OF FACTORS CONTRIBUTING TO DEVELOP- MENT OF METALLIC FLAVOR The stale metallic flavor having been identified as associated with the presence of a copper salt, the above study was continued in order to obtain more complete information on the nature of the reaction which takes place and the other contributing factors responsible for the flavor defect. It was assumed that a certain amount of a copper salt had to be present in order to make possible the development of a stale metallic flavor. An experiment in which variable amounts of CuSO 4 were added showed that the off-flavor would develop when as much as one part of copper per million parts of mix was added, but the reaction was rather slow. In most of the trials about three parts of copper per mil- lion parts of mix were added, as this amount of copper usually pro- duced the defect within a few days. Commercial Packs Differed in Tendency to Cause Off-Flavor To test possible differences in the readiness with which ice creams flavored with different brands of commercially packed berries de- veloped an off-flavor, samples of strawberries preserved in various ways were obtained from several commercial dealers and added to ice cream at the rate of 8 percent by weight. The experimental mix used contained 13 percent fat, 10.5 percent serum solids, 14.5 percent sugar, .3 percent gelatin, and .25 percent dried whole egg, and was made from fresh milk products by the condensation process. Two sets of samples 418 BULLETIN No. 407 [November, were prepared, one set containing copper sulfate added at the rate of 3 parts of copper to a million parts of mix, while the second set con- tained no additional copper.* The ice creams were stored in an ice- cream hardening room in which the temperature usually fluctuated between and -10 F. The flavor of samples after storage for 3, 10, and 40 days in the hardening room is given in Table 5. TABLE 5. DEVELOPMENT OF OFF-FLAVOR IN ICE CREAM FLAVORED WITH DIFFERENT BRANDS OF STRAWBERRIES Method of packing berries Copper added* Flavor of ice cream after 3 days todays 40 days 1 Control no berries None CuSO (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) None CuSO4 (3 p.p.m.) Good Good Good Good Good Slight stale metallic Good Slight stale metallic Good Strong stale metallic Good Strong stale metallic Good Slight stale metallic Good Stale metallic Good Good Good Good Good Good Good Slight stale metallic Good Slight stale metallic Good Very strong stale metallic Good Strong stale metallic Good Strong stale metallic Good Strong stale metallic Good Slight stale metallic Good Slight stale metallic Good Slight stale Good Stale metallic Good Slight stale metallic Good Very strong stale metallic Good Strong stale metallic Good Very strong stale metallic Good Very strong stale metallic Good Stale metallic Control no berries 2. Processed 11 Processed 1 " 3. Processed 1 " Processed 11 4. Processed 11 Processed 1 " 5. Cold pack Cold pack 6. Vacuum cold pack Vacuum cold pack 7. Cold pack . . Cold pack 8. Cold pack Cold pack 9. Cold pack Cold pack In all tests parts per million refers to parts of copper per million parts of mix. "Heated when canned but exact heat treatment not reported by manufacturer. When the mix was not contaminated with copper, there was no trouble from a stale metallic flavor in the strawberry ice cream made with any of the brands of berries used. All were rated as good at the 'In all tests either the entire mix or the condensed milk was prepared in an Allegheny metal vacuum pan. This type of metal has been shown to have no effect upon the flavor of dairy products. 1934} STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 419 end of the test periods. The heated packs Nos. 2, 3, and A had less tendency to bring about the flavor than did the unheated packs. In the plain ice cream only the 40-day sample contaminated with copper developed a stale metallic flavor and then the flavor was only slight. Thus it would appear that strawberries may contain a factor that has the power to catalyze the reaction responsible for the off-flavor described as stale metallic, and that heated packs have less tendency than unheated packs to cause the flavor. Heating of Fruit Retarded Off-Flavor Several experiments were performed to determine to what extent the heat treatment given the berries was a factor in preventing the off- flavor (Table 6). None of the ice-cream samples in which heated berries were used acquired the off-flavor as quickly as did that in which the raw fruit was TABLE 6. EFFECT OF HEATING STRAWBERRIES ON THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN ICE CREAM Treatment of berries Extent of stale metallic flavor* developed after 12 days 18 days 77 days Control unheated None None None None + + + + + + + + + + + Autoclaved at IS pounds pressure for 15 minutes Held at 150 F. for 30 minutes Held at 1 75 F. for 30 minutes Held at 200 F. for 30 minutes indicates that the presence of the flavor defect is questionable; + indicates the degree of off-flavor. used. Heating the berries to 175 F. or higher was more effective in retarding the development of the off-flavor in the ice cream than heat- ing them to 150 F. Heating did not, however, prevent the defect, for all samples developed a stale metallic flavor after storage for 77 days in the hardening room. The ice-cream mix used in this experiment was made from 40-per- cent cream, skim milk, and concentrated skim milk. Copper contami- nation, such as often occurs commercially, was introduced by pasteur- izing the mix in a tinned copper steam kettle on which much of the tin was worn away, exposing the copper. The berries used were of the Dunlap variety; they had been stored with sugar at hardening 420 BULLETIN No. 407 [November, room temperature for ten months. Ten percent of fruit was added in each test. Amount of Fruit Added Is Important Some of the same mix described in the preceding experiment was flavored with varying amounts of both raw and heated strawberries as indicated in Table 7. Within the period of the experiment (77 days) TABLE 7. RELATION BETWEEN AMOUNT OF STRAWBERRIES ADDED TO ICE CREAM AND THE DEVELOPMENT OF A STALE METALLIC FLAVOR Proportion of berries Extent of stale metallic flavor developed after 12 days 17 days 77 days Control no berries None + + + + + None None None + None None None None None + + + + + + + None None None + + + None None None None None None None +++ + + + None None None Unheated 1 percent 5 percent 10 percent 15 percent 25 percent 50 percent Antedated* 1 percent 5 percent 10 percent 15 percent 25 percent 50 percent Heated in an autoclave for 15 minutes at 15 pounds pressure. none of the samples containing 15 percent or more fruit acquired an off-flavor, whereas all the lots containing 10 percent or less fruit had a stale metallic flavor at the end of 17 days. The most pronounced off- flavor was in those samples containing the unheated berries. Juice of Berry Contains Factor Causing Off-Flavor To determine what portion of the strawberry was responsible for the development of the stale metallic flavor in strawberry ice cream, the following experiment was performed. Frozen-pack Dunlap berries were used. The mix contained 13 percent fat, 10.5 percent serum solids, 14 percent sugar, .25 percent whole egg yolk, and .3 percent gelatin. The milk products in this mix were 40-percent cream, sweetened condensed skim milk, and skim milk. Seven different lots of ice cream were prepared, six containing 10 percent of a certain portion of the berry, as follows: (1) whole ber- ries; (2) washed berry fiber; (3) unwashed berry fiber; (4) berry tis- sue and juice that passed thru cheese cloth and contained no seeds; 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 421 (5) very fine tissue and juice caught on filter paper, containing no seeds; (6) juice filtered thru quantitative filter paper. The control lot contained no berries. All the mixes contained 2.6 parts per million of copper added as CuSO 4 . After one day in storage all lots had good flavor; after 10 days in storage the lots containing the whole fruit, tissue and juice, very fine tissue and juice, and filtered juice had developed a stale metallic flavor (Table 8). After 43 days in storage the stale metallic flavor was still TABLE 8. RELATION OF DIFFERENT BERRY FRACTIONS TO THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN ICE CREAM Flavor of ice cream after Berry fraction added to mix at rate of 10 percent by weight 1 day 10 days 43 days Control no berries. Good Good Good Good Good Good Good Doubtful Stale metallic Good Good Stale metallic Stale metallic Stale metallic Slight stale metallic Stale metallic Fair Fair Stale metallic Stale metallic Stale metallic Whole fruit Washed fiber Unwashed fiber Tissue and juice Very fine tissue and juice '. . . . Filtered juice evident in these samples and in addition a slight stale metallic flavor was present in the control lot. The samples containing washed and unwashed fiber lost their fresh flavor after 43 days but did not develop the characteristic stale metallic flavor of the other samples. Strawberries apparently contain two factors related to the develop- ment of the flavor defect. One is associated with the fiber and aids in preventing the reaction responsible for the off-flavor; the other agent is contained in the juice and tissue mixture and has the effect of hastening the reaction. Flavor Defect Associated With Presence of Butterfat To determine the role that butterfat might play in the development of the off-flavor in strawberry ice cream, the following experiment was performed. Using fresh 40-percent cream and sweetened condensed sldm milk, mixes were prepared containing different proportions of fat and total solids, as indicated in Table 9. The mixes contained no gelatin and were processed at low pressure (about 200 pounds) thru a small emulsifier. Ice creams were made with each of the mixes as follows, and fro/.en in a hand freezer: (a) con- trol no additional treatment ; (b) CuSO 4 added at the rate of 4 p.p.m. 422 BULLETIN No. 407 [November, TABLE 9. RELATION OF BUTTERFAT TO THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM Description of sample* Flavor of ice cream after 4 days 40 days .144 percent fat, 24.96 percent total solids Control no berries Good Good No berries CuSOj (4 p.p.m.) Good Unclean 10 percent frozen- pack Good 10 percent frozen-pack plus CuSO (4 p.p.m.) . . Good Very unclean 4.55 percent fat, 31.44 percent total solids Control no berries Good No berries CuSOi (4 p.p.m.) Stale metallic + + Stale metallic + + + 10 percent frozen-pack Good 10 percent frozen-pack plus CuSCu (4 p.p.m.) . . Stale metallic + Stale metallic + -f + + 8.98 percent fat, 35.76 percent total solids Control no berries Good Good No berries CuSO (4 p.p.m.) Stale metallic + + + Stale metallic + + + 10 percent frozen-pack Good Good 10 percent frozen-pack plus CuSO< (4 p.p.m.) . . Stale metallic + + Stale metallic + + + + + + + In all tests parts per million refers to parts of copper per million parts of mix. of copper; (c) 10 percent frozen-pack strawberries used; (d) same as c plus CuSO 4 at the rate of 4 p.p.m. of copper. Criticisms on the samples are given in Table 9. Altho an unclean flavor developed in the mixes containing .144 percent fat, to which copper had been added, the off-flavor was not nearly so pronounced nor so pungent as that occurring in correspond- ing samples containing 4.55 percent fat. In the same way, the off-flavor in the samples containing 4.55 percent fat, to which copper had been added, was not so intense as that in the corresponding samples con- taining 8.98 percent fat. Thus the flavor defect was quite evidently associated with the presence of butterfat. It would have been of interest to study the development of the off- flavor in a fat-free ice cream. The presence of fat in all skim milk products would, however, make it impossible to build a mix from con- densed or fluid skim milk without there being enough fat present to develop a small amount of the off-flavor. Citric Acid Content of Strawberries Is Not Important Inasmuch as strawberries contain fruit acids, such as citric, the effect of variations in the citric-acid content of strawberry ice cream 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 423 upon the development of the stale metallic flavor was studied. A mix containing 10 percent fat, 10 percent serum solids, and 15 percent sugar was prepared from 40-percent cream and sweetened condensed skim milk and processed with a small emulsifier at approximately 200 pounds pressure. Instead of using the whole strawberry the filtered juice was used, since this fraction of the berry had been found to con- tain the substance responsible for the off-flavor in strawberry ice cream. A portion of the juice was reduced in acidity by the addition of NaHCO 3 before it was added to the ice cream. The following pH determinations were made: raw berry juice, 3.37; neutralized juice, 6.00; mix-control, 6.43; mix plus CuSO 4 (3 p.p.m.), 6.47; mix plus raw juice plus CuSO 4 (3 p.p.m.), 6.27. TABLE 10. EFFECT OF VARYING THE CITRIC ACID CONTENT OF STRAWBERRIES ON THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN ICE CREAM Description of sample' Flavor of ice cream after 4 days 28 days 1. Control no berries.. . . Good Good Stale metallic + + + Stale metallic + + Good Good Good Good Good Good Good Good Doubtful Doubtful Stale metallic + + + + + + Stale metallic + + + + + + + Stale metallic + + + + + + Stale metallic + + + + + Stale metallic + + + -j- + Stale metallic + + + + + Stale metallic + + + + Stale metallic + + + + Stale metallic + + + Stale metallic + + 4- 2. 10 percent raw juice 3. No berries CuSOi (3 p.p.m.) 4. 10 percent raw juice, CuSO (3 p.p.m.) . . . 5. 10 percent neutralized juice, CuSO (3 p.p.m.) 6. Same as No. 5, plus .17 percent citric acid 7. Same as No. 3, plus .17 percent citric acid 8. 10 percent raw juice, CuSO4 (3 p.p.m.), .17 percent citric acid 9. Same as No. 7, except .34 percent citric acid 10. 10 percent raw juice. CuSO (3 p.p.m.). .34 percent citric acid 11. Same as No. 7, except .68 percent citric acid 12. 10 percent raw juice, CuSO4 (3 p.p.m.), .68 percent citric acid In all tests parts per million refers to parts of copper per million parts of mix. The flavor criticisms of the ice cream are given in Table 10. Neither the addition of sodium bicarbonate nor of citric acid to the strawberry juice before the juice was added to the ice cream containing CuSO 4 (3 p.p.m.) caused an increase in the stale metallic flavor. As a matter of fact, the flavor seemed less pronounced in the samples to which the acid was added. This precludes the possibility of the citric- acid content of strawberries being responsible for catalyzing the reaction producing the stale metallic flavor. As indicated by the pH of the mix before and after 10 percent raw juice was added, the buffer 424 BULLETIN No. 407 [November, action of the mix constituents is apparently great enough to offset prac- tically all effect which the free hydrogen ions in the fruit juice may have upon the pH concentration of the flavored mix. Homogenization of Mix Retarded Off-Flavor In a previous study 7 * of the tallowy flavor in pasteurized milk, the authors found that homogenized milk contaminated with copper did not acquire so tallowy a flavor when stored at 40 F. as did the same milk unhomogenized. In the present study it was likewise found that strawberry ice cream made from a homogenized mix was less likely to develop the stale metallic flavor than one made from an unhomogenized mix (Table 11). The mix used contained 40-percent cream, skim milk, and 32-per- cent concentrated skim milk as a source of milk solids, 12 percent fat, TABLE 11. EFFECT OF HOMOGENIZATION OF Mix ON THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM Treatment of sample Flavor of ice cream after 4 days Unhomogenized No berries 10 percent berries . Metallic Stale metallic (strong- est off-flavor of all) Homogenized 1 ,000 pounds on 1st valve No berries. 10 percent berries. 2,500 pounds on 1st valve; 1,000 pounds on 2d valve No berries. 10 percent berries.. 3,500 pounds on 1st valve No berries. 10 percent berries. Good Stale metallic Good Very slight metallic Good Very slight metallic 10.5 percent serum solids, 14 percent sugar, and .3 percent gelatin. CuSO 4 was added at the rate of 3 parts of copper per million parts of mix. After being pasteurized in the usual way by being heated to 145 F. and held at that temperature for 30 minutes, samples of the mix -\vere pumped thru a homogenizer at different pressures; namely: at 1,000 pounds pressure on the first valve, at 2,500 pounds pressure on the first valve and 1,000 pounds on the second, and at 3,500 pounds pressure on 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 425 the first valve. Samples homogenized at 1,000 pounds pressure had a more pronounced off-flavor than those homogenized at the higher pressures. The freezing was done in hand freezers and the berries were added at the rate of 10 percent by weight. Frozen-pack Gibson strawberries were used. Other Fruits Than Strawberries May Cause Off-Flavor To study the effect of fruits other than strawberries on the develop- ment of the stale metallic flavor in ice cream, a batch of ice cream con- taining 13 percent fat, 10 percent serum solids, 14 percent sugar, and .3 percent gelatin, was divided into small lots which were flavored with 3, 10, and 25 percent each of different fruits and vegetables. The stale metallic flavor developed in the ice creams containing 3 and 10 percent of oranges, lemons, pineapple, apples, potatoes, peaches, and apricots, respectively. The ice creams flavored with rhubarb and tomatoes did not develop the defect. None of the ice cream containing 25 percent of the above flavoring materials developed an off-flavor. OXIDATION THEORY TESTED BY OXIDATION- REDUCTION POTENTIAL MEASUREMENTS Eh Measurements Show Off-Flavor Is Due to Fat Oxidation Evidence already presented suggests that fat oxidation in straw- berry ice cream was the cause of the stale metallic flavor. It was shown that a copper salt must be added, either to the fruit or to the mix, in order to produce the off-flavor and that when the butterfat in strawberry ice cream came from an 88-score butter, the off-flavor developed, but when a 94-score butter was used there was no sugges- tion of the stale metallic flavor. In another experiment it was found that a certain amount of butterfat must be present in the ice cream in order to develop a distinct stale metallic flavor. To secure further evidence that the stale metallic flavor is noth- ing more than a modified tallowiness, oxidation-reduction potential measurements were made in a series of experiments designed to intro- duce some of the variables already studied. This method was used by the authors in the study of tallowiness in market milk previously referred to. 7 * The test is based on the fact that as the intensity of oxidation is increased, the voltage exerted on a platinum electrode is also increased, 426 BULLETIN No. 407 [November, and vice versa. The E.M.F. was measured with a Leeds and North- rup Type K potentiometer and a sensitive galvanometer. Connections were made from the saturated KC1 calomel half-cell, as the reference electrode, to the samples under measurement by means of a saturated KG liquid junction and saturated KC1 agar bridges. Potential read- ings were reduced to the conventional hydrogen scale. A mix containing 12 percent fat, 10.5 percent serum solids, 14 per- cent sugar, and .33 percent gelatin was used. This mix was made from 40-percent cream, skim milk, and 32-percent concentrated skim milk. Frozen-pack Gibson berries were used. The fruit was added to the mix before freezing in hand freezers. The following mixes were pre- pared: (1) control mix, no berries added; (2) 10 percent berries added; (3) no berries, CuSO 4 added at rate of 1 p.p.m. ; (4) 10 per- cent berries and CuSO 4 (1 p.p.m.) added; (5) no berries, CuSO 4 added at rate of 3 p.p.m.; (6) 10 percent berries and CuSO 4 (3 p.p.m.) added. It will be observed that the addition of the berries alone to the ice cream caused the potential to shift towards the side of reduction, but that the potential reading remained practically constant during the course of the experiment (Table 12). However, when a copper salt TABLE 12. RELATION BETWEEN OXIDATION-REDUCTION POTENTIAL READINGS AND THE DEVELOPMENT OF A STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM Description of sample* Eh when made Eh after 1 day Eh after 3 days Flavor after 3 days Eh after 33 days Flavor after 33 days Control no berries .50452 . 49687 .50242 Good .50493 Good 10 percent berries . 33693 . 34623 .34893 Good .34451 Good No berries CuSO4 (1 p.p.m.) 10 percent berries, CuSOi (1 p.p.m.) .49826 .36382 .50893 .37873 .51212 .38806 Good Doubtful .50033 .45346 Slight unclean Strong No berries CuSCU (3 p.p.m.) 10 percent berries. CuSO4 (3 p.p.m.) .48823 .41182 .49957 .46357 .50757 .48097 Doubtful Strong .50093 .48403 stale metallic Slight unclean Very stale metallic strong stale metallic In all tests parts per million refers to parts of copper per million parts of mix. was added along with the berries, the potential did not drop so far towards the side of reduction even at the beginning of the experiment, and during the storage period the potential apparently gradually changed toward the side of oxidation. Furthermore, as the potential of 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 427 these samples shifted towards oxidation, the flavors of the ice cream also changed from normal to the characteristic stale metallic flavor, indicating a correlation between the oxidation reaction and the develop- ment of the flavor defect. There was but little change in potential towards reduction in those samples to which copper was added but which contained no strawberries. This bears out the contention that the berries contain a factor which, in the presence of copper, catalyzes the oxidation reaction. Undoubtedly in time the potential of the unflavored ice cream containing copper would have shifted towards oxidation and a tallowy flavor would have become evident. Different Amounts and Different Parts of Berries Cause Varying Degrees of Oxidation The stale metallic flavor having been shown by organoleptic methods to have developed faster with small additions of fruit (less than 10 percent) and to have become more pronounced than when TABLE 13. EFFECT OF INCREASING AMOUNTS OF STRAW- BERRIES ON THE OXIDATION-REDUCTION POTENTIAL OF THE ICE-CREAM Mix Proportion of berries Eh after aging the mix at 40 s F. for 24 hours Control no berries .43367 5 percent .39764 10 percent .39977 20 percent .33244 30 percent .30139 larger amounts of fruit (over 10 percent) were added, it was desired to study the oxidation-reduction potential in such samples. Accordingly the following experiment was conducted. The mix used contained 12 percent fat, 10 percent serum solids, 14 percent sugar, and .3 percent gelatin, and was prepared by the con- densation process, using 40-percent cream and skim milk as the source of the milk solids. Samples containing 5, 10, 20, and 30 percent frozen-pack Dunlap berries were tested. The potential readings were made 24 hours after the samples had been flavored and stored at 40 F. An increased amount of strawberries added to the ice-cream mix tended to cause a reduced Eh reading (Table 13). The strong reduc- ing powers of strawberries cannot be explained entirely thru dilution, however, since the berries alone gave an Eh reading of .28440. Appar- 428 BULLETIN No. 407 [November, ently the addition of a large percentage of berries sets up a system that is capable of resisting oxidation. Experiments were also made to determine the effect of different portions of frozen-pack berries on the oxidation-reduction potential of the ice-cream mix. The mix was similar and the berries were the same as those used above. The berry fractions (same as described on page 420) were added before aging for 24 hours at the rate of 10 percent by weight. The low Eh of the mix containing the washed and unwashed fiber indicated that it is partly this constituent, f the berry that causes the drop in Eh when the fruit is added to the ice cream (Table 14). The TABLE 14. EFFECT OF DIFFERENT STRAWBERRY FRAC- TIONS ON THE OXIDATION-REDUCTION POTEN- TIAL OF THE ICE-CREAM Mix Berry fraction added to mix at rate of 10 percent by weight Eh after aging the mix at 40 F. for 24 hours Control no berries . 44970 Whole fruit .40193 Washed fiber .33485 Unwashed fiber .33781 Tissue and juice .38218 Very fine tissue and juice .39361 Filtered juice .36182 TABLE 15. EFFECT OF ADDING STRAWBERRIES TO Mix 24 HOURS BEFORE FREEZING ON THE OXIDATION-REDUCTION POTENTIAL Description of sample* Eh of mix 2 hours after freezing Eh of melted ice cream 24 hours after freezing Flavor of ice cream 21 days after freezing 10 percent berries at freezer. . . . . .46469 . 43396 Good 10 percent berries at freezer, CuSO4 (3 p.p.m.) 10 percent berries to mix 24 hours before freezing, CuSOi (3 p.p.m.) .46630 .28200 .45056 .20037 Stale metallic Slight puckery In all tests parts per million refers to parts of copper per million parts of mix. juice passed thru a filter paper appeared to have similar reducing powers. When the juice was passed thru a Pasteur-Chamberlain filter, how- ever, and then added to the mix, a higher Eh resulted. The Eh of the mix to which no juice was added was .43536; with 10 percent juice 1934] STALE METALLIC FLAVOR IN STRAWBERRY ICE CREAM 429 filtered thru the paper it was .29907; with 10 percent juice filtered thru a Pasteur-Chamberlain, .40566. Apparently there was a reducing substance contained in the juice which was mostly filterable. Adding the fruit to the mix a few hours before the mix is frozen enables the factor contained in the berries that is responsible for the reducing effect to function to better advantage, as is indicated by the data in Table 15. The .mix used in this test was made from 14-percent cream and contained 15 percent sugar, 1 percent fresh eggs, but no gelatin. SUMMARY AND CONCLUSIONS The elimination of copper contamination is the most necessary step in preventing the development of a stale metallic flavor in strawberry ice cream. This off-flavor is associated with the oxidation of the but- terfat, as shown by oxidation-reduction measurements made on experi- mental batches of ice cream. The addition of copper to the ice cream mix catalyzes the oxidation reaction. Ice-cream plant operators need not be troubled with this flavor defect if they exercise proper care in the selection of dairy products and take the necessary precautions to avoid copper contamination of the mix or any of its constituents. The development of a stale metallic flavor in strawberry ice cream can be retarded by homogenizing the mix at a high pressure, by heating the berries, by soaking the fruit in the mix before freezing, or by increasing the amount of the fruit added or increasing the fiber con- tent of the berries. Since the off-flavor developed more rapidly in ice-cream mixes to which strawberries were added than in the control mix to which no berries were added, and since the use of the fruit fiber was shown to check the development of the defect, strawberries apparently contain two agents affecting fat oxidation, one serving as a catalyst and the other as a reducing agent. The former is contained in the juice and the latter is associated with the fibrous material. Increasing the citric acid content of the berries did not hasten the development of the flavor defect. The fact that different commercial pack berries varied in their ability to cause the stale metallic flavor can probably be attributed to the differences in concentration of pack or to the proportion of fiber as well as to the heat treatment given the berries before or after can- ning. Fruits other than strawberries, such as oranges, lemons, and pineapple, were also found to accelerate the reaction responsible for the off-flavor. 430 BULLETIN No. 407 Six of the most common varieties of strawberries grown in south- ern Illinois were tested for their desirability as a source of flavor in ice cream. These varieties ranked in the following order of prefer- ence: Dunlap, Parson Beauty, Gandy, Premier, Gibson, Aroma. The average net weight of Dunlap berries was found to be 24.5 pounds per case of 24 boxes. The average yield per case of 2:1 pack was 4.2 gallons; of 3:1 pack, 3.85 gallons; and 4:1 pack, 3.7 gallons. Either 2, 3, or 4 parts of berries to 1 part of sugar made a desirable pack so far as flavor was concerned. When it was desired to keep the fruit whole, a pack of 3 or 4 parts of berries to 1 part of sugar or 40 per- cent sugar sirup solution was found to be preferable. LITERATURE CITED 1. DAHLE, C. D., and FOLKERS, E. C. Cause of off-flavor in strawberry ice cream. Ice Cream Rev. 16, No. 4, 31, 1932. 2. DIEHL, H. C., MAGNEN, J. R., and GROSS, C. R. The frozen-pack method of preserving berries in the Pacific Northwest. U. S. Dept. Agr. Tech. Bui. 148. 1930. 3. HENING, J. C., and DAHLBERG, A. C. Frozen fruits for ice cream. N. Y. (Geneva) Agr. Exp. Sta. Bui. 634. 1933. 4. Internatl. Assoc. of Ice Cream Manfrs. Statis. and Accounting Bur. Spec. Bui. 42. 1933. 5. JOSLYN, M. A. Preservation of fruits and vegetables by freezing storage. Calif. Agr. Exp. Sta. Circ. 320. 1930. 6. MACK, M. J., and FELLERS, C. R. Frozen fruits and their utilization in frozen dairy products. Mass. Agr. Exp. Sta. Bui. 287. 1932. 7. TRACY, P. H., RAMSEY, R. J., and RUEHE, H. A. Certain biological fac- tors related to tallowiness in milk and cream. 111. Agr. Exp. Sta. Bui. 389. 1933. 8. WIEGAND, E. H. The "frozen-pack" method of preserving berries. Oreg. Agr. Exp. Sta. Bui. 278. 1931. 9. WOODROOF, J. G. Preserving fruit by freezing. I. Peaches. Ga. Agr. Exp. Sta. Bui. 163. 1930. 10. Preservation freezing: some effects on quality of fruits and vegetables. Ga. Agr. Exp. Sta. Bui. 168. 1931. 6.05011-34 UNIVERSITY OF ILLINOIS-URBANA