Introduction of a new family of ice creams

Author’s Accepted Manuscript Introduction of a new family of ice creams Camila Fiol, Diego Prado, Cesar Romero, Nerea Laburu, María Mora, J. Iñaki Alava

www.elsevier.com

PII: DOI: Reference:

S1878-450X(16)30064-6 http://dx.doi.org/10.1016/j.ijgfs.2016.12.001 IJGFS55

To appear in: International Journal of Gastronomy and Food Science Received date: 13 October 2015 Accepted date: 7 December 2016 Cite this article as: Camila Fiol, Diego Prado, Cesar Romero, Nerea Laburu, María Mora and J. Iñaki Alava, Introduction of a new family of ice creams, International Journal of Gastronomy and Food Science, http://dx.doi.org/10.1016/j.ijgfs.2016.12.001 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Camila Fiol 1, Diego Prado 2, Cesar Romero 1, Nerea Laburu 1, María Mora 2, J. Iñaki Alava 1. 1. Basque Culinary Center, Faculty of Gastronomy and Culinary Arts, Mondragon University, St. Paseo Juan Avelino Barriola 101, 20009 San Sebastián, Donostia, Spain. 2. BCC INNOVATION, St. Paseo Juan Avelino Barriola 101, 20009 San Sebastián, Donostia, Spain.

Abstract Usually most of the ice cream manufacture was made by experiential work in kitchens, thought years of work and experience making it a handcrafted work, proving most of the knowledge we have today making Angelo Corvitto (Corvitto, 2011), the main source of information for culinary proposals. We present and characterize a new family of ice cream formulation according to its physiochemical characteristics through the use of lactose and sodium casein as the main ingredients of the formula. Avoiding use dairy (milk, cream, etc...), we don’t have use milk fat flavor that dilute main flavor in the mixture. We may use different types of fats from any origin and different types of liquids substituting the water and milk fats from the juice and emulsion that the user liked, in this new ice cream family.

Keywords Ice cream; Milk; Casein; Lactose; Dairy; Formulation; Protein; Sodium casein.

Introduction By definition “ice cream is a liquid mixture that turns into a paste after simultaneously shaking and cooling” (Corvitto, 2011), although the definition of ice cream varies from country to country due to differing regulations and traditions of composition (Clark, 2012; Goff & Hartel, 2013). In the ice cream mix that will become ice cream are so many elements of different nature as sugars, fats, dairy, stabilizer, water, among others. And they all have to be correctly blended and emulsified together so there is nothing left behind that may reduce the quality of the final product. Making this possible considering the characteristics and behaviors of each ingredient and the relationships between them is what is known as the balancing exercise. We can make it stable and spreadable at negative temperature from -11 to -18 ºC (standard ice cream serving temperatures) (Corvitto, 2011). In ice cream making, the first step is to blend a series of liquid and solid ingredients in different orders and temperatures, obtaining a liquid mixture also called “mix”. After the processing and pasteurization process, this mixture is poured into an ice cream machine in which, it incorporates a quantity of air between 30% - 40% (overrun) that is held or set by

cooling at negative temperatures and the result is a semi-solid spreadable and moist past mixture. This liquid mixture turned into ice cream will present specific characteristics of taste, structure and texture, determined by quality of ingredients used, mix balance and manufacturing process, the standard parameters for a dairy base ice cream is 64% water, 18% sugars, 10% non-fat milk solids and 8% milk solid fats, all these parameters, is expected to have a stable structure maintaining its characteristics in negative temperature with smooth texture (without appearance of ice crystals), spreadable (can work at their preservation temperature) and stable (maintain his characteristics at serving temperature) (Corvitto, 2011). According to other authors a standard ice cream is about 30% ice, 50% air (the main role is to make it soft), 5% fat and 15% sugar solution by volume. The composition for a standard ice cream is; Fat 7–15%, Milk protein 4–5%, Lactose 5–7%, Other sugars 12– 16%, Stabilizers, emulsifiers and flavors 0.5%, Total solids 28–40%, Water 60–72% (Clark, 2012) (Goff H.D. 1997). Also the range in composition may be fat, 8 – 20%; MSNF, 8 – 15%; sugar, 13 – 20% stabilizer – emulsifier, 0 – 0.7%; and total solids, 36 – 43%. (Ice Cream W. S. Arbuckle) and an average ice cream contains 3-4 times more fat and about 12–16% more protein than milk does (Goff & Hartel, 2013). Smooth ice cream requires the majority of ice crystals to be smaller than about 50 μm in size. Ice crystals larger than 40 to 55 μm leave a coarse and sandy texture (Arbuckle & Marshall, 2012). Ice crystals in ice cream generally range from 20 to 100 μm (Buyong and Fennema, 1988). Fat content influence the size of the ice crystals in fat globules and impede the ice crystal growth (Arbuckle & Marshall, 2012). Sucrose reduces ice crystal growth rate (Buyong and Fennema, 1988) and a higher content produces smaller ice crystals. An increase in sugar content from 12 to 18% decreases ice crystal size by 25% approximately (Arbuckle & Marshall, 2012). The aim developing, this new family of ice creams was to obtain pure flavors, more stability and the use of different fats replacing the total milk fat of the mix. Pure flavors, because if you make the ice cream balance with “white cream” base you always had to dilute the flavors with dairy flavors such as cream, milk powder and milk. More stability because the making process habitually denaturalized the casein (k-casein) brings it to 85ºC in the pasteurization. Casein is the main emulsifier protein in the ice cream mix; it has good emulsifying and foaming properties. In standard ice creams (Corvitto`s white cream or ice cream mixture like), milk are not allowing to replace a 100% of different fats (such as olive oil, pork fat, peanut oil, etc.). Milk fats produce a characteristic dairy flavor, probably due their vitamins content (Shipe, W. F., & Charalambous, 1980). Also lactose can absorb 10 times its weight in water, and Milk powder contains 50% lactose, so it can absorb 5 times its weight in water (Corvitto, 2011).

Due to their composition, is near impossible, to obtain pure flavors with dairy products based ice creams. In the new ice cream presented, balance is obtained not using any dairy mix. In substitution, it will be a fully watery taste which allows us to obtain pure flavors using aromatic fats or different watery parts (fruit juices, broths, mushroom water, etc.). These ice-cream casein emulsion based, is not inside Corvitto`s 16 families of ice cream, previously described. Has all the organoleptic characteristic of a regular “white cream” ice cream but an equal or better controlled physic- chemical structure, without dairy flavour induction.

Materials Whole milk UHT, heavy cream, skimmed milk powder, dextrose (Sosa Co), sucrose , inverted sugar, stabilizer (Sevarome ice cream 64G) Natural water (pH 8.8) , Sodium casein (Sosa Co.), lactose (Mugaritz Experiences), glycerin , Refined sunflower oil (100%).

Methods Experimental Design: Both ice cream, classical and new one are prepared on time. Preliminary physic-chemical parameters such as spread ability analysis, meltdown analysis, pH, microstructure and titratable acidity were determined by standard procedures at the laboratory and kitchen at Basque Culinary Center. Six experiments are performed in each determination (n=6) and twelve in case of analysis (n=12). Data were represented as means +/- SD of n= 6 samples per group and were analyzed by Student's t test. Finally organoleptic and culinary capabilities are also compared. Ice creams preparation: Angelo Corvitto (Corvitto, 2011) formula: Weight all the ingredients separately. Pour the milk and cream in a saucepan, add the milk powder and dextrose. Place it at 40°C on medium heat. From 40 ° C pour the stabilizer mixed with some sucrose, the rest of it and the invert sugar. Stir with a manual whisk and bring the mixture to 85° C (minimum one minute). Cool as quickly as possible to 4° C in a blast chiller and let it mature in the refrigerator for 6 to 12 hours. Mix it with a hand blender, until homogeneity, before churning. Freeze at -18 ° C (Table 1). (Table 1) New ice cream elaboration process: Weight all of the ingredients separately. Pour the water in a saucepan, add the lactose, glycerin, inverted sugar, dextrose and half of the sucrose. From 40° C pour the stabilizer mixed with the rest of sucrose. Stir with a manual whisk and bring the mixture to 85° C. Cool as quickly as possible to 40° C in a blast chiller

and then add the casein and keep at higher speed with the help of an Immersion blender for 10 minutes, pour the sunflower oil little by little and emulsify. Let it mature in the refrigerator for 6 hours. After churning, put the ice cream in an ice cold steel container. Freeze in a blast chiller at -40°C until it is completely frozen. Move to a freezer at -18 ° C (Table 2). (Table 2)

Ice creams analysis Spread ability analysis: Both ice cream were placed separately on a silicon mold with cubes of 2x2cm. Place them in the blast chiller at -30°C for half hour, unmold and place them separately in two hermetic plastic containers on the freezer at -18°C for 3 hours. On a walk-in freezer at -18°C place a tray with a 30cm steel rule along, and place an ice cream cube next to a ruler with a lab glass plate and a steel weight of 100gr on top. Taking a picture every 2 minutes for 12 minutes, six times each ice cream (Fig. 1)

(Fig.1) PH: pH of both ice creams were measured with a HI98127 Waterproof PH Temperature Tester Hanna Instruments according to standard procedure as describes in AOAC 981.12 (Association of Official Analytical Chemists., 1984). pH of both ice creams were measured during production steps, freshly made, after the maturation and hardened for a month at 18°C. Titratable acidity: The acidity was determined with a standardized solution of 0.1 N sodium hydroxide (4.00 g of NaOH per liter) and taking 10gr of each sample adding 90ml of distilled water with added phenolphthalein indicator (prepared at 1% in ethanol at 95%) and titrated until the first dye of light pink is permanent. Acidity is expressed as percentage of lactic acid (1 mL of 0.1 N NaOH = 0.009 g lactic acid) (Goff & Hartel, 2013; Wehr & Frank, 2004) Meltdown: Six samples of 50 g of each ice cream at -18°C were placed on a 8 wires/645,16mm2 wire gauze fitted in a funnel that drained into a graduated cylinder on top of a balance at a room temperature of 22 ± 0.5°C at constant humidity. Take notice to the fall of the first drop

(Rigey et al., 2012) and the weight of the melted ice cream every 10 minutes to the time the ice cream is completely melted (Clark, 2012; Goff & Hartel, 2013). Microstructural analysis: Direct observation method by optical microscopy with episcopic coaxial lighting was originally developed by the physicists studying the polar ices structures (Arnaud, Gay, Barnola, & Duval, 1998) and this method was adapted to ice cream by Faydi et al. (2001) to characterize the frozen structure of an ice cream mix. This method is essentially based on the light flux reflected by the surface of the sample. For example, at the air bubbles surfaces which are present in the case of commercial ice creams containing overrun. (Goff, D.H. 1997), (Caillet et al, 2003). A think slide (1 mm thick) of new formed ice cream is stored 48 hours a -18 ºC in a dry air glove box, until the ice cream matured.(Degner BM et al, 2014) After obtaining a suitable surface quality, the ice cream sample was directly observed, still at -18 ºC inside the cold room, with a digital stereomicroscope (DINOLITE), equipped with a digital video camera and an a led light source providing the episcopic coaxial lighting. The video microscope was placed inside the cold room and the images were stored with a laptop located outside the cold chamber. All the optical material in the cold room was placed inside a dry air glove box in slight overpressure with respect to the cold chamber pressure to avoid humidity condensation or frost problems at the frozen sample surface or at the surface of the microscope oculars (Degner BM et al, 2013)

Sensory analysis: The sensory analysis were performed with a descriptive panel consisted of 53 untrained panelists from San Sebastián - Donostia (28 females and 25 males (from) 20–52 years old), less than half with gastronomic knowledge, using a structured 9-point hedonic scale ranging from 1 (disliked it extremely) to 9 (liked it extremely). Hardened ice-cream samples were tested at a serving temperature of -18°C, both samples of Ice cream were evaluated for the odor, color, taste and texture. Approximately 20 g of each sample was placed in a 50 ml disposable cup which was coded with three-digit different numbers; 509: new ice cream and 463: standard ice cream. The panelists performed the analysis in a chamber and had no specific information about the experimental design with the 2 ice cream, (standard and new), made with mushroom flavor.

Results

(Fig 2) PH values of new ice cream are greater than those of standard ice cream, but the different is continuously reducing until final gas introduction, in these step the pH of both is similar. (fig. 2)

(Fig. 3) PH evolution shows in fig. 3 shows that “standard ice cream” is stable in 30 days period and the “new ice cream” needs 24 hours to stabilized obtaining a basic pH than “standard ice cream” pH 7,8 and pH 8,3 respectively.

Spread ability analysis (Fig. 4) As seeing in the fig. 4, spread ability of both hardened ice creams at -18ºC, even that share a similar structure, the new formulation is more stable and expands less thought time and in the minute 8 the expansion starts to be significantly different.(p<0,001, 12 min).

Titratable acidity

(Fig. 5) As we can see in fig 5, the acidity of new ice cream is very low, due to lack of lactic acid, in their composition.

Meltdown

(Fig. 6)

(Table.3)

The new ice cream melts faster than standard ice cream, melting completely to a 97,2% leaving only a 2,5% of foam, and standard ice cream exhibits shape retention and melts to a 80,2% (table 3) leaving 19,8% of foam on the wire gauze, seeing that the new ice cream has a better homogenized structure. Microstructure.

(Fig.7)

(Fig.8)

(Fig.9) The comparison between ice creams shows a more regular structure inside the new ice cream. Casein micelles, fat globules and ice crystals have a very regular distribution (Fig.7) This distribution is less regular inside standard ice cream (fig. 8) and no regular with too much gas bubbles inside the commercial one’s.(fig.9)

Sensory analysis (Fig. 10) The sensory evaluation carried out by the panelists recognized the new ice cream as very strong and pure in flavor, it was characterized by the highest scores of smell, taste and texture. Both ice creams show a similar acceptability in consumers with a preference tendency for the new ice cream.

Discussion The use of natural emulsifiers as source of industrial food emulsions is growing day bay day (Ozturk, B. and McClements, D.J.) Ice cream is a three stage colloidal dispersion, air bubbles, ice crystals and emulsified and dispersed fat globules. (Marshall y col., 2003; Clarke, 2012). A key component in the dispersed phase is fat. The fat which is incorporated in ice cream is mainly dairy, vegetable, or both. Use addition of different types of vegetable fat with different degrees of unsaturation (such as sunflower oil or palm

oil) may result in different structural units, improving the stability and melting time of ice cream (Mendez-Velasco and Goff 2012b). Fat plays a vital role in the ice cream as it, lowers melting point, stabilizes and promotes the incorporation and dispersion of air, increases the viscosity, imparts aroma and promotes the formation of ice crystals (Bolliger et al., 2000; Chung et al., 2003; Clarke, 2012; Granger et al., 2005; Goff, 1997). The traditional ice cream is formed starting with a standard “white” base of dairy emulsifiers (milk o milk derived products). This standard base is use to obtain others flavors than dairy one’s, but at the end all the other flavors will be secondary because it already has the main lactic flavor, always diluting the wished flavor. This doesn’t happen with the new family of ice creams because it doesn’t have lactic flavors, it has an aqueous flavor like a sorbet (Clark, 2012; Goff & Hartel, 2013), but with all the organoleptic characteristics of a white cream base ice cream, allowing to get primary flavors without the interference of lactic flavor, being a neutral ice cream base “not white”. The main difference is also the absence of milk vitamins in the composition besides the preparation methods. The use of pure sodium casein and pure lactose create new ice creams with pure flavors without dairy flavors interference. Similar methods has been used in the ice cream industry using sodium casein as substitute of a concentrated milk protein and inulin to get fat reduced ice creams (Mahdian & Karazhian, 2013). In terms of ice cream properties in relationship with “standard” ice cream the new ice cream has pH evolution during production but the same pH those standards in bubble generation step (fig 2). Better pH evolution during the maturation time (obviously lack of acid lactic fermentation) (fig 3). The new ice cream family have less spreadability (fig 4) and less acidity (fig 5), better meltdown and melting point (fig 6, table 3) an in general a more ordered microstructure (fig 7, 8, 9). At the end they are not significate differences in consumer’s perception between new and standard ice cream for the same flavor level. (Fig. 10) Even melting analysis shows that the new ice cream melted faster (Fig 6 ), later works shows that with modified the actual process parameters we can adjust the melting time depending on which product we need (data not showed). We have seeing many future possibilities depending on the test methods, getting different results with a same formula even getting stable mousse textures at -11 ºC which allow us to investigate a new spectrum of more controllable and stable frozen desserts.

Conclusions This new ice cream family shows many improvements for the ice cream production scene, opening new possibilities in the ice cream field and even in different frozen desserts. In the case of this new ice cream it can show that is equal or more stable than standard ice cream, has a purest flavor and may be produced with or without any kind of fat (animal,

vegetable o synthetic) without residual dairy flavor, and equally accepted by consumer or even more accepted in some parameters. In addition, the more ordered the structure the easier to control microstructure with small variations of formulation. Acknowledgements We express our gratitude to Basque Culinary Research Centre, to provide us the labs to perform analysis of this study.

References Arnaud, L., Gay, M., Barnola, J. M., & Duval, P. (1998). Imaging of firn and bubbly ice in coaxial reflected light: A new technique for the characterization ofthese porous media. Journal of Glaciology, 44(117), 326–332 Arbuckle, W., & Marshall, R. (2012). Ice cream (5ta ed.). Aspen Publisher Inc.(USA),(2012) Association of Official Analytical Chemists. (1984). Official methods of analysis of the AOAC, (14th ed.). VA USA: Arlington. Bolliger, S., Goff, D., and Tharp, W. (2000). Correlation between colloidal properties of ice cream mix and ice cream. International Dairy Journal. 10: 303-309. Buyong, N., & Fennema, O. (1988). Amount and size of ice crystals in frozen samples as influenced by hydrocolloids. Journal of Dairy Science, 71(10), 2630-2639. doi:http://dx.doi.org/10.3168/jds.S0022-0302(88)79856-2 Caillet A., Cogne C., Andrieu J., Laurent P., Rivoire A., (2003). Characterization office cream structure by direct optical microscopy. Influence of freezing parameters, Lebensm.Wiss. u.-Technol. 36 743–749 Clark, C. (2012). The science of ice cream. London: RSC publishing. Corvitto, A. (2011). The secrets of ice cream = los secretos del helado ice cream without secrets = El helado sin secretos (2“ ed.). Sant Cugat del Valles: Vilbo. Spain Chung, S., Heymann, H., and Grun, I. (2003). Temporal release of flavor compounds from low-fat and high-fat ice cream during eating. Journal of Food Science. 68: 2150-2156. Degner BM, Chung C, Schlegel V, Hutkins R, McClements DJ. (2014). Factors Influencing the Freeze-Thaw Stability of Emulsion-Based Foods. Comprehensive Reviews in Food Science and Food Safety . 13, 98-113.

Degner BM, Olson KM, Rose D, Schlegel V, Hutkins R, McClements DJ. (2013). Influence of freezing rate variation on the microstructure and physicochemical properties of food emulsions. J Food Eng 119:244–53. Donhowe, D.P., Hartel, R.W., Bradley Jr. R.L.(1991).Determination of Ice Crystal Size Distributions in Frozen Desserts. Journal of Dairy Science, 74 (10) 3334-3344 Faydi, E., Andrieu, J., & Laurent, P. (2001). Experimental study and modelling of the ice crystal morphology of model standard ice cream. Part I: Direct characterization method and experimental data. Journal of Food Engineering, 48, 283–291. Granger, C., Leger, A., Barey, P., Langendorff, V., and Cansell, M. (2005). Influence of formulation on the structural networks in ice cream. International Dairy Journal. 15: 255262. Goff, D.H. (1997). Review. Coloidal aspects of ice cream-A review. Int. Dairy Journal. 7, 363-373 Goff, D.H., & Hartel, R. (2013). Ice cream (7th ed.). Springer Ed.. USA. Marshall, T., Goff, D., and Hartel, W. (2003). Ice Cream. Gaithersburgh: Aspen Publishers. USA. Mahdian, E., & Karazhian. (2013). Effects of fat replacers and stabilizers on rheological, Physicochemical and sensory properties of Reduced-fat ice cream. Journal of Agricultural Science and Technology, 15(8) Méndez-Velasco, C. and Goff, H. D. (2012b). Fat structure in ice cream: A study on the types of fat interactions. Food Hydrocolloids. 29: 152-159. Rigey, L., Posada, D., Uriel, J., Sepulveda, V., Alonso, D., & Molina, R. (2012). Selección y evaluación de un estabilizante integrado de gomas sobre las propiedades de calidad en mezclas para helado duro. Vitae, Revista De La Facultad De Química Farmaceutica., 19(2) Ozturk, B. and McClements, D.J., (2016). Current Opinion in Food Science. 2016, 7:1–6 Shipe, W. F., & Charalambous, G. (1980). Analysis and control of milk flavor.The analysis and control of less desirable flavors in foods and beverages., 201-239. Wehr, H., & Frank, J. (2004). Standard methods for the examination of dairy products. (17th ed.). Washington, DC: American Public Health Association.

Fig.1. Photo of spread ability assay. Measure of hardened ice creams spread at -18ºC. The cube is 2 cm3 the image analysis has been performed using Fiji image analysis program and time-lapsed photos.

Fig 2.Evolution of pH values during different production steps (n=6). 1 - Before 85ºC, 2 – Ice cream mix, 3 – ice matured, 4 – Overrun.

Fig. 3.pH of both hardened ice creams at -18ºC in days (n=6).

Fig. 4.Spread ability of both hardened ice creams at -18ºC (n=12)

Fig. 5.Titratable acidity of both hardened ice creams (final ice cream) diluted in distilled water (n=6).

Fig. 6 Meltdown of both hardened ice creams at -18ºC (n=6 in each time)

Fig.7. New ice cream microstructure (x 250 magnification).

Fig.8 Standard ice cream microstructure (x 200 magnification)

Fig.9. Comercial ice cream microstructure (x 200 magnification).

Fig. 10. Sensory evaluation of both mushroom flavors, ice creams at -18ºC.

Table 1. Angelo Corvitto’s cream base -18 ºC Classic (Corvito’s) ice Cream formulation 567 cc Whole milk 172 cc Heavy cream 42 gr Skimmed milk powder 137 gr Dextrose 26 gr Inverted sugar 50 gr Sucrose 6 gr Stabilizer

Table 2. New ice cream base -18 ºC

New ice cream formula 630 cc Water 38 gr Casein 52 gr Lactose 52 gr Sucrose 70 gr Dextrose 19 gr Glycerin 53 gr Inverted sugar 6 gr Stabilizer 80 cc Sunflower oil Table.3. First drop and meltdown of both hardened ice creams at -18ºC

Samples Fall firt drop (min) Fall last drop (min) Foam (%) 90 New ice Cream 11:25 2,5 200 Standard Ice Cream 11:53 19,8