Food Research International 39 (2006) 4046 www.elsevier.

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Acrylamide content and color development in fried potato strips

Franco Pedreschi
a

a,

, Karl Kaack b, Kit Granby

Departmento de Ciencia y Tecnologia de los Alimentos, Facultad Tecnologica, Universidad de Santiago de Chile (USACH), Av. Ecuador 3769, Santiago, Chile b Department of Horticulture, Danish Institute of Agricultural Sciences, Kirstinebjergvej 10, 5792 Aarslev, Denmark c Department of Food Chemistry, Danish Institute for Food and Veterinary Research, Moerkhoej Bygade 19, 2860 Soeborg, Denmark Received 19 April 2005; accepted 2 June 2005

Abstract Acrylamide formation and changes in color of fried potato strips was investigated in relation to frying temperature and three treatments before frying. Potato strips (0.8 0.8 5 cm) of Bintje variety were fried at 150, 170 and 190 C until reaching moisture contents of 40 g water/100 g (total basis). Prior to frying, potato strips were treated in one of the following ways: (i) immersed in distilled water for 0 min (control), 60 min and 120 min; (ii) blanched in hot water at six diVerent timetemperature combinations (50 C for 40 and 80 min; 70 C for 10 and 45 min; 90 C for 3 and 10 min); (iii) immersed in a citric acid solution of 10 g/L for an hour; (iv) immersed in a sodium pyrophosphate solution of 10 g/L for an hour. Acrylamide content and color was determined in the potato strips after frying. Immersed strips in water for 120 min showed a reduction of acrylamide formation of 33%, 21% and 27% at 150, 170 and 190 C, respectively, when they were compared against the control. Potato strips blanched at 50 C for 80 min had the lowest acrylamide content when compared against strips blanched at diVerent conditions and fried at the same temperature (135, 327 and 564 m acrylamide/kg for 150, 170 and 190 C, respectively). Potato strip immersion in citric acid solution of 10 g/L reduced much more the acrylamide formation after frying than the strip immersion in sodium pyrophosphate solution of 10 g/L (53% vs. 17%, respectively, average values for the three temperatures tested). Acrylamide formation decreased dramatically as the frying temperature decreased from 190 to 150 C for all the pre-treatments tested. Color represented by the parameters L* and a* showed high correlations (r2 of 0.79 and 0.83, respectively) with French fry acrylamide content. 2005 Elsevier Ltd. All rights reserved.
Keywords: Potato strips; Frying; Acrylamide; Color; Blanching; Immersing

1. Introduction Immersion frying, or deep-fat frying, is a widespread operation used throughout food processing industries as well in catering operations and home preparation of foods. Potato (Solanum tuberosum) is one of the worlds major agricultural crops and it is consumed daily by millions of people from diverse cultural backgrounds. Potatoes are grown in approximately 80% of all countries and worldwide production stands in excess of 300 mil*

Corresponding author. Tel.: +56 93 591 679; fax: +56 26 823 536. E-mail address: fpedresc@lauca.usach.cl (F. Pedreschi).

lions tons/year, a Wgure exceeded only by wheat, maize and rice. US produces over 17.4 billion pounds of frozen and French fried potato products per year (National Potato Council, 1988). Immersion frying has been deWned as the immersion of a food product in an edible oil or fat heated above the boiling point of water (Hubbard & Farkas, 1999), and may therefore be considered a dehydration process. These conditions lead to high heat transfer rates, rapid cooking, browning, texture and Xavor development. High heat transfer rates are largely responsible for the development of the desired sensorial properties in fried potatoes (Farkas, Singh, & Rumsey, 1996).

0963-9969/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.foodres.2005.06.001

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Color of potato chips is an important parameter to be controlled during processing together with crispness, oil and acrylamide content (Pedreschi, Kaack, & Granby, 2004; Pedreschi, Moyano, Kaack, & Granby, 2005; Rosen & Hellens, 2002; Scanlon, Roller, Mazza & Pritchard 1994). Besides, fried potato color is the result of Maillard reaction as well, that depends on the superWcial reducing sugar content, and the temperature and frying period (Mrquez & An, 1986). Color of fried potatoes has been measured usually in units L*a*b* using either a colorimeter or speciWc data acquisition and image processing systems. L*a*b* is an international standard for color measurements, adopted by the Commission Internationale dEclairage (CIE) in 1976. L* is the luminance or lightness component, which ranges from 0 to 100, and parameters a* (from green to red) and b* (from blue to yellow) are the two chromatic components, which range from 120 to 120 (Papadakis, Abdul-Malek, Kamdem & Yam 2000). In the L*a*b* space, the color perception is uniform which means that the Euclidean distance between two colors corresponds approximately to the color diVerence perceived by the human eye (Hunt, 1991). Acrylamide has been classiWed as probably carcinogenic in humans (Rosen & Hellens, 2002; Tareke, Rydberg, Karlsson, Eriksson, & Tornqvist, 2002). In April 2002, Swedish researchers shocked the food safety world when they presented preliminary Wndings of acrylamide in some fried and baked foods, most notably potato chips and French fries, at levels of 302300 m/ kg. As acrylamide has not been detected in unheated or boiled foods, it was considered to be formed during heating at high temperatures. They attributed this fact to the higher temperatures reached in Maillard nonenzymatic browning reactions required for desirable color, Xavor and aroma production (Coughlin, 2003). The data published so far indicate that a temperature >100 C is required for acrylamide formation (Becalski, Lau, Lewis, & Seaman, 2003). Tareke et al. (2002) showed that acrylamide was formed by heating above 120 C certain starch-based foods, such as potato chips, French fries, bread and processed cereals. Recently, research has focused on possible mechanisms of acrylamide formation in foods (Zyzak et al., 2003). Some international research groups have separately conWrmed a major Maillard reaction pathway for acrylamide formation (Mottram & Wedzicha, 2002; Stadler et al., 2002; Weihaar & Gutsche, 2002). SigniWcant amounts of acrylamide are formed by the high-temperature reaction of glucose and the common amino acid asparagine (Coughlin, 2003). Since potato products are specially high in asparagine, it is now thought that this Maillard reaction is most likely responsible for the majority of the acrylamide found in potato chips and French fries. Acrylamide in fried potatoes is largely derived from heat-induced reactions between the amino

group of the free amino acid asparagine and the carbonyl group of reducing sugars such as glucose during frying. For frying temperatures between 120 and 150 C, it was found a linear correlation between acrylamide content of potato chips and their color represented by the chromatic redness component a* (Pedreschi et al., 2005). The actual mechanism of acrylamide formation has been recently published (Yaylayan, Wnorowski, & Perez Locas, 2003). Asparagine needs carbohydrates to generate acrylamide. Potential of acrylamide formation is strongly related to the sugar content such as glucose and fructose (Biedermann, Biedermann-Brem, Noti, & Grob, 2002; Pedreschi et al., 2004). For instance, some authors reported that the reduction of the sugar content by blanching or soaking could decrease acrylamide concentration by about 60% in potato chips (Haase, Matthus, & Vosmann, 2003; Pedreschi et al., 2004). Wide variations of acrylamide concentration in foods are, at least partially, caused by diVerent levels of precursors of acrylamide in various batches of raw materials (levels of asparagine and sugars Xuctuate widely in raw potato tubers). Potato variety, Weld site and processing conditions (pre-treatments, temperatures and times) had a noticeable inXuence upon acrylamide formation. Foods rich in both asparagine and glucose are largely derived from plant sources such as potatoes, but apparently not animal foods such as poultry, meat and Wsh. Martin and Ames (2001) found that asparagine was the free amino acid present in the highest amount in potatoes (93.9 mg/ 100 g). Asparagine content in potatoes depends on factors like variety, location, fertilization, storage and processing (Davies, 1977; Hippe, 1988). The analytical methods for acrylamide determination relies on using: (i) gas chromatography and mass spectrometry GCMS (Tareke et al., 2002), (ii) liquid chromatography and tandem mass spectrometry LC MSMS (Rosen & Hellens, 2002). French fries and potato crisps exhibit relatively high values of acrylamide 424 and 1739 g/kg, respectively. Recently an analytical method for analyzing acrylamide in coVee was validated (Granby & Fagt, 2004). Jung, Choi, and Ju (2003) showed that lowering the pH with citric acid before frying was an eYcient way to considerably diminish acrylamide formation in French fries. On the other hand, some authors reported that by lowering frying temperature at atmospheric pressure of potato chips from 185 to 165 C, it was possible to reduce the acrylamide formation to a half (Haase et al., 2003; Pedreschi et al., 2004). Granda, Moreira, and Tichy (2004) applied vacuum frying for producing potato chips and they could reduce acrylamide formation by 94%. These results suggest that there may be ways to reduce or prevent acrylamide formation by changing production and preparation methods. The objective of this work was to study acrylamide formation in potato strips

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processed under diVerent conditions and determine its relation to the frying temperature and the color of the potato pieces.

2. Materials and methods 2.1. Materials Potatoes (variety Bintje, 80 g/100 g of dry solids, higher diameter 710 cm) and vegetable oil (Fritao, Denmark) were the raw materials. Potatoes stored at 8 C and 95% of relative humidity were washed and peeled in an industrial peeler IMC (model M591E4, England). Strips of cross sections of 0.8 0.8 cm2 were cut from the pith of the parenchymatous region of potato tubers. A ruler and a knife were used to provide strips with a length of 5 cm. 2.2. Pre-treatments Strips were rinsed immediately after cutting for 1 min in distilled water to eliminate some starch material adhering to the surface prior to frying. Then, 30 potato strips were immersed in one liter of distilled water for the following times: 60 and 120 min before frying. Rinsed strips in water without the water immersing treatment were considered as the control. Blanching was accomplished by immersing 30 raw potato strips in 10 liters of distilled water (ratio of potato to water (g/g) of 0.012). The following temperaturetime blanching treatments were applied over the potato strips: (i) 50 C for 40 min, (ii) 50 C for 80 min, (iii) 70 C for 10 min, (iv) 70 C for 45 min, (v) 90 C for 3 min, (vi) 90 C for 10 min. Additionally, 30 raw potato strips were immersed for 60 min either in one liter of 10 g/L citric acid (J.T. Baker, Deventer, Holland) solution or in one liter of 10 g/L sodium pyrophosphate (SigmaAldrich, St. Louis, MO, US) solution. All experiments were run in triplicate. 2.3. Frying conditions Thirty strips of each pre-treatment were fried in an industrial fryer containing 100 L of oil at the following temperaturetime conditions: (i) 150 C for 11 min, (ii) 170 C for 8.5 min, (iii) 190 C for 6.5 min. These conditions allowed the fried strips to reach Wnal moisture contents of 40 g water/100 g (wet basis). Frying temperature was maintained constant since the potato mass to oil mass ratio (g/g) was kept very low (0.001333). 2.4. Analysis For acrylamide analysis, acrylamide (2-propene amide) [CAS No. 79-06-1] (>99.5%) was obtained from

SigmaAldrich (St. Louis, MO, US). Labelled d3-acrylamide (>98%) was from Polymer Source Inc. (Dorval, Quebec Canada). The SPE columns were Isolute Multimode 300 mg from International Sorbent Technology (Hengoed, Mid Glamorgan, UK). Mini uniprep TeXon Wlter vials 500 L, Wlter pore size 0.45 m, Whatman Int. Ltd (Kent, UK). The water used was MilliQ water (Millipore Corp., Bedford, MA, USA). The acetonitril was of HPLC grade from Rathburn Chemicals (Walkerburn, Scotland). Formic acid for the eluent (0.1% in water) was from Merck (Darmstadt, Germany). All stock solutions of acrylamide and d3-acrylamide (1000 and 10 g/mL) as well as calibration standards (230 ng/L) were prepared in water and kept at 18C until use. 4.00 g of homogenised potato were extracted with 40.0 mL MilliQ water by an Ultra-turrax mixer (Janke & Kunkel, Staufen, Germany) (after addition of 200 L d3acrylamide 10 g/mL as internal standard). Each analytical batch included 12 spiked samples for recovery measurements. The samples were centrifuged for 10 min at 3500 rpm (Hereaus Sepatech Megafuge 3.0 R, Osterode, Germany). The clean up was made on 300 mg Isolute Multimode SPE columns (IST), using an ASPEC TM XLi automatic SPE clean up system (Gilson Inc., Middleton, WI, US). The SPE columns were conditioned with acetonitrile (1 mL) and water (2 2 mL). The Wrst 500 L was discharged and the following 400 L of sample was collected in Mini uniprep TeXon Wlter HPLC vials. A HP1100 HPLC system (Agilent Technologies, Palo Alto, CA, USA) was used for acrylamide separation on a Hypercarb column, 5 m, 50 mm 2.1 mm (ThermoHypersil, Cheshire, UK, www.thermohypersil.co.uk) after a guard column (Phenomenex SecurityGuardTM, C18 ODS, 4 mm 2.0 mm, Cheshire, UK). 10 L was injected and eluted with 0.1% formic acid in water at a Xow of 250 L min1. The MS/MS detection was performed on a Quattro Ultima triple quadrupole instrument with masslynx software (Micromass Ltd., Manchester, UK). The electrospray was operated in the positive ion mode, and the capillary was set to 3.0 kV, the cone voltage was 31 V, and the collision energy 10 eV. The source temperature was set at 120 C and the desolvation temperature at 400 C. Nitrogen was used as nebulizer gas (Xow 500 L h1) and desolvation gas (Xow 150 L h1), and argon was used as collision gas at a pressure of 2.3 e3 mbar. The multiple reaction monitoring (MRM) mode of the degradation patterns m/z 72 ! 55 (acrylamide) and m/z 75 ! 58 (d3-acrylamide) were used for quantiWcation. Acrylamide analyses were done in a laboratory accredited for acrylamide analysis in foods by The Danish Accreditation Body. Fried potato strip color was measured using a Minolta Chromo Meter CR 200b attached to a dataprocessor DP-100 using the CIE Lab L*, a* and b* color scale. Triplicate readings were carried out at 20 C on

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each three equidistant locations of each strip (in the four bigger sides) and the mean value was recorded. Color changes were followed by the lightness (L*) and redness (a*) parameters since these color components presented the highest and signiWcant variations during frying due to non-enzymatic browning reactions. 2.5. Statistical analysis Analysis of variance was carried out using Statgraphic Statistical Package (Statistical Graphics Corporation, Version 4, Rockville, USA) including multiple range tests (P > 0.05) for separation of least square means.

acrylamide formation of 16%, 15% and 9% at 150, 170 and 190 C, respectively, when they were compared against the control. Besides, immersed samples for 120 min showed a signiWcant reduction (P > 0.05) in acrylamide formation of 32%, 21% and 27% at 150, 170 and 190 C, respectively, when they were compared against the control. These results are coincident with those reported by Jung et al. (2003) who reported that dipping potato strips in distilled water for 1 h induced almost 25% reduction of acrylamide formation in French fries after frying at 190 C. 3.2. Blanching Acrylamide formation increased signiWcantly (P > 0.05) in blanched samples when the frying temperature was increased (Fig. 2). For instance, acrylamide contents were 287, 1338 and 2128 g/kg after frying at 150, 170 and 190 C, respectively, in the case of potato slices blanched at 70 C for 10 min. Long time blanching treatments such as that of 50 C for 80 min and 70 C for 45 min resulted in the lowest levels of acrylamide formation (342 and 538 g/kg as average values for the three frying temperatures tested). These two blanching treatments, after frying at 190 C, lead to the lowest acrylamide contents (564 and 883 g/kg, respectively). Blanching in general, removes much more glucose and asparagine from the potato slices than the water immersing treatment consequently leading, to signiWcant lower acrylamide formation in the resultant fried potatoes (Pedreschi et al., 2004). Haase et al. (2003) reported that a reduction of the sugar content by blanching could reduce the acrylamide concentration by about 60% according to the raw material (potato variety and Weld site) and the production process variables (e.g. blanching conditions and frying temperatures). Blanched samples resulted in prepared potato strips lighter in color than those of the control or the samples immersed in water at ambient

3. Results and discussion 3.1. Immersion in water Both, the fried control and water immersed samples, showed a signiWcant increase (P > 0.05) in acrylamide formation as the frying temperature increased from 150 to 190 C (Fig. 1). The reduction of the frying temperature from 190 to 170 and to 150C, decreased acrylamide formation with 21% and 66%, respectively (average values for control and water soaked samples). These results are in agreement with those of Haase et al. (2003) and Pedreschi et al. (2004). Average acrylamide contents for control and immersed strips were 1416, 3259 and 4134 g/kg after frying at 150, 170 and 190 C, respectively. For the three temperatures tested, acrylamide formation was higher in the control than in immersed samples suggesting that the water immersing process leads to a higher leaching of important acrylamide precursors (such as glucose and asparagine) that Wnally results in lower acrylamide formation. Immersed samples in distilled water for 60 min showed a reduction in

Fig. 1. Acrylamide content of potato strips immersed 0 min (control), 60 min and 120 min in distilled water after being fried at 150, 170 and 190 C.

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F. Pedreschi et al. / Food Research International 39 (2006) 4046

Fig. 2. Acrylamide content of potato strips blanched at diVerent temperaturetime combinations after being fried at 150, 170 and 190 C. First numbers inside parenthesis indicate the blanching temperature (C); second numbers indicate the blanching time (min). Control corresponds to potato strips not blanched.
6000 Control TetraPyroposphate Na (1%) Citric Acid (1%) 4000

Acrylamide content (g/kg)

2000

0 150 170 Frying temperature (C) 190

Fig. 3. Acrylamide content of control and potato slices dipped in 10 g/L citric acid and tetrapyrophosphate Na solutions for 60 min after being fried at 150, 170 and 190 C. Control corresponds to potato strips not immersed in any solution.

temperature (visual observations). Besides, as the frying temperature increased, the potato chips got darker as perceived by the naked eye. 3.3. Immersion in citric acid and sodium pyrophosphate solutions The eVect of immersing potato slices in citric acid and sodium pyrophosphate solutions of 10 g/L over acrylamide formation after frying was also studied. As in the previous pre-treatments studied, acrylamide formation increased drastically with increasing frying temperature not only for the potato strips immersed in citric acid solution but also for those immersed in sodium pyrophosphate solution (Fig. 3). Immersion in citric acid solution was a more eVective pre-treatment in reducing acrylamide formation in French fries than immersion in sodium pyrophosphate solution. Strip immersion in sodium pyrophosphate solution of 10 g/L reduced acrylamide formation in

30%, 7% and 14% with respect to the control, for the frying temperatures of 150, 170 and 190 C, respectively. The Wnal acrylamide contents of the French fries previously immersed in this solution were 1180, 3427 and 4028 g/kg for 150, 170 and 190 C, respectively (Fig. 3). On the other hand, strip immersion in citric acid solution of 10 g/L reduced signiWcantly (P > 0.05) acrylamide formation in 86%, 47% and 28% with respect to the control, for the frying temperatures of 150, 170 and 190 C, respectively. Jung et al. (2003) reported that dipping potato strips in a 10 g/L citric acid solution induced 73.1% reduction of acrylamide formation potato strips fried at 190 C. However in our frying experiments the percentage of acrylamide reduction by the immersion in the citric acid solution previous to frying diminished as the oil temperature increased (from 86% to 28%). In our experiments this pre-treatment reduced acrylamide formation in potato strips fried at 190 C in only 28%. This result is in agreement to that found by Pedreschi et al. (2004) for potato chips previously

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immersed in a citric acid solution of 10 g/L. In this case acrylamide formation was reduced signiWcantly (P > 0.05) in potato slices fried at 150 C (70% with respect to the control). However, when the pre-treated potato slices were fried at 170 and 190 C, there were no detected signiWcant diVerences between the acrylamide content of these samples and that of the control. Jung et al. (2003) attributed the reduction of acrylamide formation in French fries by dipping the potato strips in citric acid solutions to both pH lowering and leaching out of free asparagine and the reducing sugars from the surface layer of potato cuts to the solutions. These authors also explain the mechanism by which lowering the pH of the potatoes reduces acrylamide formation after frying. Fried potato color is the result of Maillard, non-enzymatic browning reactions that depends on the superWcial reducing sugar content, and the temperature and frying period (Mrquez & An, 1986). Acrylamide concentration showed a good linear correlation with the color of the fried potato strips pre-treated in diVerent ways (Wnal moisture content 40 g/100 g total basis). Luminosity color component (L*) which ranges from 0 to 100 tends to decrease with the frying temperature and time since the potato strips get darker. On the other hand, the chromatic color component a* which ranges from 120 to 120 tends to increase with both frying time and frying temperature as a result of the formation of compounds from the Maillard non-enzymatic reaction. An increase in a* values means that the potato strips get more red. Fig. 4(a) and (b) shows that not only L* but also a* presented good correlation with the acrylamide content of the fried potato strips previously treated in the diVerent ways mentioned in this research (r2 D 0.79 and r2 D 0.83, respectively). As the frying temperature increase from 150 to 190 C, the resultant chips get more red and darker as a result of non-enzymatic browning reactions that are highly dependant on oil temperature and frying time. Blanching reduces the L* and a* values of French fries probably due to the leaching out of reducing sugars previous to frying inhibiting in this way nonenzymatic browning reactions and leading to lighter and less red French fries (Pedreschi et al., 2004). Lightness of French fries decreased as the acrylamide formation increased (Fig. 4(a)) since the pieces get darker as a result of Maillar reactions. Besides, the redness chromatic component of French fries increased with the acrylamide formation since the pieces tend to get more red as the Maillard non-enzymatic reaction develops (Fig. 4(b)).

Fig. 4. Acrylamide content vs. color parameters L* (a) and a* (b) for potato strips fried at 150, 170 and 190 C for all the pre-treatments tested.

acrylamide formation in potato strips after frying at the three frying temperatures tested. The previously reported citric acid immersion eVect in acrylamide reduction in French fries was conWrmed in this research. For all the pre-treatments tested, acrylamide formation diminished signiWcantly (P < 0.05) as the frying temperature decreased from 190 to 150 C. There were detected linear correlations between color parameters L* and a* and acrylamide formation in French fries. This fact suggests a relationship between the acrylamide formation and the degree of non-enzymatic browning developed during frying according to the pre-treatments employed.

Acknowledgments Authors acknowledge Wnancial support from FONDECYT Project No. 1030411 and the Danish Ministry for Food, Agriculture and Fisheries (Project: Reduction of the Formation and Occurrence of Acrylamide in Food).

4. Conclusions Immersion of potato strips in distilled water decreased the acrylamide formation after frying. The longer the immersion time the lower acrylamide formation after frying. Blanching lead to a signiWcant (P < 0.05) reduction of References
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