W H I T E P A P E R

Natural Antioxidant Solutions

for Nuts and Omega Rich
Food Applications
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Introduction
Lipid oxidation is one of the leading causes of shelf-life failure in fat containing foods, generating
off-flavors and off-aromas. Oxidation is often accompanied by a loss of
color pigments, nutrients and vitamins. In some cases, it can lead to
changes in texture and to a loss of (protein) functionally.
Oxidation affects a wide array of foods and edible
oils, including omega-3 specialty oils, fried foods,
meats, cereals, baked goods, snacks, sauces,
dressings, beverages, dairy products, and nuts.

The use of antioxidants constitutes a major

oxidation defense strategy. Synthetic
antioxidants like BHA, BHT and TBHQ (some of them
initially developed for the plastics industry), have been
routinely used in foods for a number of years. Although they are
proven to be effective, they usually come with a negative consumer image: they are derived
from fossil fuels, and they have long chemical names like butylated hydroxyanisole, butylated
hydroxy toluene, and tert-butylhydroxyquinone. There is an increasing demand for natural
alternatives, beyond tocopherols, to replace synthetic antioxidants, in order to delay lipid
oxidation in foods and maintain freshness.

Kalsec® Solution
Rosemary has been used in culinary applications since ancient times, and there have been
hundreds of reports on its antioxidant activity published since the 1950’s. Today, it is the
dominant herb antioxidant extract on the market, both in Europe and the United States. Its
activity is mainly attributed to its predominantly oil soluble phenolic diterpenes like carnosic acid,
and the water soluble phenolics such as rosmarinic acid. Two main issues limit the use of
rosemary extracts as an effective antioxidant for foods:

 The inherent high (rosemary) flavor profile in taste sensitive food applications such as snacks,
nuts, spreads, cereals, enriched dairy products, fried applications, beverages, and many
others. This issue is mainly attributed to the residual essential oils in the rosemary antioxidant
extract.

 The need for different types of functionality in certain systems: the main active antioxidant
components of rosemary function as radical scavengers or primary antioxidants, and they
have a defined range of polarity. Certain complex food systems, especially emulsions,
require a multiple antioxidant blend approach, with a varying range of both antioxidant
functionality and polarity.

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To overcome these challenges, Kalsec®, the market leader in natural antioxidants, has
developed multiple solutions.

Solution to the Rosemary Flavor Issue

Kalsec® has developed a low flavor rosemary, with a unique functionality fingerprint. This highly
deflavorized rosemary extract is extremely low in essential oils, and at the same time, high in
active rosemary antioxidant components. It is further standardized and diluted for easy and
efficient incorporation into a multitude of food products. The unique extract profile goes beyond
the known active phenolic diterpenes, and allows the use of antioxidant-effective dosage of
rosemary extract, without the typical flavor, aroma or color implications.

Solution to the Limited Functionality and Polarity of Primary Antioxidant Extracts:

Success Stories
Market trends are driven by consumer preferences, resulting in continuous food reformulation.
Recently, food reformulations have been focused on replacing oxidatively stable saturated
(and especially hydrogenated) fats, with healthier unsaturated fats. The incorporation of the
oxidatively unstable nutritional ingredients (polyunsaturated fats-PUFA’s) will require powerful
strategies to control oxidation, due mainly to the high oxidation reactivity of PUFA’s. Formulators
are turning to natural antioxidants for cleaner labels; however, they do not have the
effectiveness reputation of synthetic antioxidants.

Case Study 1: Walnuts

Background
Nuts contain high levels of fats, but it is mostly their fatty acid profile that
makes them desirable and potentially beneficial from a dietary intake
perspective due to their levels of MUFA’s (monounsaturated fatty
acids) and PUFA’s (polyunsaturated fatty acids). This value can
be delivered by the nuts alone or as an ingredient in an inclusive
food system such as granola bars. The polyunsaturated fatty
acid profile, however, makes them prone to oxidation.

Objective
Assess, measure and quantify oxidation in walnuts, and evaluate natural antioxidants as a
solution. Methods of antioxidant incorporation vary based on the type of nuts and the finished
food formulation, but in this example, the nut type was brine salted walnuts.

Summary of Experimental Details

Fresh walnuts were treated with a 10% solution of table salt. The untreated control did not
contain antioxidants, and was compared to nuts treated with the same brine solution,

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containing an Herbalox® extract at a 0.1% final pickup concentration in the nuts. Nuts were then
vacuum tumbled at -15 psi for 30 minutes, followed by roasting in a conveyer oven at 176 °C
(350 °F) for 7 minutes. Subsequently, roasted nuts were stored in foiled bags and incubated in
the dark at 40 °C. The nuts were analyzed by SPME GC-MS for secondary oxidation product
development (with hexanal as a marker). Samples of treated and untreated nuts were analyzed
right after roasting (time zero), and after 6 days incubation.

Results
Data showed lower levels of hexanal in the Herbalox® treated nuts even at time zero (right after
roasting). The trend continued throughout incubation, resulting in hexanal levels ~ 55% lower in
the treated sample vs. the control, as shown in Graph 1.

Graph 1: Decrease in secondary oxidation marker hexanal measured by SPME GC-MS in

Walnuts incubated for 6 days in the dark at 40 °C.

Hexanal Reduction in Roasted Walnuts

Aged at 40°C for Six Days

120
Hexanal as percent of control

100

80

60

40

20

0
Control 0.1% Herbalox®

Case Study 2: Fish Oils

Background
There is heightened consumer awareness about the health benefits of marine oils rich in omega-
3 fatty acids like docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). As a result,
there is an increasing number of food products, ranging from milk, yoghurt, juice, energy bars,
snacks and eggs enriched with either fish oil, algal oil, or the individual purified fatty acids.
Omega-3 fatty acids, however, are highly prone to oxidation due to their high degree of
unsaturation. This will often result in an objectionable fishy odor that can develop very quickly
and can cause the enriched food product to become less palatable and decrease shelf-life.

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Objective
Assess, measure and quantify oxidation in fish oil emulsions, and evaluate natural antioxidants as
a solution. The antioxidants needed to stabilize omega-3 oils in a finished final product may be
different than the ones used to preserve omega-3 oils in the bulk (or capsule) form. Therefore,
newly developed Duralox® oxidation management systems were customized for emulsion needs
and were evaluated for their performance.

Summary of Experimental Details

Two types of emulsions were prepared: 20% oil-in-water emulsion (10% canola oil with 10% fish
oil, and 5% fish oil with 15% canola oil) using Tween-20 (Polysorbate-20) at 0.2% in an oil-in-water
emulsion buffered with phosphate at ~ pH 7. Both emulsions were homogenized through a two-
stage homogenizer to a particle size smaller than 1 μm. The emulsion with the lower fish oil level
(5%) was aged at room temperature in an orbital shaker for five days. The emulsion with the
higher fish oil level (10%) was aged under further accelerated conditions by incubating in an
orbital shaker at 45 °C for two days. The oxidation was tracked through measurement of
hydroperoxides throughout the incubation time (method adapted from J. Agric. Food Chem.,
48, 213-219). In each case, the control without antioxidants was compared to an emulsion
treated with Duralox® -1 and Duralox® -2 Oxidation Management Systems at 500 ppm containing
rosmarinic acid, metal chelating vegetable derived extract, and catechins.

Results
Data showed lower levels of hydroperoxides in the treated samples throughout oxidation,
consistently in both emulsions (5% fish oil at ambient temperature and 10% fish oil at 45 °C) as
shown respectively in Graph 2 and Graph 3.

Graph 2: Progression of primary oxidation markers, hydroperoxides, over time in 5% fish oil
emulsion incubated at ambient temperature in the dark.

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Graph 3: Progression of primary oxidation markers, hydroperoxides, over time in 10% fish oil
emulsion incubated at 45 °C in the dark.

Conclusion
By applying the highest level of scientific discipline to test, document and replicate advances,
products such as our rosemary based Herbalox® Rosemary Extracts in combination with Duralox®
Oxidation Management Systems have demonstrated the ability to naturally increase shelf life
and stability of challenging unstable oils and food formulations. Managing the natural oxidation
of food can be best achieved by developing customized solutions for a variety of application.
Kalsec®’s relationship and application specific approach can assist customers in meeting their
reformulation needs with a consumer friendly clean label. Kalsec®’s team of specialists is
dedicated to helping you build lasting relationships with our brand, by making your products last
longer naturally.

About Kalsec®
Kalsec is a privately held producer and marketer of natural extracts for use in food, beverage
and pharmaceutical applications (www.kalsec.com). Selling and marketing in more than 70
countries worldwide, Kalsec is dedicated to delivering the best products on time and backed
with unparalleled technical expertise. Founded in 1958, the company is headquartered in
Kalamazoo, Mich., with additional facilities in the U.S., Europe and Asia.

Copyright Kalsec® 2012 All Rights Reserved.

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