3.1. Nutritional and Technological Characteristics
Almond skin powder is particularly rich in fiber (52.6 g/100 g), as shown by the analysis of its nutritional characteristics (
Table 3).
This by-product of almond processing also showed a relevant presence of lipids (21.3 g/100 g). The lipid fraction of almond skins, however, is particularly healthy, being composed mainly of mono and polyunsaturated fatty acids (mostly oleic and linoleic acids) [
6] associated with high amounts of vitamin E [
6]. The composition of the lipid fraction of skins parallels the lipid composition of the whole seed [
35]. The protein content of almond skins accounted for about 11 g/100 g, and low amounts of carbohydrates were observed. The overall composition of almond skin powder agreed with the current literature [
6,
36]. The composition of wheat flour was quite different than that of almond skins, being rich in carbohydrates and poor in fiber, with negligible levels of lipids.
The analysis of the nutritional features of biscuits (
Table 4) shows that the protein content was not significantly influenced by the addition of almond skins, the latter having a protein content similar to wheat flour. However, AS20 biscuits had a significantly (
p < 0.05) higher lipid content than control, due to the relevant contribution of almond skins. The lipid content of all biscuits was in the range of those commonly marketed [
37].
As for the content of dietary fiber, it progressively increased with the increase of almond skin addition. EC Regulation n. 1924/2006 [
38], relating to nutrition and health claims made on food products, defines that a food is a “source of fiber” only if contains at least 3 g/100 g fiber, or at least 1.5 g/100 kcal fiber, while “high in fiber” applies only if a food contains at least 6 g/ 100 g fiber, or at least 3 g/100 kcal fiber. The level of fiber ascertained in AS10 and AS20 biscuits met the requirements for applying the “source of fiber” and the “high in fiber” claims, respectively.
Moisture content increased, but not significantly, after the addition of almond skins due to their contribution of fiber. The higher the protein and fiber content, the higher the water absorption by the dough and moisture retention are found of the final product [
39].
As a consequence of the increase in fats and fiber, the level of carbohydrates significantly decreased in almond skin-added biscuits compared to control. The energy value did not vary significantly by adding almond skins, because the increase of lipids was compensated for by an increase of fiber and a decrease in carbohydrates.
As for the main physical characteristics (
Table 5), the a
w of AS10 and AS20 was slightly higher than control, but without a significant difference. The a
w values observed in all biscuits agreed with moisture content and showed that they were conveniently dry and stable from the microbiological point of view (a
w < 0.6).
The addition of almond skins, which were brown colored, resulted in an expected substantial alteration of biscuit color (
Figure 1), with a significant decrease of
L* and
b*, and an increase of
a* in AS10 and AS20 compared to the control (
Table 5). The total color difference (∆E) of AS10 and AS20 biscuits compared to the control was greater for AS20 than for AS10, but in both cases with very high values, confirming that the control had a distinct color [
40]. ∆E values >12.0, in fact, indicate a very obvious color difference [
32].
The textural analysis showed that the addition of almond skins caused a decrease in the strength necessary to break the biscuits, i.e., an increase of friability, which is a particularly important characteristic. Friability is a salient textural characteristic for biscuits [
41,
42]. Tough, non-crumbly biscuits have low acceptance values in consumer tests [
43]. This variation of breaking strength was significant when comparing control with AS20 and was due to the high presence of fiber in the almond skins. Fibers are highly hygroscopic and interfere with the formation of a strong and complete gluten network [
44]. Preliminary work, in fact, showed that the rheological properties of the dough [
7] significantly worsened after the addition of almond skin powder. However, among baked goods, biscuits are the most suitable for being reformulated with the addition of fibrous raw materials, since for their production a weak gluten network is not only sufficient but even necessary. In addition, although the difference in lipid content with control was significant only for AS20, the lipid fraction deriving from almond skins could have positively influenced the friability [
45]. Therefore, the addition of almond skins did not harden biscuits at all; on the contrary, it gave a crumblier texture.
As for the dimensional variations induced by baking (
Table 6), due to the thermal expansion of gases (carbon dioxide developed by the baking powder, dough moisture, and air entrapped during kneading), all biscuits increased more in thickness than in diameter. This result, commonly observed in biscuit baking [
19], is due to the retaining effect of gluten, which tends to limit enlargement, whereas the upward thrust of the oven heat (oven rise) is less opposed [
45]. AS10 and AS20 showed a greater diameter increase than control, which was significantly different for AS20, but had a lower increase in thickness. The easier enlargement observed in almond-skin added biscuits was due to the coupled effect of the dilution of gluten by a non-gluten raw material and the interference with gluten formation by the fiber and lipids of the same material. These findings agreed with studies where other fibrous and gluten-free ingredients were added to biscuit dough [
18,
19]. In addition, better expanded biscuits are usually less compact and more friable than those which expand less, in agreement with the observed textural data.
The spread factor increased progressively as the amount of almond skins increased, with a significant difference between control and AS20. A higher spread factor indicates a better quality and is linked to an increase in consumer acceptability [
46]. The observed values were higher than those reported for biscuits enriched with pure fiber of various cereals [
47].
Weight loss, primarily due to the moisture loss from dough during baking, decreased by increasing the amount of almond skins as a consequence of the greater hygroscopicity of fibers, which limited water migration. The values ascertained were in the range of other researches [
48,
49,
50].
The sensory profiles of the biscuits showed significant differences in odor, color and textural descriptors (
Table 7). As for taste, the bitter note was negligible in the biscuits investigated, while sweetness was moderately intense, both without significant difference among formulations.
A slight odor note of caramel, derived from sugar caramelization and Maillard reaction, was perceived by the panelists in all biscuit types, without statistically significant differences between them. Instead, differences between the samples were found in the intensity of leafy odor. This odor note, absent in the control, was perceived with low intensity in biscuits formulated with almond skins, with the highest perception in AS20 and with an intermediate value in AS10. In previous research [
7] this characteristic smell note was observed in the dried almond skins used in biscuit-making, albeit much more pronounced than in the finished product.
The color of biscuits became progressively and significantly darker as the level of addition of almond skin powder increased, as already indicated by colorimeter determinations.
As for friability, evaluated as the way biscuit fractured when broken by finger, the sensorial results were similar to those obtained instrumentally by the texture analyzer (snap test). AS20 was significantly more friable than control.
Dryness and graininess, on the other hand, were evaluated during chewing. Dryness did not show significant differences, whereas graininess was scored higher in almond-skin added biscuits, due to their granular and fibrous crumbles.
3.2. Functional Characteristics
Almond skins are rich in phenolic compounds [
7], therefore the content of these bio-actives was evaluated in biscuits, as well as antioxidant activity (
Table 8). The total sum of phenolic compounds, determined by HPLC, was significantly higher in AS10 and AS20 than in control.
In more detail, the variation of the single phenolics did not show the same trend for all the compounds, which showed different behavior according to the phenolic composition of the raw materials. In particular, among the phenolic acids, the
p-hydroxy benzoic and protocatechuic acids showed a relevant increase after the addition of almond skins. The flavan-3-ols catechin and epicatechin also followed the same trend, being not detectable in control and showing a concentration-effect increment between the AS10 and AS20. In fact, these phenolic compounds are the most abundant in almond skins [
7]. A smaller increase, but always statistically significant, was observed for syringic acid, vanillic and
p-coumaric acids.
Instead, the most abundant phenolic acid, namely the ferulic acid, followed by the sinapic acid, decreased when comparing control biscuits with the almond-skin added, because these phenolic acids are typically present in wheat [
33,
51], but not in almond.
The flavonol glycosides and their aglycones, as well as the flavanone glycosides and their aglycones, despite their presence in almond skins [
7], were not detected in biscuits. Probably, since their starting quantity was not remarkably high, they became undetectable in the biscuits, due to the dilution effect of wheat flour. In addition, oxidation and other degradation phenomena could not be excluded during processing (kneading and baking) since a decrease in phenolic compounds had already been observed when raw almond skins were thermally dried [
7]. In any case, the total phenolic compounds of AS20 were approximately double that of the control, indicating that the addition of almond skins in the formulation can concretely contribute to enhance the nutritional value and the potential health benefits of the end products.
The antioxidant activity followed the same trend as the phenolic and showed higher values in the almond skin supplemented biscuits, compared to the control, also highlighting a concentration effect. Indeed, in the AS20, the antioxidant activity was about five times higher than the control. The observed values of antioxidant activity were consistent with those of the almond skins added [
7].