3.1. Drying kinetics
Fresh blood orange slices had an initial moisture percentage of 83.10% ± 0.26%. On a wet basis, the slices were dried until they had a final moisture percentage of 10%. Drying was performed using HAD, VD, and UAVD methods at temperatures of 50, 60, and 70 °C, as well as through FD.
Figure 1 shows the pictures of fresh and dried blood oranges with HAD, VD, UAVD, and FD. The samples that were dried using HAD were found to have less volume.
Figure 2 indicates the experimental data for the moisture ratio (MR) vs time curves of blood oranges dried with HAD, UAVD, and VD methods. Regardless of the drying methods, the moisture ratio (MR) continuously diminished during drying period. There is no constant rate period in these curves, only a decreasing rate period is observed. The MR values were utilized to assess the eleven models delineated in
Table 1.
Table 2 displays the predicted model parameters and the statistical metrics for blood orange slices. The model that most accurately represented the thin-layer drying kinetics was selected based on the greatest R² values and the lowest RMSE and χ² values.
Table 2 indicates that the Logarithmic model was the most effective for the HAD, VD, and UAVD approaches, with R2 values ranging from 0.997 to 0.998, 0.999 to 1.000, and 0.999 to 1.000, respectively. The k values for the Logarithmic model were established as 0.131, 0.166, and 0.330 for 50, 60, and 70 °C for HAD drying, and 0.156, 0.156, and 0.152 for VD, respectively. Consequently, a vacuum facilitates the transfer of water from the inside to the exterior due to the elevated water vapor pressure at reduced temperatures. Akdas and Baslar [
39] identified the logarithmic model as the most effective model for Mandarin. The remaining 10 models exhibited high determination coefficients (R²) ranging from 0.979 to 0.998 for HAD, from 0.983 to 1.000 for VD, and from 0.982 to 1.000 for UAVD methods.
Table 3 indicates the drying time, drying rate, effective moisture diffusivity, and total energy consumption of the blood orange slices. Drying times were recorded as 22.5 hours, 12.5 hours, and 9 hours for HAD; 11.5 hours, 9.5 hours, and 8.5 hours for VD; and 10 hours, 8.5 hours, and 7.5 hours for UAVD at 50, 60, and 70 °C, respectively. A reduction in drying time was observed with increasing temperatures. Further analysis revealed that ultrasonic pretreatment significantly decreased the drying period. The effectiveness of ultrasound in minimizing drying durations has also been reported in other studies involving various fruits [
37,
40,
41]. The gradual increase in the product's temperature throughout the hot air-drying process, due to external heat transfer, impedes internal moisture migration, thereby extending the drying duration. In contrast, vacuum drying decreases pressure, which reduces the water boiling point in the food, hence increasing the surface evaporation rate. The combination of ultrasound with vacuum has been shown to significantly reduce drying times. This effect is attributed to cavitation, which creates microscopic voids within the structure of fruits and vegetables, facilitating easier water removal and thereby shortening the drying process. The secondary consequence is the mechanical impact induced by ultrasound, which diminishes the adhesion between moisture and the microtube, hence expediting moisture evacuation [
42]. Furthermore, ultrasonic treatment can diminish internal viscosity and enhance the heat transfer coefficient [
13]. The last impact of ultrasound is the thermal effect, which induces a marginally accelerated temperature rise, advantageous for the internal diffusion and evaporation of moisture [
40].
3.2. Total phenolic content and antioxidant capacity
Citrus fruits are abundant in phenolic acids and flavonoids, two principal categories of natural antioxidants that underlie their functional qualities. The differences in flavonoid content in fruits are primarily due to biological factors [
45]. These secondary metabolites serve several functions in the plant; specifically, in the fruit, they are linked to color, sensory attributes (flavor, astringency, texture), nutritional properties, and antioxidant activity [
46].
TPC values and antioxidant capacity values determined by DPPH and ABTS methods of fresh blood orange slices and blood orange slices dried with HAD, VD, and UAVD at 50, 60, and 70 °C, as well as through freeze-drying are shown in
Table 4. The TPC value of the fresh blood orange slice was 154.25 mg GAE/100g. The drying techniques and temperatures substantially influenced the total bioactive phenolic compounds and antioxidant activity levels. The FD dried blood orange slices have the highest TPC value (131.27 mg GAE/100g) within the dried blood orange slices. The TPC result of the samples dried by UAVD at 50 °C (128.77 mg GAE/100g DM) is comparable to that of the FD-dried samples (131.27 mg GAE/100g DM)(p<0.05). The preservation of TPC is due to the low temperature and vacuum conditions inherent to the FD process. Tekin-Cakmak et al. [
15] and Goztepe et al. [
33] indicated that some red fruits, when dried using similar procedures, had the greatest TPC values in freeze-dried samples. The TPC of dried blood orange slices diminished as a result of thermal degradation at rising temperatures throughout the drying process. For UAVD, TPC values decreased from 128.77 mg GAE/g DM to 65.25 mg GAE/g DM by increasing the temperature from 50 °C to 70 °C. Similarly, research on Tunisian eggplants examined how different drying techniques impacted their drying properties and bioactive compounds. Chouaibi et al. [
47] established that both freeze-drying and ultrasound-assisted drying reduced product deterioration, corroborating results from analogous research. The elevated TPC value of UAVD-dried blood orange slices has been implicated in the occurrence of cavitation, resulting in the extraction of components that are released from cells during the drying process.
The antioxidant activity of many foods has been extensively studied due to its ability to counteract oxidation processes that reduce chronic illnesses associated with oxidative stress in the human body [
48]. Various antioxidant chemicals, including ascorbic acid, flavonoids, and phenolic acids, were regarded as natural sources in horticulture goods. The ABTS analysis was employed to assess the antioxidant potential of both lipophilic and hydrophilic antioxidants, encompassing flavonoids (flavones, flavanones, and flavonols) and phenolic acids, particularly ferulic acid and p-coumaric acid [
49]. The antioxidant capacity of fresh blood orange slices was determined to be 7380.01 mg TE/100g DM in the DPPH assay and 242.67 mg TE/100g DM in the ABTS assay. Consistent with the TPC results, the maximum DPPH and ABTS values recorded were 7330.09 mg TE/g DM and 226.46 mg TE/g DM, respectively, in FD-dried blood orange slices. At 50 °C, the UAVD technique yields 6907.63 mg TE/100g DM, followed by the FD method at 7339.09 mg TE/100g DM for DPPH, with the VD method resulting in 5990.63 mg TE/100g DM thereafter. A comparable pattern observed with DPPH is also evident with ABTS. Thermal treatments and oxidative processes may have caused the breakdown of phenolic compounds and reduced the antioxidant activity of the samples [
50]. The antioxidant capacity of fruits dried using the UAVD technique surpasses that of samples dried using HAD, as indicated by TPC findings. The results indicate that the UAVD approach could be beneficial as an alternative to the HAD method.
3.3. Vitamin C
The concentrations of different chemical constituents, such as vitamins, minerals, and phenolics, which are recognized for their potent antioxidant qualities, impact the quality of citrus fruits [
51]. Fresh juice has high levels of vitamin C, which is measured as ascorbic acid among the vitamins [
52]. Rapisarda [
53] reported that vitamin C is rich in blood oranges; in fact, Moro and Tarocco have a higher concentration of vitamin C than many other blood orange cultivars, with juice containing 0.50 to 0.80 g/kg. The vitamin C content of both fresh and dried blood orange slices is also shown in
Table 4. Fresh blood orange slices have a vitamin C level of 55.32 mg/100g, whereas dried blood orange slices have a vitamin C content of 29.79 to 49.01 mg/100g, which is quite comparable to what has been found in other studies [
46,
54].
3.4. Individual phenolic compounds
Table 7 shows the effect of different drying methods and temperatures on individual phenolic compounds of blood orange slices. The HAD method caused greater reductions in the amount of all phenolic compounds identified than other drying methods. Hirsch [
55] indicated that the activation of oxidative enzymes, including polyphenol oxidase, during hot air oven drying results in a reduction of flavonoid concentration. The loss was reduced due to the diminished activity of the polyphenol oxidase enzyme during freeze-drying at lower temperatures [
56].
There are 6 hydroxycinnamic acids found in blood orange slices which are caffeic acid, chlorogenic acid, ferulic acid, o-coumaric acid, p-coumaric acid, and sinapic acid. Ferulic acid was the most dominant hydroxycinnamic acid in fresh and dried blood orange slices, accounting for the largest proportion of the total hydroxycinnamic acid contents. Ferulic acid is found mostly in fresh blood oranges (2442.164 mg/100gDM). Among dried blood oranges, freeze-dried blood oranges contained the most ferulic acid (2307.669 mg/100 gKM), followed by blood oranges dried with UAVD at 50 °C with a ferulic acid content of 2142.062 mg/100 gKM. Ellagic acid is a hexahydroxydiphenic acid abundantly found in fruits, pomegranates, cranberries, and other plant foods. This study found that it is the most abundant compound in blood orange after ferulic acid. Ellagic acid exhibits a wide range of biological properties, such as playing an active role in anti-cancer treatment [
57].
Flavonoids isolated from citrus fruits are a group of natural compounds with phenolic structures. This study found 6 flavonoids chrysin and rutin were flavon, catechin, myricetin and quercetin were flavanol, and hesperidin was flavanone. Flavanone is the major flavonoid in orange varieties.
Table 7 shows that hesperidin was a flavanone and the most abundant individual phenolic compound in fresh and dried blood orange slices. Hesperidin is found mostly in fresh blood oranges (12,201.82 mg/100gDM), followed by freeze-dried blood oranges (11,766.77 mg/100gDM).
3.5. Color
The critical factor of dried products influencing consumer acceptance is product color.
Table 8 displays the color characteristics of fresh and dried blood orange slices. The L*, a*, and b* values of fresh blood orange slices are 54.07, 18.35, and 16.15, respectively. In contrast, the L* values of dried blood orange slices vary from 40.44 to 52.70, the a* values range from 9.90 to 19.38, and the b* values range from 5.11 to 16.15. The L*, a*, and b* values of the FD dry blood orange slices were the highest among all dried blood orange slices and were closer to the L*, a*, and b* values of fresh blood orange slices. The L*, a*, and b* values of blood orange slices dried using the freeze-drying method are then compared to those dried using the UAVD method at 50 °C. According to certain researches [
10,
11,
37], the UAVD approach can avoid color changes throughout the drying process. Turan et al. [
37] indicated elevated L*, a*, and b* values for UAVD-dried goji berries in comparison to HAD-dried samples. The reduction in the L* value of dried samples is mostly attributable to Maillard reactions and nonenzymatic browning, which are inevitable during drying operations [
58]. Furthermore, drying may diminish essential substrates for the Maillard reaction, including sugars and soluble pigments, resulting in a decrease in the a* value of the dried samples [
59].
The drying of various foods under constant conditions typically results in curves with distinct shapes during the falling rate period [
43]. Damage to the cell structure of foods may result in deviations during the constant drying rate period [
10]. Ultrasonic treatment enhances the drying rate by leveraging the beneficial impacts of heating through attenuation and adsorption, in conjunction with the mechanical effects of pressure waves [
10,
12,
13].
Table 3 indicates that the drying rate values for the HAD, VD, and UAVD methods varied with drying temperature. The drying rate values obtained through the UAVD method, as presented in
Table 3, exceeded those of the HAD and VD methods during the falling rate period, attributable to the beneficial effects of ultrasound. The drying rate values escalated with all drying techniques as the temperature increased. A shortened period is essential for the material to attain equilibrium moisture content.
Figure 3 illustrates the drying rate vs kg water/kg drymatter.
In the current study, the D
eff rose as the temperature rose in all of the drying processes. The D
eff values of the HAD, VD, and UAVD dried samples varied from 9.08*10
-6 to 2.82*10
-5 m
2/s, from 2.60*10
-5 to 2.96*10
-5m
2/s, from 2.20*10
-5 to 2.99*10
-5, respectively.
Table 3 displays the D
eff values for the HAD-, VD-, and UAVD-dried blood orange slices at 50, 60, and 70 °C. The D
eff values of the UAVD-dried samples are higher than those of the HAD-dried and VD-dried blood oranges.
Table 3 presents the D
eff values for the HAD, VD, and UAVD methods at 50, 60, and 70 °C. The D
eff values of the UAVD-dried samples exceed those of the HAD-dried and VD-dried blood oranges. The data in
Table 3 suggest that D
eff increases as the temperature rises, which is because the hydration content of the blood oranges decreases due to the rapid evaporation of water molecules. As the temperature increased, Huang and Chen [
44] noted that the D
eff of sewage sludges increased.
Energy consumption varies with drying methods and temperature, and it decreases as the temperature increases. This study found that total energy consumption varied from 0.163 to 0.266 kWh with HAD, from 0.196 to 0.286 kWh with VD, and from 0.298 to 0.372 kWh with the UAVD method. The total energy consumption of samples dried using the UAVD method exceeded that of other drying methods; however, the drying times with UAVD were shorter, suggesting that UAVD drying may be more economical.