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Enhanced extraction of essential oil from Cinnamomum cassia

bark by ultrasound assisted hydrodistillation

Guanghui Chen, Fengrui Sun, Shougui Wang, Weiwen Wang,

Jipeng Dong, Fei Gao

PII: S1004-9541(20)30443-2
DOI: https://doi.org/10.1016/j.cjche.2020.08.007
Reference: CJCHE 1875

To appear in: Chinese Journal of Chemical Engineering

Received date: 30 April 2020

Revised date: 16 July 2020
Accepted date: 2 August 2020

Please cite this article as: G. Chen, F. Sun, S. Wang, et al., Enhanced extraction of
essential oil from Cinnamomum cassia bark by ultrasound assisted hydrodistillation,
Chinese Journal of Chemical Engineering (2020), https://doi.org/10.1016/
j.cjche.2020.08.007

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© 2020 Published by Elsevier.

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Enhanced extraction of essential oil from Cinnamomum

cassia bark by ultrasound assisted hydrodistillation

Guanghui Chen1, Fengrui Sun1, Shougui Wang2, Weiwen Wang1, Jipeng Dong1, Fei Gao1,*

1
Key Laboratory of Mutiphase Flow Reaction and Separation Engineering of Shandong

Province, College of Chemical Engineering, Qingdao University of Science and

Technology, Qingdao 266042, China

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2
Fundamental Chemistry Experiment Center (Gaomi), Qingdao University of Science and

Technology, Gaomi 261500, China

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* Corresponding author. Tel./fax: +86 532 84022957. E-mail address: feigao@tju.edu.cn
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ABSTRACT

Cinnamon essential oil with many bioactivities is an important raw material for the
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production of various chemicals, and the conventional hydrodistillation (HD) for cinnamon
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oil extraction always require a longer extraction time. In this work, ultrasound-assisted

hydrodistillation extraction (UAHDE) technique was employed to enhance the extraction

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efficiency of essential oils from cinnamon barks. The parameters with significant effects on

the essential oil extraction efficiency (ultrasound time, ultrasound power, extraction time,

liquid-solid ratio) were optimized, and the proposed UAHDE was compared with the

conventional HD extraction in terms of the extraction time, extraction yield, and

physicochemical properties of extracted oils. Compared to the HD extraction, the UAHDE

resulted in a shorter extraction time and a higher extraction yield. Using GC-MS analysis,

the UAHDE provided more valuable essential oil with a high content of the vital

trans-cinnamaldehyde compounds compared with the HD. Scanning electron micrograph

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(SEM) confirmed the efficiency of ultrasound irradiation for cinnamon oil extraction. In

addition, the analysis of electric consumption and CO2 emission shows that the UAHDE

process is a more economic and environment-friendly approach. Thus, UAHDE is an

efficient and green technology for the cinnamon essential oil extraction, which could

improve the quantity and quality of cinnamon oils.

Graphical abstract

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Keywords: Cinnamon oil; Extraction; Ultrasound; Distillation; Optimization; Chemical

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1. Introduction
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Essential oil, generally defined as volatile oils containing different organic components

extracted from the aromatic plants, has been widely used in foods, drinks, cosmetics,
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cleaning products, fragrances, pesticides and medicines industries [1-3]. Among the
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essential oil-producing plants, Cinnamomum cassia (also called cinnamon) belonging to the
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Lauraceae family is an important spices and traditional medicinal materials extensively

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distributed in China, India, Vietnam, Seychelles, Madagascar and SriLanka, and China is

the major cultivating country of cinnamon distributed in the southern provinces [4,5].

The essential oil extracted from the cinnamon plant contains some vital bioactive

components of terpenes and aromatic compounds, making cinnamon oil exhibits

remarkable antimicrobial, antibacterial, anti-inflammatory, antiallergy and anticancer

activities [6,7]. Thus, cinnamon oil has been widely used in medicine industry as an

important raw material for the production of various pharmaceuticals. In addition, recently,

for human health, extensive efforts have been devoted to the elimination of synthetic

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chemical additives from the food production, and cinnamon oil has been used in food

industry as the natural additives, condiments and flavoring agents due to their excellent

carminative, antioxidant and preservative activities [8,9]. Cinnamon oil can be extracted

from different parts of cinnamon plants including barks, leaves, twigs, calyxs, seeds, etc.

Among them, the bark of cinnamon is regarded as the most ideal commercial source of

cinnamon raw materials owing to its higher contents of essential oils and

trans-cinnamaldehyde than other parts of cinnamon which is a major and important

bioactive ingredient for cinnamon oils [10,11].

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The traditional technologies for the essential oil extraction from plant materials mostly

rely on expression, organic solvent extraction, hydrodistillation (HD) and steam distillation
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[12-14]. The traditional technologies have some inherent disadvantages, such as the lower
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extraction yield of the expression method and the toxic solvent residue in essential oils of
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the organic solvent extraction. HD is currently the most widely used commercial

technology for the essential oil extraction from the medicinal herbs/plants due to low costs
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and easy operations. However, it also suffers from some disadvantages of the longer
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extraction time, resulting in the loss of the volatile and thermally sensitive components of
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essential oils during the extraction process, which seriously affect the quantity and quality
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of essential oils [15,16]. Recently, several novel techniques have been developed for the

essential oil extraction from plants, including supercritical fluid extraction [17],

microwave-assisted extraction (MAE) [18], and ultrasound-assisted extraction (UAE) [19].

Among them, UAE has the remarkable advantages of time- and energy- savings, higher

extraction yield and better quality of essential oils owing to its cavitation, mechanical and

thermal effects accelerating the extraction process [20-22]. Consequently,

ultrasound-assisted hydrodistillation extraction (UAHDE), as a complementary extraction

method with both advantages of UAE and HD, has been widely used for extracting

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essential oils from several plant materials [23]. There are two types of UAHDE approaches

for the essential oil extraction including ultrasound pretreatment followed by

hydrodistillation and simultaneous ultrasound-assisted hydrodistillation extraction, e.g.,

Hashemi et al. [24] and Morsy [25] extracted essential oils from Aloysia citriodora Palau

leaves and cardamom seeds using ultrasound pre-treatment with a ultrasound probe

followed by the conventional HD, Damyeh et al. [26] extracted essential oils from Prangos

ferulacea Lindl. and Satureja macrosiphonia Bornm. Leaves using ultrasonic pretreatment

in an ultrasonic water bath prior to HD, and Liu et al. [27] and Solanki et al. [15] extracted

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essential oils from Iberis amara seeds and java citronella grass by simultaneous HD and

sonication performed in a Clevenger HD apparatus equipped with a ultrasound probe.

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Compared with the conventional HD, both of the above two different UAHDE approaches
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were obvious characterized by faster extraction rate, less extraction time and energy
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consumption and better product quality, and could be regarded as green techniques for

extracting essential oils from natural plants.

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For the essential oil extraction process, the extraction efficiency can be significantly
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affected by the extraction parameters, so it is valuable to explore and optimize the

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extraction parameters. The conventional optimization of keeping one parameter variable

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and all other constant is a time consuming, expensive and arduous task. In addition, the

conventional approach does not provide any information about the interactive effects

between various process variables on the process output. Hence, it is imperative to use the

statistical design of experimental (DOE) approach for the optimization of technological

processes, and the most commonly used DOE methods for the optimization of operational

variables are the orthogonal array design, Central Composite Design and Box-Behnken

design (BBD) [28-30]. Among them, the orthogonal experimental design has become an

easier, cheaper and faster DOE methodology since it allows optimization with a minimum

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number of experiments based on a fractional factorial design. Numerous factors can be

simultaneously optimized, resulting in a fast estimation of the individual factors with main

effects and easy determination of the optimal combination of process factors. In addition,

the orthogonal design methodology optimizes the process by minimizing the variation in

process output caused by uncontrollable factors like ambient temperature. The above

distinct features make it a robust design solution, and widely used to optimize operating

parameters for improving the essential oil extraction processes.

Herein, the aim of this work is to evaluate the influence of the ultrasound pretreatment

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prior to hydrodistillation on the essential oil extraction from cinnamon barks. The

extraction parameters significant affecting the extraction process were optimized by the
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single-factor experiments and orthogonal test design. In addition, the proposed extraction
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method was compared with traditional HD in terms of the extraction time, extraction yield
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and environmental impact. Moreover, the extraction mechanism was elucidated with the

microscopic structural changes of cinnamon barks before and after the ultrasound treatment,
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and the physicochemical properties of the obtained cinnamon oil were analyzed.
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2. Materials and methods

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2.1 Materials
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Cinnamomum cassia (cinnamon) bark supplied by Luoding Rongxing Perfumery Co.,

Ltd of Guangdong Province in China was used as experimental raw material in this work.

The fresh cinnamon barks were contaminated by some sand particles, so the raw material

was cleaned to remove these substances as much as possible. Firstly, the fresh sample was

washed with the flowing deionized water for 30 min, and then dried naturally at ambient

temperature of 25-30 °C for 2 days, making the relative humidity of raw material reaches

about 35%. After that, the samples were crushed and grinded physically, and sieved using a

sieve with the mesh of 60. And then the cinnamon bark powders were dried at 105 °C until
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the weight did not change. The dried cinnamon bark powder sample was kept in a

desiccator for the utilization of UAHDE and HD extraction studies.

2.2 Extraction procedures

2.2.1 Conventional hydrodistillation

Hydrodistillation was carried out using a Clevenger-type apparatus, and a schematic of

the apparatus is shown in Figure 1. Forty grams of the dried cinnamon bark powder was

added into a 1 L round bottom flask with a ratio of solid (g): water (ml) of 1:7, and then the

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mixture was subjected to the hydrodistillation with a electric heating mantle at 500 W

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power. On the basis of our preliminary research results, the optimal extraction time for HD

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was determined to be 2 h. The extracted essential oils were dried over anhydrous sodium
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sulfate. And then the collected yellow oils were weighed and stored in sealed vials at 4 °C

for the further analysis. The essential oil yields were reported as grams of essential oils per
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100 g of dried cinnamon bark powders. Each extraction was repeated for three times and
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the mean values of the extraction yields were reported.

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Figure 1. Schematic of experimental apparatus for essential oil extraction from cinnamon

barks: (a), Conventional hydrodistillation; (b), Ultrasound-assisted hydrodistillation.

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2.2.2 Ultrasound-assisted hydrodistillation extraction (UAHDE)

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Forty grams of the dried cinnamon bark powder sample was accurately weighed and
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added into a 1 L round bottom flask containing a certain amount of distilled water, and then
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the mixtures of (cinnamon bark + H2O) were subjected to the ultrasonic treatment using a

ultrasonic cell pulverizer (JY92-IIN, 25 kHz, Ningbo xinzhi biotechnology Co., Ltd., China)

at different power levels for different time. Consequently, the various cinnamon bark

samples treated with ultrasound irradiation at different power levels for different time were

obtained to investigate the effects of the ultrasound power and time on the cinnamon oil

extraction. After the ultrasonic treatment, the resulting mixture was immediately submitted

to the hydrodistillation for the cinnamon oil extraction using a Clevenger-type apparatus as

previously described in the conventional hydrodistillation part. The different extraction

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time and solid-liquid ratios were conducted to investigate the effects of these factors on the

essential oil yield for the UAHDE method.

2.3 Optimization of UAHDE conditions

In the present work, the single-factor experiments and orthogonal test design were

conducted to optimize the UAHDE conditions (ultrasound time, ultrasound power,

extraction time, liquid-solid ratio). Before the orthogonal experiment, the single-factor

experiments were conducted to evaluate the effects of four factors on the essential oil

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extraction yield and determine the range of each parameter. On the basis of single-factor

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test result, four parameters were investigated at three levels using a standard orthogonal

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array L9 as shown in Table 1, and the cinnamon oil yield was taken as responses. Minitab

18.0 software (Minitab Inc., PA, U.S.A.) was used for planning the experiments, analyzing
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the influence of individual factors and determining the optimal conditions.
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2.4 Scanning electron microscopy (SEM)

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Morphological changes of the dried cinnamon bark powder before and after the

ultrasound treatment were observed by a JSM-6700F scanning electron microscopy (JEOL,

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Japan), operating at an accelerating voltage of 8.0 kV and at a working distance of 8 mm.

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Prior to the SEM observation, the samples were fixed on a specimen holder with
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conductive tape and then sputtered with gold.

2.5 Gas chromatography-mass spectrometry (GC-MS)

The components of the cinnamon oil were analysed using a 7890B-7000C gas

chromatography-mass spectrometry (GC-MS) (Agilent, American) equipped with a mass

selective detector operating in the electron impact mode with the ionization energy of 70

eV (source temperature 230 °C). The GC part (Agilent 7890B) was fitted with an Agilent

HP-5MS capillary column (30 m × 0.25 mm, film thickness 0.25 μm). The temperature

program of the oven was as follows: initially keeping 60 °C for 3 min, and then heating to
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280 °C at 20 °C·min-1 and holding for 10 min. The test samples were diluted with

dichloromethane at a ratio (1/10, V/V), and 1 μl sample was injected at 310 °C to GC with

the injector in split mode at a split ratio of 1/100. Helium was used as the carrier gas at a

rate of 15 ml·min-1. The components of the extracted oil were identified by comparing their

recorded mass spectra with the standard mass spectra from the National Institute of

Standard and Technology (NIST) libraries database.

2.6 Environmental impact

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Regarding the environmental impact, the electric consumption and CO 2 emission of

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different extraction methods were calculated. The electric consumption per gram of

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obtained essential oil (EO) was calculated using the following equation [31]:

Pt
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EC  (1)
m
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where EC is the electric consumption per gram of EO (kWh·g−1), P is the power

consumption (kW), t is time (h), and m is the mass of obtained essential oil (g).
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The process of generating 1 kWh electricity by burning fossil fuels will release 800 g
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of CO2 into the atmosphere [32]. Based on this calculation, the CO2 emission per gram of
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EO was estimated using the following equation:

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EC  800
ECO2  (2)
1000  m

where ECO2 is the CO2 emission per gram of EO (kg·g−1).

3. Results and discussion

3.1 Influence of the ultrasound time, power, extraction time and liquid-solid ratio on

essential oil yield

Some operation factors can potentially affect the extraction process, so the extraction

conditions of cinnamon oils were investigated. Figure 2 shows the influence of the

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ultrasound time on essential oil yield. The cinnamon bark powders treated with different

ultrasound time of 10, 20, 30, 40, 50 and 60 min at the ultrasound power level of 300 W

were subjected to the essential oil extractions for 2 h. It can be seen that the cinnamon oil

yield increases with increasing the ultrasound time from 10 to 30 min, and decrease

gradually with further increasing the ultrasound time. The increase of the ultrasound time

would improve the cell disruption degree of the cinnamon bark sample, conducive to the

release of essential oils to the solution, resulting in an increase of the cinnamon oil yield.

However, the longer the ultrasound time, the more oil compounds were degraded into small

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molecule species [33]. In addition, the localised temperatures would increase with the

increase of ultrasound time, leading to the loss of easy volatile components and the
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degraded components [34], causing the decrease of essential oil yield at the ultrasound time
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of longer than 30 min. Hence, ultrasound time of 30 min was chosen for the subsequent
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optimization.
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Figure 2. Effect of ultrasound time on essential oil yield.

Figure 3 illustrates the effect of the ultrasound power on essential oil yield. The

ultrasound treated samples with different ultrasound powers of 100, 200, 300, 400 and 500

W for 30 min were subjected to the essential oil extractions for 2 h. It can be seen that at

ultrasonic powers of lower than 300 W, the extraction yield increases steadily with the

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increase in the ultrasonic power, while it decreases with further increasing the ultrasonic

power of higher than 300 W. During the ultrasonic irradiation, the shear forces and

localised pressures generated with the cavitation bubbles collapse around the cinnamon

bark surfaces would lead to the destruction of the plant tissue and consequently accelerate

the release of intracellular substances into the solution, resulting in the essential oil yields

increase [35]. However, at too higher ultrasonic powers, the superheated localised

temperatures and more free radicals generated as more cavitation bubble collapse would

lead to the degradation of targeted compounds, resulting in a decrease of essential oil yield

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[36]. A similar behavior was observed in the ultrasound-assisted extraction of the essential

oil from chickpea [37]. Thus, 300 W was regarded as the appropriate ultrasound power for

the subsequent experiment.

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Figure 3. Effect of ultrasound power on essential oil yield.

Extraction time is also an important factor for the essential oil extraction process, and

it is necessary to determine the appropriate extraction time to avoid the excessive use of

energy. Thereby, the effect of the extraction time on essential oil yield was investigated.

The cinnamon bark samples were treated with ultrasound at the power of 300 W for 30 min,

and subjected to the essential oil extractions for the different time of 15, 30, 60, 90 and 120

min. From Figure 4, it can be seen that the extraction yield increases steadily with the

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increasing the extraction time to 60 min, and then decreases slightly with further increasing

the extraction time. The decrease may be due to the loss of some volatile components

during the longer time of extraction. Liu et al. [27] reported the similar result in the

ultrasound-assisted extraction of essential oil from Iberis amara seeds. Hence, 60 min was

selected as the extraction time for the subsequent optimization.

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Figure 4. Effect of extraction time on essential oil yield.

The liquid-solid ratio is another crucial factor and was also investigated to optimize
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the extraction yields. Generally, within a certain range, a higher liquid-to-solid ratio could
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dissolve the target constituents more effectively, and resulting in a better extraction yield
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[38]. However, the use of excess solvent, apart from the energy consumptions for the
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solvent separation, will cause unnecessary waste and decrease the ultrasound adsorption of

materials. Thus, a series of extraction experiments were carried out with different

liquid-solid ratios of 4, 6, 8, 10 and 12 (V/m, ml·g-1) to evaluate the effect of the

liquid-to-solid ratio on the essential oil yield, and the results are illustrated in Figure 5. It

can be seen that the extraction yield increases with increasing the moisture content for

liquid-solid ratios up to 6, but decreases slightly with the corresponding rise in moisture

content. The higher liquid-solid ratios would lead to the decrease of the ultrasound

adsorption of the cinnamon bark material, resulting in the insufficient energy in facilitating

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the cell wall breakage for the release of the essential oil compounds. A similar observation

was reported by Zhao et al. [39] in the extraction of saikosaponins from Radix Bupleuri.

Therefore, liquid-solid ratio of 6 was chosen as the suitable moisture content for further

optimization.

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Figure 5. Effect of liquid-solid ratio on essential oil yield.
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3.2 Optimisation of extraction conditions of cinnamon oils

From the preliminary single-factor analysis, the various factors can potentially affect
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the extraction process, so the extraction conditions of cinnamon oils by UAHDE were
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further optimized utilizing an orthogonal L9(34) test. As shown in Table 1, based on the
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results of preliminary single-factor analysis, nine extraction tests were conducted with four
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factors and three levels as follows: ultrasound time (25, 30, 35 min), ultrasound power (250,

300, 350 W), extraction time (45, 60, 75 min) and liquid-solid ratio (5, 6, 7 ml·g-1). The

cinnamon oil yield was selected as the responses and required to be maximized. The above

nine tests were carried out randomly to minimize the effects of unexpected variability. From

Table 1, based on the analysis of R values, the order of impact of the three factors on the

cinnamon oil yield is ultrasound time > extraction time > ultrasound power > liquid-solid

ratio. Moreover, the optimum extraction condition was determined as A3B2C2D3, meaning

that the combination of the ultrasound time of 35 min, the ultrasound power of 300 W, the

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extraction time of 60 min, and the liquid-solid ratio of 7 is the optimum condition for the

cinnamon oil extraction. The extraction experiments under the above optimal extraction

were conducted with three repetitions, and the average yield was 2.14%.

Table 1. Orthogonal test design L9(34) and essential oil yields.

Factors
No. Yield/%
A, ultrasound B, ultrasound C, extraction D, liquid-solid
-1
time/min power/W time/min ratio/ml· g

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1 1 (25) 1 (250) 1 (45) 1 (5) 1.51

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2 1 2 (300) 2 (60) 2 (6) 1.83
3 1 3 (350) 3 (75) 3 (7) 1.63
4
5
6
2 (30)
2
2
1
2
3
2
3
1
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1
2
2.12
1.98
1.73
e-
7 3 (35) 1 3 2 2.02
8 3 2 1 3 1.93
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9 3 3 2 1 2.11
①
K1 1.66 1.88 1.72 1.87
①
K2 1.94 1.91 2.02 1.86
①
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K3 2.02 1.82 1.88 1.89

②
R 0.36 0.09 0.30 0.03
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①
Average response of each level about extraction yield.
②
R value means range between three average responses of each level about extraction yield.
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3.3 Comparison of UAHDE and HD

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3.3.1 Comparison of extraction time, yield, and physicochemical properties of essential oil

In this work, UAHDE was compared with the HD extraction in accordance with the

extraction time, the extraction yield, and the chemical composition of the extracted

essential oil, and the comparison results are demonstrated in Figure 6 and Table 2.

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Figure 6. GC-MS chromatograms of cinnamon essential oils extracted by HD technique (a),

UAHDE (b).

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Table 2. Chemical compositions of cinnamon essential oils obtained by UAHDE compared

to HD.pr
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Mass percentage of
RT/ Molecular
No Compounds chemical compounds/%
min Formula
UAHDE HD
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Monoterpenes
1 Butylbenzene 7.004 C10H14 0.17 –
2 Bicyclo[3.1.1]hept-2-ene, 3,6,6-trimethyl- 9.456 C10H16 0.16 –
3 1,3,6-Heptatriene, 2,5,5-trimethyl 10.32 C10H16 0.10 –
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Oxygenated monoterpenes
4 1(2H)-Naphthalenone, 3,4-dihydro- 9.352 C10H10O – 0.68
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5 1,4-Epoxynaphthalene, 1,2,3,4-tetrahydro- 9.404 C10H10O 0.53 0.39

6 2-Methoxycinnamaldehyde 9.929 C10H10O2 5.07 8.55
7 2-Methoxyphenylacetone 9.982 C10H10O2 – 0.51
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(3S,6R)-3-Hydroperoxy-3-methyl-6-(prop-1-en-2-yl)cyclohex-1-
8 10.919 C10H16O2 0.16 –
ene
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Sesquiterpene hydrocarbons
9 Copaene 8.857 C15H24 3.66 1.50
10 Bicyclo[3.1.1]hept-2-ene,2,6-dimethyl-6-(4-methyl-3-pentenyl)- 9.742 C15H24 – 0.69
11 α-Muurolene 9.747 C15H24 1.46 –
Naphthalene,1,2,3,5,6,8ahexahydro-4,7-dimethyl-1-(1-methyleth
12 9.898 C15H24 1.55 –
yl)-, (1S-cis)-
13 α-Calacorene 10.06 C15H20 0.32 –
14 Bicyclo[4.1.0]-3-heptene,2-isopropenyl-5-isopropyl-7,7-dimethyl 10.367 C15H24 tr –
15 Cyclohexene, 4-(1,5-dimethyl-1,4-hexadienyl)-1-methyl- 10.96 C15H24 0.15 –
Oxygenated sesquiterpenes
16 Caryophyllenyl alcohol 10.284 C15H26O tr –

17 Di-epi-1,10-cubenol 10.622 C15H26O 0.49 –

1-Naphthalenol,1,2,3,4,4a,7,8,8a-octahydro-1,6-dimethyl-4-(1-m
18 10.705 C15H26O 1.18 –
ethylethyl)-,[1R-(1.alpha.,4.beta.,4a.beta.,8a.beta.)]-
3-Cyclohexene-1-methanol,.alpha.,4-dimethyl-.alpha.-(4-methyl-
19 10.789 C15H26O 0.18 –
3-pentenyl)-,[R-(R*,R*)]-

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Other oxygenated compounds

20 Benzaldehyde 4.656 C7H6O 0.14 0.73
21 Phenylethyl Alcohol 6.499 C8H10O – 0.50
22 Benzenepropanal 6.993 C9H10O – 0.80
23 Bicyclo[3.2.2]nona-6,8-dien-3-one 7.045 C9H10O – 0.24
24 cis-Cinnamaldehyde 7.54 C9H8O 0.62 0.53
25 Benzaldehyde, 2-methoxy- 7.738 C8H8O2 – 0.60
26 trans-Cinnamaldehyde 8.019 C9H8O 81.86 78.31
27 Benzeneethanol, .beta.-methylene- 8.279 C9H10O 0.31 –
28 Acetic acid, cinnamyl ester 9.294 C11H12O2 0.27 0.79
29 1,3-Bis (cinnamoyloxymethyl) adamantane 10.101 C30H32O2 – 0.19
30 1,3-Bis-(2-cyclopropyl,2-methylcyclopropyl)-but-2-en-1-one 10.497 C18H26O 0.17 –

Total identified compounds 98.53 96.05

Total extraction time/min 60 120
Essential oil yield/% 2.14 1.68

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Note: tr, trace compound (<0.10%);−, not detected.

From Table 2, a significant saving in the extraction time was clearly observed in the
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UAHDE process, and HD required 120 min to complete the extraction process whereas
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UAHDE required only half of the time (60 min), indicating that the UAHDE is a faster
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extraction process. Moreover, it can be seen that the cinnamon oil yield extracted by

UAHDE (2.14%) is about 27% higher than that extracted by HD (1.68%). This 27%
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enhancement is higher than the 6.4% enhancement of ultrasound auxiliary extraction

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reported by Jadhav et al. [40], and slightly lower than the 34% enhancement of microwave
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auxiliary extraction reported by Jeyaratnam et al. [41], which may be due to the stronger
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thermal effect of microwave irradiation than ultrasonic irradiation [42].

The chemical compositions of essential oils extracted from cinnamon barks by

UAHDE and HD were analyzed by GC-MS (Figure 6 and Supplemental material), and the

analysis results are listed in Table 2. The relative percent contents were calculated by peak

areas using normalization method. It can been seen from Table 2 that, 22 components were

identified in the essential oil obtained by UAHDE representing 98.53% of the total oil

content, and 15 components were identified in the essential oil obtained by HD representing

96.05% of the total oil content. Trans-cinnamaldehyde is a major and vital component in

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cinnamon oils owing to its great medicinal and curative properties. It can be obviously

observed that trans-cinnamaldehyde is the primary compound in the extracted cinnamon oil

with UAHDE and HD, suggesting that the results obtained herein are consistent with the

results of previous studies [10,11,43]. However, the content of trans-cinnamaldehyde was

found to be different in the two cinnamon oils obtained by different methods, and 81.9%

and 78.3% were obtained from UAHDE and HD respectively, indicating that UAHDE is a

promising technique for obtaining the cinnamon oil with a higher content of

trans-cinnamaldehyde from cinnamon barks. In addition, from Figure 6 and Table 2, the

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other main compounds in HD cinnamon oil, such as 2-methoxycinnamaldehyde and

copaene, can also be observed in UAHDE oil, and some monoterpenes and sesquiterpene
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hydrocarbons in UAHDE oil are absents in the essential oil obtained by HD. The above
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results prove that ultrasound irradiation would not alter the main effective components in
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cinnamon essential oils, but improve the content of effective compositions. This may be

attributed to more effective liberation of certain components from the secretory structures
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of cinnamon bark tissues undergo ultrasound irradiation and the shorter extraction time
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with UAHDE preventing the labile components from thermal degradation which is
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common with HD [44].

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To determine the quality of the cinnamon oils extracted by HD and UAHDE methods,

the usual physical constants defining the essential oil (specific gravity, refractive index,

optical rotation) were measured according to the standard method suggested by ISO 3126:

1977 (E) and ISO 3524: 2003 (E), and the analysis result was compared with quality

standards data. As shown in Table 3, there is no significant difference in physical constants

of essential oils extracted by UAHDE and HD methods. In addition, it can be seen that the

physical properties of obtained cinnamon oils meet the requirements of quality standards.

Table 3. Physical properties of cinnamon oils obtained by UAHDE and HD from cinnamon

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barks.

Physical properties HD UAHDE Quality standards

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Specific gravity ( d 20 ) 1.056 1.057 1.052-1.070a

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Refractive index ( nD ) 1.6053 1.6055 1.6000-1.6140a

Optical rotation ( [ ]D )
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-0.398 -0.394 -2.5 to +2b
a
ISO 3126: 1977 (E); bISO 3524:2003 (E).

3.3.2 Mechanism analysis with morphological characterization

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To elucidate the mechanism of UAHDE for the essential oil extraction from cinnamon

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barks, the morphological changes in surface structure of the cinnamon bark samples before

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and after the ultrasonic pretreatment, HD extraction and UAHD extraction were observed

by SEM. As shown in Figure 7a, the external structure of the sample without any treatment
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is intact and smooth, and no significant disruption is observed. It can be seen from Figure
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7b, after the ultrasonic pretreatment, the cinnamon bark samples are crushed into some

small granules, and many cracks and gaps on these particle surfaces are clearly visible. In
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addition, the sample particles are dispersed more evenly after ultrasonic treatment. From
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Figures. 7c and d, after the extraction, the cinnamon bark tissues are ruptured, and the
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obvious porosity with many irregular cavities are observed on the sample surfaces.
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Moreover, obviously, the surface structures of the sample extracted by UAHDE are

disrupted more severely than those of the sample extracted by HD, which is attributed to

the cracks and gaps on the sample surfaces generated by the ultrasonic pretreatment.

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Figure 7. SEM images of cinnamon bark samples before (a) and after ultrasonic
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pretreatment (b), HD (c) and UAHDE (d).

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Based on the SEM results, the extraction mechanism for UAHDE process was
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elucidated as shown in Figure 8. During the ultrasonic irradiation, cavitation bubbles are
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produced near the plant substrate surfaces, and the bubbles grow in successive cycles.

When reaching the critical value, the bubbles will collapse violently, generating a localised

high pressure (200 MPa) of the micro-jets with a very high speed (>400 km·h-1) to the

cinnamon bark tissue surfaces [45-47]. Consequently, on the one hand, sonication broke up

the large particles and homogenized the cinnamon bark particles, promoting the contact of

cinnamon bark tissues with water. On the other hand, the cell walls of cinnamon bark

tissues were destroyed during the ultrasonic irradiation, and a direct contact was established

between the intracellular active components and the external water, facilitating the

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penetration of water into the inner cells and the release of active components. Compared

with the conventional HD, UAHDE destroyed the cinnamon bark tissues more seriously,

which could enhance the mass transfer, leading to a more and faster release of active

components along with water in vapor state for the UAHDE process, resulting in a higher

essential oil yield, shorter extraction time and better essential oil quality.

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Figure 8. Schematic representation of possible mechanism for UAHDE process.

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3.3.3 Comparison of energy and environmental impact

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In order to highlight the vantage of the UAHDE method, the energy consumption and

CO2 emissions resulted from this extraction process with the optimum extraction condition

were also compared with the traditional HD method, and the result was summarized in

Figure 9. A significant energy saving was clearly observed in the UAHDE method. The

required electrical energy consumption to obtain one gram of cinnamon oil is 1.49 kWh for

HD, while is only 0.79 kWh for UAHDE, which was ascribed to the breakage of cinnamon

bark tissues by the ultrasonic irradiation, resulting in a fast and efficient extraction for

UAHDE. Regarding the environmental impact of pollution, the calculated amount of CO2

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rejected into the atmosphere per gram of cinnamon oil extracted by HD (1.19 kg) is much

higher than that of UAHDE (0.63 kg). Therefore, UAHDE can be suggested as an

economic and environment-friendly approach for the extraction of essential oil from the

cinnamon plants.

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Figure 9. Electric consumption and CO2 emission of HD and UAHDE for the extraction of

cinnamon oil.
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4. Conclusions
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UAHDE technique was successfully applied for the extraction of essential oil from
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cinnamon barks. The optimum extraction conditions for the UAHDE are: ultrasound time
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of 35 min, ultrasound power of 300 W, extraction time of 60 min, and liquid-solid ratio of 7.

Under the optimum condition, the cinnamon oil yield of UAHDE is 2.14%, which is about

27% higher than that of HD (1.68%). Meanwhile, the extraction time of UAHDE (60 min)

is significantly lower than that of HD (120 min), indicating that the UAHDE is a faster

extraction approach. From GC-MS analysis, 22 and 15 components were identified in the

essential oil obtained by UAHDE and HD, respectively, and UAHDE would not alter the

types of main effective components in cinnamon essential oils like trans-cinnamaldehyde,

2-methoxycinnamaldehyde and copaene. Furthermore, the cinnamon oil extracted by the

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UAHDE could obtain a higher content of the vital trans-cinnamaldehyde compound (81.9%)

than that of HD (78.3%). The physical constants analysis suggests that the physical

properties of the obtained cinnamon oil meet the requirements of quality standards. The

SEM analysis confirms that the primary driving force for the efficient extraction by

UAHDE is the structure destruction of the cinnamon bark tissues generated by the

ultrasonic irradiation. In addition, using UAHDE could reduce the energy consumption and

CO2 emission compared with the HD. In summary, UAHDE is a promising technique for

the cinnamon essential oil extraction, and thus can be used for the essential oil extractions

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from other plant materials.

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