You are on page 1of 10

Journal of Food Measurement and Characterization

https://doi.org/10.1007/s11694-018-9942-x

ORIGINAL PAPER

Aroma compound profile of mature coconut water from tall variety


through thermal treatment
Zuraidah Nasution1 · Wannee Jirapakkul1   · Yaowapa Lorjaroenphon1

Received: 25 September 2017 / Accepted: 27 September 2018


© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Mature coconut water has inferior flavor characteristics compared to young coconut water. Thermal treatment can potentially
be used not only to prolong the shelf life of coconut water, but also to alter its aroma compound profile. Therefore, the effect
of heating on aroma compound profile of mature coconut water from tall variety was investigated in this study. Thermal treat-
ment was performed at 85 °C for 15 min, 90 °C for 10 min, and 95 °C for 10 min. Volatile aroma compounds were extracted
with solvent extraction and HS-SPME and analyzed with GC-TOFMS. The results showed that heat treatment affected the
concentration of volatile aroma compounds in mature coconut water. Major changes were in esters, especially fatty acid
esters that increased by 2–20%, and ketones that decreased by 2–21%, which mostly consisted of acetoin. Further analysis
with descriptive sensory evaluation showed that heat treatment could reduce the undesirable ferment aroma attribute, most
likely due to the decreased concentration of acetoin. Moreover, heat treatment also led to a slight increase in the intensity
of sweet, floral, and creamy attributes, which could be related to the increased concentration of fatty acid esters. Heating at
85 °C for 15 min had slightly higher intensity for sweet and creamy characteristics compared to the other heat treatments.
Thus, this study has shown that heat treatment could alter the aroma compound profile of mature coconut water.

Keywords  Mature coconut water · Heat treatment · Volatile compounds · Aroma · GC-TOFMS

Introduction young aromatic coconut in Thailand [3]. Another study by


De Marchi et al. identified 73 volatile compounds in the
Coconut water has been reported to contain volatile flavor headspace of young green Thai coconuts (Cocos nucifera
compounds. Jirovetz et al. identified the main aroma com- cv. Nam Hom) including alcohols, aldehydes, and ketones,
pounds in the headspace of mature coconut water from Cam- followed by smaller amounts of esters, lactones, terpenes,
eroon as nonanal, nonanol, heptanal, ethyl octanoate, hep- ethers, and heterocycles [4].
tanol, and 2-nonanol [1]. Prades et al. reported that immature Mature coconut fruit from the tall variety is highly uti-
coconut water from tall and hybrid varieties had higher lized by the industry since it has a high amount of lipid in
level of ketones, while dwarf varieties had higher percent- the kernel, which is important for the production of coconut
age of aldehydes [2]. In terms of variety, there are generally milk and coconut oil. Unfortunately, the water from this type
three varieties of coconut plants: tall, dwarf, and a hybrid of coconut is inferior in terms of flavor, since it has higher
between those two varieties. Coconut water from the tall fat content as the coconuts become more mature [5]. It also
varieties usually has the reducing sugar to total sugar ratio contains high level of ketones (creamy or butyric character-
below 75%, while the dwarf varieties have a ratio higher istic) and lactones (coconut aroma), but low in aldehydes
than 75% [2]. Jirapong et al. listed alkenes and terpenes as (green, fresh and almond notes) [2]. Therefore, it has been
the main volatile organic compounds found in the water of described as far less aromatic than young coconut water [6].
Processing methods have been found to affect and
improve aroma of food products, such as reported by De
* Wannee Jirapakkul
fagiwnc@ku.ac.th Marchi et al. in their study on pasteurized young aromatic
coconut water [4]. Among several processing methods
1
Department of Food Science and Technology, Faculty applied on coconut water, heat is the most utilized method
of Agro‑Industry, Kasetsart University, Bangkok 10900, currently. Adequate heat treatment can help prolong the shelf
Thailand

13
Vol.:(0123456789)
Z. Nasution et al.

life of coconut water by inactivating its natural enzymes, [10]. Three hundred milliliters of mature coconut water was
thus delaying enzymatic degradation [7]. In Thailand, the heated on a hot-plate stirrer that had been pre-heated at the set
water of young aromatic coconut whose whole fruit is burnt temperature. Heating time was started when the center of the
in fire is traditionally perceived as sweeter in taste and bet- sample reached the desired temperature (within 10–15 min)
ter in aroma compared to the unheated one, as reported by and low speed of stirring was applied. During heat treatment,
Jirapong et al. who found changes in volatile compounds of the temperature was monitored using a thermocouple. Once
the sample due to the application of heat, with some com- the heating process was completed, the sample was immedi-
pounds either decreased, increased, or unchanged, and few ately immersed in the ice water to cool it down. The experi-
new volatiles were formed [8]. Similarly, De Marchi et al. ment was repeated using the second batch of the coconut water.
concluded that pasteurization caused changes in volatile
compounds of young aromatic coconut water, where there Isolation of volatile aroma compounds
was an increase in aldehydes, ketones, and 2-acetyl-1-pyr-
roline [4]. Solvent extraction
Unfortunately, there has been a lack of published reports
on the aroma compound profile of mature coconut water Solvent extraction was performed following the method modi-
from tall variety as affected by thermal treatments. In order fied from Saemah and Jirapakkul [11]. Coconut water sample
to gain a complete profile of volatile aroma compounds of of 250 mL was added with 60 g of NaCl and extracted with
coconut water, two types of extraction methods were used in 250 mL dichloromethane using 30 µL of 2-methyl-3-hep-
the analysis of volatile compounds with GC–TOFMS: sol- tanone (1.45 mg/mL; Sigma-Aldrich, USA) as the internal
vent extraction, or also called as liquid–liquid extraction, and standard. Extraction was performed twice at low stirring
headspace–solid phase microextraction (HS–SPME). Sol- speed, each for 1 h at ambient temperature. The solvent frac-
vent extraction is highly regarded for its simplicity and abil- tion collected was concentrated using a Vigreux column in
ity to extract a broad spectrum of volatile compounds, while a water bath set at 45 °C until the volume reached 50 mL.
HS–SPME is not only a convenient solventless technique, Next, the extract was purified by high-vacuum distillation
but it also performs well with highly volatile compounds in ­(10−5 Torr) at ambient temperature for 2 h and at 50 °C for
foods such as flavor compounds [9]. The heat treatment used 1 h. The purified extract was further concentrated under gentle
in this study was based on the conditions suggested by Tan stream of ­N2 gas to 5 mL, passed through a column of anhy-
et al. who studied enzyme inactivation in mature tall coconut drous ­Na2SO4, and stored at − 40 °C. Prior to chromatography
water by using heat treatment [10]. analysis, it was concentrated to a final volume of 0.5 mL under
gentle stream of ­N2 gas. Lastly, 1 µL of extract was injected by
on-column mode to a gas chromatography-time of flight mass
Materials and methods spectrometry (GC–TOFMS).

Sample preparation Headspace–solid phase microextraction (HS–SPME)

Fresh mature coconut water from tall variety with maturity HS–SPME method was carried out on mature coconut water
age of 10–12 months old was collected from a local supplier (5 mL) using a 50/30 µm divinylbenzene/carboxen/polydi-
and packed in an ice box to prevent chemical changes. Upon methylsiloxane SPME fiber (Supelco, USA). The sample was
arrival in the laboratory, the coconut water was immediately placed in a 20 mL vial and added with 5 µL internal standard
filtered with food-grade industrial filter bag and stored in (50 ng/mL) and 1 g NaCl. Next, the sample was equilibrated
clean HDPE containers. The coconut water was temporar- at 45 °C for 10 min in a water bath while being stirred at
ily kept at − 20 °C for not more than 48 h. Prior to heat low speed. A manual SPME holder containing the fiber was
treatment and volatile aroma compound analysis, coconut inserted into the vial and exposed to the sample headspace for
water was thawed at 4 °C overnight. Sample collection and 20 min at 45 °C. Thermal desorption of volatile compounds
preparation was duplicated in March and June 2016. For from the fiber was carried out for 15 min in an SPME inlet
each batch of the coconut water, heat treatment and analysis liner (0.75 mm I.D.; Supelco, USA) with splitless mode at
of parameters were carried out. 250 °C.

Heat treatment of coconut water

Three combinations of temperature and time were used as the


heat treatments: 85 °C for 15 min, 90 °C for 10 min, and 95 °C
for 10 min, based on the conditions suggested by Tan et al.

13
Aroma compound profile of mature coconut water from tall variety through thermal treatment

Gas chromatography–time of flight mass detector (6890N; Agilent Technologies, USA) after extrac-
spectrometry (GC–TOFMS) analysis of volatile aroma tion of 50 mL sample with hexane and derivatisation with
compounds 3% ­H2SO4 in methanol, followed by concentration under
gentle stream of N ­ 2 gas [12]. Separation of fatty acids was
The samples were analyzed using GC (7890A; Agilent performed with DB-FFAP fused silica capillary column
Technologies, USA) equipped with a TOFMS (Pegasus (30 m × 0.25 mm I.D. × 0.25 µm film thickness; Agilent
4D, LECO Corp., USA). Separation of compounds was Technologies, USA). Helium as carrier gas was flown at
performed on polar Stabilwax® capillary column with 1 mL/min and oven temperature was set to start at 50 °C,
polyethylene glycol stationary phase and non-polar Rxi- held for 5 min, raised to 220 °C at 4 °C/min, and held for
5ms capillary column with diphenyl dimethyl polysi- 15 min. Inlet and detector ports were set at 250 °C and 1 µL
loxane stationary phase, both with similar dimensions of extract was injected with splitless mode. Fatty acid C17
(30  m × 0.25  mm I.D. × 0.25  µm film thickness; Restek (Sigma-Aldrich, USA) in methanol was used as an inter-
Corp., USA). The inlet port, transfer line, and M/S source nal standard at 1 mg/mL and the results were matched with
were set at 250 °C, 250 °C, and 200 °C, respectively. Helium FAME standard (Sigma-Aldrich, USA). The relative concen-
was used as the carrier gas at a flow rate of 1.5 mL/min. tration of a fatty acid in the sample was calculated in relation
The oven temperature was programmed to start from 35 °C, to the internal standard.
held for 5 min, ramped at 4 °C/min to 225 °C, and held for
10 min. Other conditions were set as follows: scanning mass Descriptive sensory evaluation
range at 30–300 m/z with an acquisition rate of 20 scans/s
and electron ionization energy at 70 eV. Descriptive sensory analysis with consensus method was
utilized to profile the aroma of coconut water samples by
Identification and quantification of volatile aroma using trained panelists, following the steps described by
compounds Zhou et al. [13]. The panel consisted of graduate students
(three males and seven females, with the age range of
The measured mass spectra were compared to NIST data- 20–30 years old), who have been trained previously to per-
base and the volatile compounds were identified by matching form sensory descriptive analysis on various food samples
their retention indices (RI), which were calculated based on including coconut-based products. The panelists were fur-
a series of n-alkanes (C6-C30 for polar column and C6-C22 ther trained for 10 h to identify aroma attributes of coconut
for non-polar column), with data of RI found in the litera- water, determine the appropriate aroma references, and rate
ture. Several selected coconut-related compounds were fur- the intensity of each reference. The intensity of the refer-
ther identified through injection of standard compounds into ences was referred to by the panelists when they evaluated
similar GC–TOFMS system. the samples (Table 1). Ten milliliter of samples and refer-
Concentration of a compound was reported as relative to ences was prepared in non-transparent cups, labeled with
the internal standard and odor activity value (OAV) of the three digit random codes, and presented to the panelists at
compound was calculated as a ratio between the compound’s room temperature. The containers were given minor shaking
relative concentration and its odor detection threshold in to ensure the volatile aroma of the samples to equilibrate in
water that was obtained from the literature. the headspace. Next, the panelists evaluated the samples by
sniffing the headspace as soon as they opened the cover of
Fatty acid composition analysis the container. Rating of the intensity of the aroma attributes
was conducted using 15-cm scales, with “0” as “none” and
The analysis of fatty acids in fresh mature coconut water “15” as “extremely strong”. Evaluation session was repli-
was conducted using a GC equipped with flame ionization cated twice and the intensity of aroma attributes for each

Table 1  Sensory references Aroma attribute Reference Intensity

Coconut-like 5 g of fresh shredded mature coconut meat, steamed for 5 min 7
Floral 10 mL of 30 mg/L aqueous solution of commercial jasmine flavoring (brand: 6
Best Odour)
Sweet 10 mL of 5% (w/v) aqueous solution of brown sugar (brand: Wangkanai) 3
Creamy 10 mL of fresh thick coconut milk (shredded coconut meat:water = 2:1) 7
Rancid 10 mL of rice bran oil (brand: King), microwaved (800 W) for 3 min 4
Ferment 10 mL of 0.5% (v/v) aqueous solution of brown rice vinegar (brand: Kewpie) 6

13
Z. Nasution et al.

sample was determined by discussion and consensus among and C12 were identified in volatile compound extraction,
panelists at the end of the session. with octanoic acid as the dominant one. Similarly, analysis
of the headspace of 8 month old coconut water from West
Statistical analysis African Tall variety also detected C6, C8, C9 and C10
fatty acids, with octanoic acid as the most abundant one
A completely randomized design was used in this study. [2]. According to descriptive sensory analysis carried out
Data were collected from two replications and reported as by Santos et al., the presence of octanoic acid in the head-
mean followed by standard error of the mean. The data were space of virgin coconut oil was responsible for the rancid
also analyzed with hierarchical cluster analysis. Statistical and acidic aroma [21].
analysis was performed using SPSS v.17 (SPSS Inc., USA). Lactones, the group of aroma compounds commonly asso-
ciated with coconut crop, were also identified in this study.
They were butyrolactone, δ-hexalactone, δ-octalactone,
Results and discussion and δ-decalactone. Jirovetz et al. also detected δ-lactones
(C6, C8, C10, and C12) in the headspace of mature coconut
Volatile aroma compounds in fresh mature coconut water sample from Cameroon [1]. Meanwhile, Prades et al.
water from tall variety reported the existence of C8, C9, and C10 δ-lactones in the
headspace of 8 months old coconut water [2]. Lactones are
Volatile aroma compounds found in fresh mature coco- important for the coconut-like, peach-like, creamy-fatty, and
nut water were grouped into alcohols, esters, fatty acids, sweet characteristics of coconut products [1, 2, 16]. Coco-
ketones, aldehydes, lactones, and thiols (Table 2). A high nuts of tall variety have been reported to contain higher
percentage of volatile aroma compounds in mature coconut lactones compared to other varieties, with δ-octalactone as
water belonged to ketone group. Among all the ketones, ace- their characteristic compound. Tall coconut variety starts
toin (3-hydroxy-2-butanone) contributed the largest amount. storing lipids at an earlier maturity stage, which is at about
A study by da Fonseca et al. found the presence of acetoin 5 months old. Therefore, fatty acid synthesis starts earlier,
in the solvent extract of coconut water of green and yellow which provides precursors for lactone production through
varieties [14]. Lasekan and Abbas also identified acetoin, fatty acids anabolism pathway [2].
with its buttery attribute, as one of important odorants in Coconuts of the tall variety were reported to contain low
palm toddy [15]. Meanwhile, Tinchan et al. identified it as amount of aldehydes (green, fresh, and almond odor). In
the most abundant ketone in coconut milk [16]. Not only in contrast, coconut water from dwarf variety has a high per-
coconut sample, a study performed by Uckun and Selli also centage of aldehydes, in particular trans-but-2-enal, which
reported acetoin as the most powerful ketone that provided gives the floral note contributing to higher consumers’ pref-
fatty odor in astragalus and citrus honeys [17]. erence toward the coconut water coming from dwarf variety
The second major group is the alcohols. In coconut water, [2]. Some low-molecular aldehydes can possibly come from
alcohols were reported to provide various characteristics autoxidation of fatty acids or from the work of lipoxygenase
[2]. They are responsible for the fresh-floral-fruity notes in on polyunsaturated fatty acids [2]. In terms of fatty acids,
coconut water when they existed together with aldehydes short- to medium-chain saturated fatty acids are common
and esters [1]. One of the alcohols found, 1-hexanol, was to be contained in coconuts of the tall variety, along with
stated to be responsible for the typical coconut aroma when several longer chain polyunsaturated fatty acids [22]. These
it was present together with the lactones [1, 2]. Ethanol, fatty acids were also detected in this study, through both
the most abundant alcohol found, was detected only with analysis of volatile compounds (Table 2) and analysis of
HS–SPME method. HS–SPME managed to extract fewer fatty acid composition (Table 3). Moreover, Meethaworn
volatile aroma compounds compared to solvent extraction. and Siripanich have reported the presence of lipoxygenase
However, highly-volatile compounds can be picked up by and lipase in young coconut water [23]. Therefore, the exist-
HS–SPME more conveniently [10]. Moreover, this method ence of all these factors can contribute to the formation of
does not use solvent; thus, compounds that are eluted early aldehydes in the sample.
would appear on the chromatogram without the risk of get- Esters were also detected in the sample and several of
ting co-eluted with solvent peak. Therefore, the combina- them were fatty acid ethyl esters. Fatty acid ethyl esters are
tion of both solvent extraction and HS–SPME methods was formed from fatty acids and ethanol [12], where both were
expected to provide a complete volatile aroma compound found naturally in the sample. The most abundant fatty acid
profile of the sample. ester identified in this study was ethyl octanoate, which was
The third largest group identified was fatty acids, indicat- also reported as the highest amount of ester found in coconut
ing the oily nature of the sample. Fatty acids of C6, C8, C10, milk [16].

13
Aroma compound profile of mature coconut water from tall variety through thermal treatment

Table 2  Volatile aroma compounds in fresh mature coconut water


No. Volatile aroma compound Method of extraction Retention index Odor ­descriptiona Method of
­identificationb
Solvent HS–SPME Stabilwax® Rxi-5ms
extraction

1 Acetaldehyde No Yes < 1000 ND Nutty, alcoholic (a) MS, RI


2 Ethyl acetate No Yes < 1000 ND Winey (a) MS, RI
3 Ethanol No Yes < 1000 ND Sweet, ethereal (a) MS, RI
4 3-Pentanone No Yes < 1000 ND Ethereal (a) MS, RI
5 2-Methyl-1-propanol Yes Yes < 1100 ND Sweet, whiskey-like (a) MS, RI
6 1-Propanol No Yes 1033 ND Alcohol, sweet (a) MS, RI
7 1-Butanol Yes Yes 1145 ND Winey (a) MS, RI, SC
8 2-Heptanone No Yes 1165 916 Fruity, cheesy, cinnamon (a) MS, RI
9 3-Methyl-1-butanol Yes Yes 1203 ND Alcoholic (a) MS, RI, SC
10 Ethyl hexanoate Yes Yes 1223 1003 Fruity, winey (a) MS, RI
11 Acetoin Yes Yes 1277 ND Buttery, creamy, yogurt-like (a) MS, RI, SC
12 2-Heptanol Yes Yes 1311 ND Green lemon, herbaceous (a) MS, RI
13 1-Hexanol Yes Yes 1343 ND Winey, slightly fatty-fruity (a) MS, RI
14 Trans-3-hexen-1-ol Yes No 1357 ND Green, grass, leafy (a) MS, RI
15 2-Nonanone No Yes 1368 ND Fruity, fatty-cheese (a) MS, RI
16 Ethyl octanoate Yes Yes 1416 1196 Fruity, winey, sweet (a) MS, RI
17 2-Ethyl-1-hexanol Yes Yes 1474 ND Sweet, oily, weak rose (a) MS, RI
18 Benzaldehyde Yes No 1515 ND Almond, bitter (a) MS, RI, SC
19 2-(Methylthio)-ethanol Yes No 1523 ND sulfury, vegetable-like (a) MS, RI
20 1-Octanol No Yes 1553 ND Sweet, waxy, orange-rose (a) MS, RI
21 2,3-Butanediol Yes No 1568 ND Fruity, sweet (b) MS, RI
22 Ethyl decanoate Yes Yes 1606 1395 Sweet, fatty, nut-like, winey (a) MS, RI
23 Butyrolactone Yes No 1615 ND Coconut-like, buttery, creamy, nutty (a) MS, RI
24 3-(Methylthio)-1-propanol Yes No 1702 ND Meaty, soup-like (a) MS, RI
25 δ-Hexalactone Yes No 1783 ND Coconut, creamy (a) MS, RI, SC
26 Ethyl dodecanoate Yes Yes 1825 1594 Fatty, floral (a) MS, RI
27 Hexanoic acid Yes No 1831 ND Fatty, cheesy (a) MS, RI, SC
28 4-Methyl-5H-furan-2-one Yes No 1883 ND Roast, nutty, sweet, caramel (c) MS, RI
29 Phenylethyl alcohol Yes No 1898 ND Floral, rose-like (a) MS, RI, SC
30 δ-Octalactone Yes No 1960 ND Coconut, creamy (a) MS, RI, SC
31 Octanoic acid Yes No 2047 ND Fatty, rancid (a) MS, RI, SC
32 δ-Decalactone Yes No 2188 ND Sweet, creamy, milky, peach, nutty (a) MS, RI, SC
33 Decanoic acid Yes No 2259 ND Fatty, waxy, cheesy, dairy (a) MS, RI, SC
34 Dodecanoic acid Yes No 2467 ND Fatty, waxy (a) MS, RI

ND not detected
a
 Odor description was obtained from (a) Leffingwell [18], (b) Kim et al. [19], and (c) Kabir and Lorjaroenphon [20]
b
 Each compound was identified based on: MS = mass spectrometry, RI = matching of the retention index with the literature, SC = injection of the
standard compound into similar GC–TOFMS system

Thiols, sulfur analogs of alcohols, were discovered in Effect of heating on volatile aroma compounds
the sample. A study by da Fonseca et al. detected a rela- in mature coconut water from tall variety
tively high amount of thiols in the essential oil of coconut
water from yellow variety in Brazil [14]. One of the thiols, Table 4 shows that heat treatment caused changes in the con-
3-(methylthio)-1-propanol or methionol, was reported to centration of several volatile aroma compounds in mature
be associated with sulfury, soup-like, meaty, boiled potato- coconut water. De Marchi et al. reported change of flavor
like, vegetable-like, and savory characteristics [24]. in pasteurized coconut water from Thai aromatic coconut

13
Z. Nasution et al.

Table 3  Fatty acid composition of fresh mature coconut water losses of lactones might come from thermal degradation
Fatty acid Relative
rather than evaporation [32]. Saittagaroon et al. reported
concentration that in roasted shredded coconut, the decrease in δ-lactones
(g/L)a brought reduction in sweet and coconut-like aroma of the
sample [33].
Caprylic acid (C8:0) 5.5 ± 1.2
In terms of alcohols, there was a diverse pattern among
Capric acid (C10:0) 3.6 ± 0.8
the alcohols in their content pre- and post-heat treatment
Lauric acid (C12:0) 20.9 ± 4.0
as shown in Table 4. De Marchi et al. found similar results
Myristic acid (C14:0) 8.4 ± 0.0
where some alcohols in the water of Thai aromatic coconut
Palmitic acid (C16:0) 12.0 ± 0.4
increased after pasteurization, while others decreased or
Stearic acid (C18:0) 7.2 ± 2.2
relatively unchanged [4]. Alcohol losses were most possibly
Oleic acid (C18:1) 10.2 ± 1.2
due to evaporation during heating, while increase in some
Linoleic acid (C18:2) 12.5 ± 1.6
alcohols might be caused by hydrolysis [32]. Meanwhile for
a
 Each value is the mean of two replications followed by standard aldehydes, there was a reduction in the sample, which was
error of the mean also reported in a study performed by Nisperos-Carriedo and
Shaw on orange juice that was heat-processed with pasteuri-
variety, which was mostly caused by fluctuation in the con- zation and canning procedures [34].
centration of each compound, with few new compounds Figure 1 shows a decrease (2–21%) of the ketone group in
formed after the pasteurization process at 90 °C for 1 min heated samples, which were contributed largely by acetoin
[4]. It can be observed from Table 4 that several compounds (Table 4). The decrease can be considered desirable since it
showed a declining trend as the heating temperature was might bring a lower level of fatty, buttery, and yogurt-like
increased, which was due to possible thermal degradation aroma. Several studies have reported possible conversion of
and interaction between sugars and amino acids during acetoin into 2,3-butanediol through enzymatic reaction by
heating. A similar trend was also observed in sap syrup and acetoin reductases [35]. Based on an aroma extract dilution
coconut sugar when they were heat-processed from fresh analysis using gas chromatography/olfactometry by Kim
coconut sap [25]. et al., 2,3-butanediol was reported to provide fruity and
There was an increasing trend of fatty acid content as sweet characteristics [19].
shown in Fig. 1. In their report on changes of volatile com- For other ketones, they were seen to also change in
pounds in canned coconut milk, Tinchan et al. stated that concentration due to heat treatment, either increased or
degradation of lipids in the sample can possibly start from decreased. A similar trend was reported by Aili et al. in ther-
the sample preparation step, even before heat was applied mally-processed vinegar, where a higher amount of ketones
[16]. Furthermore, thermal process can also cause heat- post-processing was hypothesized to be caused by Maillard
induced lipolysis. The fatty acids released might be impor- reaction, while reduction of ketones was described as the
tant to the flavor of the sample, where fatty acids with carbon possible effect of oxidation reaction or thermal degradation
atoms fewer than 8 or 10 usually provide acidic, pungent, [36].
and rancid characteristics, while those with more than 12 An OAV is used to predict contribution of a compound
carbons bring soapy taste [16]. Octanoic acid maintained to to the perceived odor of a foodstuff and compounds with
be the major volatile fatty acid identified in heated mature OAVs > 1 are considered to have contribution to the aroma
coconut water. of a food product [37]. Based on their relatively high OAVs,
A slight increase in lactones, for example butyrolac- ethyl acetate (winey odor) and acetoin (buttery, creamy,
tone, was most probably due to thermal treatment. This yogurt-like odor) had major contribution to the aroma of
phenomenon can be considered beneficial since lactones fresh mature coconut water. Meanwhile, ethyl hexanoate
are the aroma-impact compounds in coconut-related prod- (fruity, winey odor), ethyl octanoate (fruity, winey, sweet
ucts. Hydroxy fatty acids, the precursors of lactones, could odor), and ethyl decanoate (sweet, fatty, nut-like, winey
be produced from free fatty acids that are formed through odor) were the compounds that increased their OAVs to be
heat-induced lipolysis or from enzymatic lipolysis [16]. higher than 1 after heating, indicating their potential impor-
Specifically for butyrolactone, it could involve the release tance in the aroma compound profile of the sample after
of 4-hydroxybutanoic acid during heating, which was fur- heat treatment.
ther interesterified into the lactone [32]. After an initial The increased amount of fatty acid ethyl esters by 2–20%
increase at a lower heating temperature, there was a decreas- that was found in heated sample was assumed to come from
ing trend in δ-lactones observed when heating temperature the esterification reaction of alcohols and fatty acids [12,
was increased. A study on dried mango saw similar trend of 36]. After an initial increase at lower heating temperature,
increasing butyrolactone and decreasing δ-lactones, where formation of fatty acid ethyl esters seemed to slow down at

13
Table 4  Effect of heating on volatile aroma compounds in mature coconut water
No. Volatile aroma compound Odor detection Relative concentration (µg/L)b Odor activity value (OAV)
threshold (µg/L)a
Fresh 85 °C, 15 min 90 °C, 10 min 95 °C, 10 min Fresh 85 °C, 15 min 90 °C, 10 min 95 °C, 10 min

1 Acetaldehyde 15 (a) 2.5 ± 1.0 0.3 ± 0.0 0.2 ± 0.1 0.2 ± 0.1 < 1 < 1 < 1 < 1
2 Ethyl acetate 5 (a) 7.4 ± 7.2 9.0 ± 8.7 1.6 ± 1.3 0.2 ± 0.1 1.5 1.8 < 1 < 1
3 Ethanol 100,000 (a) 89.0 ± 4.3 84.7 ± 0.8 62.2 ± 16.2 62.1 ± 21.1 < 1 < 1 < 1 < 1
4 3-Pentanone 40 (b) 0.4 ± 0.2 0.8 ± 0.4 0.4 ± 0.0 0.3 ± 0.0 < 1 < 1 < 1 < 1
5 2-Methyl-1-propanol 7000 (a) 27.8 ± 7.0 ND ND ND < 1 ND ND ND
6 1-Propanol 9000 (a) 1.4 ± 0.1 2.9 ± 0.6 2.5 ± 0.5 2.3 ± 0.4 < 1 < 1 < 1 < 1
7 1-Butanol 500 (a) 34.1 ± 3.7 39.2 ± 10.2 29.1 ± 4.2 18.0 ± 9.2 < 1 < 1 < 1 < 1
8 2-Heptanone 140 (a) 0.8 ± 0.8 1.6 ± 1.4 1.2 ± 1.1 1.1 ± 1.1 < 1 < 1 < 1 < 1
9 3-Methyl-1-butanol 250 (a) 101.1 ± v8.4 161.8 ± 8.9 4.0 ± 0.5 6.7 ± 0.7 < 1 < 1 < 1 < 1
10 Ethyl hexanoate 1 (a) 0.9 ± 0.6 10.2 ± 1.6 4.5 ± 1.2 3.5 ± 2.5 < 1 10.2 4.5 3.5
11 Acetoin 800 (a) 967.0 ± 105.3 760.2 ± 218.2 857.7 ± 367.3 878.6 ± 351.2 1.2 < 1 1.1 1.1
12 2-Heptanol 41 (b) 4.4 ± 1.1 5.7 ± 3.3 1.0 ± 0.8 0.3 ± 0.0 < 1 < 1 < 1 < 1
13 1-Hexanol 2500 (a) 5.1 ± 1.6 4.5 ± 0.4 3.3 ± 0.9 4.5 ± 0.3 < 1 < 1 < 1 < 1
14 Trans-3-hexen-1-ol 110 (c) 3.8 ± 0.4 4.3 ± 0.7 4.5 ± 0.2 5.1 ± 0.1 < 1 < 1 < 1 < 1
15 2-Nonanone 5 (a) 0.6 ± 0.6 1.2 ± 1.1 0.9 ± 0.9 0.9 ± 0.9 < 1 < 1 < 1 < 1
16 Ethyl octanoate 15 (c) 13.2 ± 7.6 114.6 ± 44.1 20.9 ± 14.3 40.1 ± 23.8 < 1 7.6 1.4 2.6
17 2-Ethyl-1-hexanol 270,000 (a) 4.5 ± 0.3 6.0 ± 1.9 4.7 ± 0.1 3.6 ± 0.1 < 1 < 1 < 1 < 1
18 Decanal 2 (a) ND ND ND 0.2 ND ND ND < 1
19 Benzaldehyde 350 (a) 2.7 ± 0.0 ND ND ND < 1 ND ND ND
20 2-(Methylthio)-ethanol 120 (d) 13.1 ± 0.1 ND ND ND < 1 ND ND ND
Aroma compound profile of mature coconut water from tall variety through thermal treatment

21 1-Octanol 110 (a) 0.1 ± 0.1 0.5 ± 0.1 0.3 ± 0.2 0.2 ± 0.2 < 1 < 1 < 1 < 1
22 2,3-Butanediol 100,000 (e) 206.6 ± 127.9 241.6 ± 108.1 93.9 ± 18.8 332.4 ± 0.5 < 1 < 1 < 1 < 1
23 Butyrolactone 1000 (e) 5.4 ± 1.8 5.8 ± 0.9 5.4 ± 1.2 7.4 ± 1.9 < 1 < 1 < 1 < 1
24 Ethyl decanoate 23 (c) 1.9 ± 1.0 24.3 ± 17.8 17.4 ± 0.6 1.9 ± 1.1 < 1 1.1 < 1 < 1
25 3-(Methylthio)-1-propanol 250 (f) 4.3 ± 1.9 14.0 ± 3.4 3.5 ± 3.2 12.3 ± 1.9 < 1 < 1 < 1 < 1
26 δ-Hexalactone n/a 2.4 ± 0.1 11.3 ± 7.6 0.5 ± 0.2 1.3 ± 0.4 n/a n/a n/a n/a
27 Ethyl dodecanoate 400 (c) 8.3 ± 3.9 151.2 ± 6.6 37.8 ± 0.2 4.5 ± 1.5 < 1 < 1 < 1 < 1
28 Hexanoic acid 3000 (a) 1.4 ± 1.0 13.7 ± 4.2 42.0 ± 11.0 52.1 ± 31.2 < 1 < 1 < 1 < 1
29 4-Methyl-5H-furan-2-one n/a 2.5 ± 0.5 0.3 ± 0.2 1.1 ± 0.1 4.5 ± 1.9 n/a n/a n/a n/a
30 Phenylethyl alcohol 750 (a) 3.5 ± 0.2 6.8 ± 2.3 1.7 ± 1.6 6.9 ± 0.8 < 1 < 1 < 1 < 1
31 δ-Octalactone 400 (a) 4.2 ± 1.7 5.0 ± 0.5 0.3 ± 0.1 2.8 ± 0.5 < 1 < 1 < 1 < 1
32 Octanoic acid 3000 (a) 12.1 ± 3.1 37.9 ± 5.5 116.3 ± 6.1 185.0 ± 12.0 < 1 < 1 < 1 < 1
33 δ-Decalactone 100 (a) 0.3 ± 0.3 ND ND ND < 1 ND ND ND
34 Decanoic acid 10,000 (a) 0.8 ± 0.2 1.3 ± 0.1 6.7 ± 2.1 7.9 ± 0.9 < 1 < 1 < 1 < 1

13
Z. Nasution et al.

higher heating temperatures. This phenomenon can be linked

 Odor detection thresholds (in water) were obtained from: (a) Leffingwell & Associates [26], (b) van Gemert [27], (c) Boonbumrung et al. [28], (d) Hansen et al. [29], (e) Buttery and Ling [30],

 Each value is the mean of two replications followed by standard error of the mean; relative concentration was calculated from data of solvent extract, except for compounds that were detected
95 °C, 10 min
to the lower availability of ethanol as can be seen in Table 4,
since it evaporated during heat treatment. Availability of
alcohol has been stated as one of the important factors in
< 1
esterification of fatty acids [38].
A hierarchical cluster analysis was performed on the
90 °C, 10 min

compounds’ relative concentrations. As shown in the den-


dogram (Fig. 2), the four treatments were sorted into three
clusters. Fresh sample was differentiated from heat-treated
< 1

samples, indicating the difference in its volatile aroma com-


Odor activity value (OAV)

pound profile. The heat treatment at 85 °C for 15 min was


85 °C, 15 min

differentiated from the other two heat treatments that were


clustered together, signaling the difference in the composi-
tion of aroma compounds resulted in this treatment. These
< 1

differences were also shown by OAV of the compounds


(Table 4). Heat treatment managed to reduce volatile aroma
Fresh

< 1

compounds that may give undesirable odor in mature coco-


nut water such as acetoin (yogurt-like aroma) and increase
several other volatile aroma compounds that might contrib-
95 °C, 10 min

ute to pleasant odor, such as the fatty acid ethyl esters that
6.8 ± 0.6

can bring sweet and floral aroma.

Sensory evaluation
90 °C, 10 min

Figure 3 shows the results of descriptive aroma analysis of


9.6 ± 5.9

mature coconut water samples. Fresh mature coconut water


was described by the panelists to be more dominant in fer-
ment and rancid aroma, where both attributes are considered
undesirable in coconut water. Heat treatment decreased the
85 °C, 15 min
Relative concentration (µg/L)b

ferment aroma, which was most likely due to reduction of


2.3 ± 0.2

acetoin. Heat treatment also managed to lower the intensity


of rancid aroma in heated samples compared to the fresh one.
Moreover, it increased the coconut-like aroma of samples,
as well as the floral, sweet, and creamy attributes, which
could be due to higher amount of fatty acid esters in heated
1.9 ± 0.8

samples (Table 4). Heating of mature coconut water sample


Fresh

at 85 °C for 15 min gave slightly higher intensity of sweet


and creamy aroma compared to the other heat treatments.
threshold (µg/L)a
Odor detection

10,000 (a)

Conclusions

Several volatile compound groups namely ketones, alco-


hols, esters, fatty acids, lactones, thiols, and aldehydes were
n/a not available, ND not detected
Volatile aroma compound

identified as the volatile aroma compounds contained in


(f) Fritsch and Schieberle [31]

fresh mature coconut water from tall variety, with acetoin


as the most abundant compound. Heat treatment managed
Dodecanoic acid

to alter the aroma profile of mature coconut water sam-


only with HS–SPME
Table 4  (continued)

ples compared to the fresh one. Analysis of volatile aroma


compounds showed that concentration of acetoin (buttery
and yogurt-like characteristics) decreased in heated sam-
ples. This finding was supported by the results of sensory
No.

evaluation that showed a reduction in intensity of ferment


35

b
a

13
Aroma compound profile of mature coconut water from tall variety through thermal treatment

Fig. 1  Comparison of relative
concentration percentage of
groups of volatile aroma com-
pounds in mature coconut water
as affected by heat treatment
(n = 2)

Fig. 2  Dendogram of hierarchi-
cal classification of volatile
aroma compounds extracted
90 °C, 10 min
from fresh and heat-treated
mature coconut water

95 °C, 10 min

Fresh

85 °C, 15 min

0 10 20 30 40 50 60
Dissimilarity

Fig. 3  Descriptive aroma Coconut -like


profiles of fresh and heat-treated 6
mature coconut water
5

4
Ferment 3 Floral

2 Fresh
1
85 °C, 15 min
0
90 °C, 10 min

95 °C, 10 min

Rancid Sweet

Creamy

13
Z. Nasution et al.

attribute in heated samples. Furthermore, heat treatment also 15. O. Lasekan, K.A. Abbas, Trends Food Sci. Technol. 21, 494–501
increased the concentration of fatty acid esters (sweet and (2010)
16. P. Tinchan, Y. Lorjaroenphon, K.R. Cadwallader, S. Chaiseri, J.
floral aroma), which was further shown in descriptive sen- Food Sci. 80(1), 49–54 (2015)
sory analysis where the intensity of floral, sweet and creamy 17. O. Uckun, S. Selli, J. Food Meas. Charact. 11, 1118–1127 (2017)
attributes was slightly higher in heated samples compared 18. J.C. Leffingwell, Flavor-Base Database (Leffingwell & Associ-
to the fresh sample. ates, Georgia, 2004)
19. T.H. Kim, J.H. Shin, H.H. Baek, H.J. Lee, J. Sci. Food Agric. 81,
569–575 (2001)
Acknowledgements  The authors would like to thank Faculty of Agro- 20. Md.A. Kabir, Y. Lorjaroenphon, in The Proceeding of 52nd Kaset-
Industry, Kasetsart University and Kasetsart University Research and sart University Annual Conference: Agro Industry (Kasetsart Uni-
Development Institute (KURDI) for their support. versity, Bangkok, 2013), pp. 239–246
21. J.E.R. Santos, B.J. Villarino, A.R. Zosa, F.M. Dayrit, Philipp. J.
Sci. 140(2), 161–171 (2011)
22. W. Twishri, P. Runheem, S. Usathit, S. Watanayothin, P. Naka,
References Acta Hortic. 1024, 427–432 (2014)
23. K. Meethaworn, J. Siriphanich, Thai J. Agric. Sci. 45(3/1), 273–
276 (2014)
1. L. Jirovetz, G. Buchbauer, M.B. Ngassoum, Ernährung/Nutr. 27, 24. Y.-X. Seow, P.K.C. Ong, S.-Q. Liu, Int. J. Food Microbiol. 143,
300–303 (2003) 235–240 (2010)
2. A. Prades, R.R.A. Assa, M. Dornier, J.-P. Pain, R. Boulanger, J. 25. H. Purnomo, ASEAN Food J. 14(1), 45–49 (2007)
Sci. Food Agric. 92, 2471–2478 (2012) 26. Leffingwell & Associates, Odor & Flavor Detection Thresholds
3. C. Jirapong, C. Wongs-Aree, S. Noichinda, A. Uthairatanakij, S. in Water (In Parts per Billion) (Leffingwell & Associates, 2008),
Kanlayanarat, J. Hortic. Sci. Biotechnol. 90(5), 477–482 (2015) http://www.leffi​ngwel​l.com/odort​hre.htm. Accessed 1 July 2017
4. F. De Marchi, E. Aprea, I. Endrizzi, M. Charles, E. Betta, M.L. 27. L.J. van Gemert, Odour Thresholds: Compilations of Odour
Corollaro, M. Cappelletti, G. Ferrentino, S. Spilimbergo, F. Gas- Threshold Values in Air, Water, and Other Media, 2nd edn. (Ollie-
peri, Food Bioprocess Technol. 8, 1393–1404 (2015) mans Punter & Partners BV, Utrecht, 2011)
5. J.C. Jackson, A. Gordon, G. Wizzard, K. McCook, R. Rolle, J. Sci. 28. S. Boonbumrung, H. Tamura, J. Mookdasanit, H. Nakamoto, M.
Food Agric. 84, 1049–1052 (2004) Ishihara, T. Yoshizawa, W. Varanyanond, Food Sci. Technol. Res.
6. A. Prades, M. Dornier, N. Diop, J.-P. Pain, Fruits 67(2), 87–107 7(3), 200–206 (2001)
(2012) 29. M. Hansen, R.G. Buttery, D.J. Stern, M.I. Cantwell, L.C. Ling, J.
7. N.d.C. Murasaki-Aliberti, R.M.S. da Silva, J.A.W. Gut, C.C. Agric. Food Chem. 40, 850–852 (1992)
Tadini, Int. J. Food Sci. Technol. 44, 2662–2668 (2009) 30. R.G. Buttery, C.L. Ling, J. Agric. Food Chem. 46, 2764–2769
8. C. Jirapong, A. Uthairatanakij, S. Noichinda, S. Kanlayanarat, (1998)
Acta Hortic. 943, 111–115 (2012) 31. H.T. Fritsch, P. Schieberle, J. Agric. Food Chem. 53(19), 7544–
9. C.-H. Xu, G.-S. Chen, Z.-H. Xiong, Y.-X. Fan, X.-C. Wang, Y. 7551 (2005)
Liu, Trends Anal. Chem. 80, 12–29 (2016) 32. A. Bonneau, R. Boulanger, M. Lebrun, I. Maraval, Z. Gunata, Int.
10. T.-C. Tan, L.-H. Cheng, R. Bhat, G. Rusul, A.M. Easa, Food J. Food Sci. Technol. 51, 789–800 (2016)
Chem. 142, 121–128 (2014) 33. S. Saittagaroon, S. Kawakishi, M. Namiki, Agric. Biol. Chem.
11. C. Saemah, W. Jirapakkul, in The Proceeding of 49th Kasetsart 48(9), 2301–2307 (1984)
University Annual Conference: Agro Industry (Kasetsart Univer- 34. M.O. Nisperos-Carriedo, P.E. Shaw, J. Agric. Food Chem. 38(4),
sity, Bangkok, 2011), pp. 564–572 1048–1052 (1990)
12. M. Gallart, S. Francioli, A. Viu-Marco, E. López-Tamames, S. 35. T.H. Yang, C. Rathnasingh, H.J. Lee, D. Seung, J. Biotechnol.
Buxaderas, J Chromatogr. A 776, 283–291 (1997) 172, 59–66 (2014)
13. Q. Zhou, C.L. Wintersteen, K.R. Cadwallader, J. Agric. Food 36. W. Aili, S. Huanlu, R. Changzhong, L. Zaigui, Flavour Fragr. J.
Chem. 50, 2016–2021 (2002) 27, 47–53 (2012)
14. A.M. da Fonseca, A.M.C. Bizerra, J.S.N. de Souza, F.J.Q. Monte, 37. W. Grosch, Chem. Senses 26, 533–545 (2001)
M.d.C.F. de Oliveira, M.C. de Mattos, G.A. Cordell, R. Braz- 38. B. Freedman, E.H. Pryde, T.L. Mounts, J. Am. Oil Chem. Soc.
Filho, T.L.G. Lemos, Rev. Bras. Farmacogn. 19(1B), 193–198 61(10), 1638–1643 (1984)
(2009)

13

You might also like