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Industrial Crops and Products 65 (2015) 429436

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Industrial Crops and Products

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / i n d c r o p

The yield, composition and hydrodistillation kinetics of the essentialoil of dill seeds (Anethi fructus) obtained by different hydrodistillationtechniques

Ljiljana P. Stanojevic a,, Niko S. Radulovic b, Tatjana M. Djokic c, Biljana M. Stankovic a,Dusica P. Ilic a, Milorad D. Cakic a, Vesna D. Nikolic a

a Faculty of Technology, Leskovac, University of Nis, Serbiab Faculty of Science and Mathematics, University of Nis, Nis, Serbiac The Academy of Criminalistic and Police Studies, Belgrade, Serbia

a r t i c l e i n f o

Article history:

Received 21 July 2014

Received in revised form 27 October 2014

Accepted 30 October 2014

Available online 20 November 2014

Keywords:

Dill (Anethum graveolensL.)

Essential oil

Carvone

Hydrodistillation techniques

Hydrodistillation kinetics

a b s t r a c t

In this work the impact of four different techniques of Clevenger-type hydrodistillation (technique IIV)

on the yield, hydrodistillation kinetics andcomposition of the essentialoils ofAnethum graveolens L. seedswasinvestigated.The highest oil yield, after fiveconsecutive hydrodistillation runs(3.74 ml/100 g of plantmaterial), was achieved by the utilization of filtrated (from plant material) water used in the previous

hydrodistillationrun plusnewly addedwater in the subsequentruns (techniqueIII). Thehydrodistillationofdill seeds tookplace intwo stages: a rapid,earlydistillation of theoil followedby a much slowersecond

phase. Twokinetics models were successfully used to interpret the hydrodistillation rate of the essentialoil of dill. Independent of the technique used, the oil contained the same components but in differing

amounts as inferred from detailed gas chromatographymass spectroscopy (GCMS) analyses. Carvonewas found to be the major component in all obtained oils.

2014 Elsevier B.V. All rights reserved.

1. Introduction

Dill (Anethum graveolensL.) is an aromatic spice plant from thegenus Anethum of the family Apiaceae (Umbelliferae) (Leung and

Foster, 2003). This plant is an important condiment crop with acharacteristic aroma and odour (Pino et al., 1995).It is well knownas a medicinal herb with antimicrobial, hypotensive, antihyper-lipidemic, diuretic, antiemetic, laxative and spasmolytic effects

(Koppula and Choi, 2011; Hosseinnzadeh et al., 2002; Tucakov,1997).The medicinal parts of the plant are its seeds, fresh or driedleaves and the upper stem (Leung and Foster, 2003; Faber et al.,1997). Various plant parts of dill have different odours (Faber et al.,

1997).Dill seeds contain the highest concentration of medicinal and

aromatic compounds, but an appreciable amount is also present inthe leaves and flowers (Koppula and Choi, 2011).The essential oils

from dill seeds, leaves and herb were used as a flavouring agentin the food industry, especially for their characteristic aroma andodour (Jirovetz et al., 2003).Dill seeds are considered as a valuable

Corresponding author. Tel.: +381 16247203; fax: +381 16242859.

E-mail addresses:[email protected],[email protected](L.P. Stanojevic).

source of essential oil (Ortan et al., 2009). The main compoundsof the herb essential oil are -phellandrene and dill ether whichare responsible for the typical herb odour. Besides -phellandreneand dill ether, limonene and carvone are present in large amounts.

Carvone is mainly responsible for the typical caraway note of theoils. This monoterpene ketone is the main component of the seedsessential oil (Faber et al., 1997).With 25% of the essential oil dillseeds are deemed to be rich in the essential oil (Leung and Foster,

2003).Carvone was reported to be the major constituent (2060%)inanumberofinstances( Leungand Foster, 2003; Callanet al., 2007;Radulescu et al., 2010; Delaquis et al., 2002).Limonene, apiole, dillapiole,-phelandrene,-pinene,-terpinene,1,8-cineole, dihydrocarvone andp-cymene are also present in the oil (Leung and Foster,2003; Pino et al., 1995).Dill leaves and herb contain significantlyless essential oil when compared to the seeds (0.51.5%) ( Faberet al., 1997; Leung and Foster, 2003).

Essential oils are used in pharmaceutical, cosmetic and foodindustries and as natural remedies (Bakkali et al., 2008).The yield,taste, flavour and chemical composition (amount and ratio of com-ponents) of essential oil depends on a number of parameters, such

as plant variety, season, soil, environmentalconditions,drying pro-cedure,storage conditions, method of distillation,and the analyticsused for identification of the compounds (Leung and Foster, 2003;

http://dx.doi.org/10.1016/j.indcrop.2014.10.067

0926-6690/ 2014 Elsevier B.V. All rights reserved.
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430 L.P. Stanojevic et al. / Industrial Crops and Products 65 (2015) 429436

Faber et al., 1997;Ghassemi-Golezani et al., 2008; Nautiyal and

Tiwari, 2011; Jirovetz et al., 2003; Callan et al., 2007; Stanojevicet al., 2011; Stankovic et al., 2001, 2005, 2004).

Despite of the generally successful practical hydrodistillationtechnology used to extract essential oils, there is still a need to

consider a procedure or method in detail that would enable theproduction of essential oils at an optimum output. Each essentialoil should be considered on its own due to its specificities includ-ing the type of the plant material used for the extraction and the

varying chemical composition of the oil produced. The objective ofthis study was to investigate the influence of the hydrodistillationtechnique on the extraction of dill oil from A. graveolens seeds interms of oil yield and oil quality (physical properties and chemical

composition). Then a developed mass transfer mathematical modelwasvalidated with the experimentalresults to describe theprocessbehaviour.

Up to now many investigators have modelled the kinetics of

essential oil hydrodistillation from plant material (Milojevic et al.,2013 and references cited therein). However, no data on theinfluence of different hydrodistillation techniques on the yield,composition or hydrodistillation kinetics of the essential oil from

dill seeds can be found in the literature. In this work the essentialoil from dill seeds was obtained by four different hydrodistilla-

tion techniques and the yields, as well as the composition of theresulting essential oils was compared. Also, the hydrodistillation

kinetics were compared, with an aim to choose the optimal tech-nique affording maximal oil yield.

2. Materials and methods

2.1. Plant material

Dried dill (Anethum graveolensL.) seeds (Anethi fructus) werepurchased from Planta Mell (Svrljig, Southeast Serbia). Non-disintegrated dill seeds were used for the investigations. The

moisture content of dill seeds determined by drying at 105 C to

a constant weight was 7.33%. The initial oil content in the dill seedswas 4.0 ml/100g dry plant material.

2.2. Essential oil isolation hydrodistillation

Influence of the hydrodistillation hydromodule. A separate (perhydromodule) batch of 15g of dill seeds was subjected to standardClevenger-type hydrodistillation conditions (the condensed water

was recirculated) with water used in the following ratios (w/v,g/cm3): 1:10, 1:15, 1:20 and 1:25. The oil yield (v/w) was recordedafter hydrodistillation time of 5180 min.

Influence of hydrodistillation techniques. Four hydrodistillation

techniques of essential oil from dill seeds were applied ( Stankovicet al., 2004; Stanojevic et al., 2011).

Technique I Classic Clevenger-type hydrodistillation(cohobation)(Stankovic et al., 2004; Stanojevic et al., 2011).The amount of 15 g

of seeds was suspended in 300 ml of water and subjected to Cle-venger hydrodistillation. The essential oil volume was recordedafter hydrodistillation time of 5180 min. The data from five con-

secutive runs was used to calculate the average oil yield.

Technique II(Stankovic et al., 2004).This technique is the sameas technique I, only the condensate water was not cohobated,but itwas saved and combined with fresh waterto a volume of300 mlfor

the subsequent distillation of a new batch of dill seeds (Stanojevicet al., 2011). A new quantity of plant material (15g) was usedfor each successive distillation. The oil volume was recorded afterhydrodistillation time of 5120 min. This procedure was repeated

in successive four distillation runs with a new quantity of plant

material (15 g).

Technique III (Stankovic et al., 2004; Stanojevic et al., 2011).

The same as technique I, only the residual water from a previoushydrodistillation was, after the separation of plant debris by vac-uumfiltration, mixed with a newamount ofwater(the total volumeof the residual water from a previous run and thenewly added one

was adjusted to 300 ml) utilized for the next distillation of a newbatch of dill seeds. A new batch of 15 g of seeds was subjected toeach successive distillation run. The oil volume was recorded afterhydrodistillation time of 5180 min. This procedure was repeated

in successive four distillation runs with a new quantity of plantmaterial (15 g).

Technique IV(Stankovic et al., 2004).The same as technique I,only the condensate and residue still water from previous distil-

lation were combined and made up with unused water to a finalvolume of 300 ml, and used as such in the subsequent hydrodis-tillation of a new quantity of dill seeds. The oil volume wasrecorded after hydrodistillation time of 5120 min. This procedure

was repeated in successive four distillations with a new quantityof plant material (15 g).

After the fifth run of each hydrodistillation technique (I-IV),iso-lated essentialoils of the five runs (15) were separated,dried with

Na2SO4 (anhydrous), and used to determine the physicochemicalproperties and for GCMS analysis.

2.3. Hydrodistillation kinetics models

The hydrodistillation kinetics of the essential oil from dill seeds

was modelled by two models (Table 1):the model of Ponomarev(Ponomarev, 1976; Stanojevic et al., 2011)(Model A) and a non-stationary diffusion model through the plant material (Veljkovicand Milenovic, 2002; Milojevic et al., 2008)(Model B).

Table 1

Hydrodistillation kinetics models of essential oil from dill seeds.

Kinetics model Kinetics equation Linearized form of equation

Non-stationary diffusion

model through the plant

material (Model B)

qiq0

= (1 b) ekt(1) ln qiq0

= ln(1 b) k t (2)

Model of Ponomarev

(Model A)

q0 qiq0

= b+ k t(3)

q0 the initial essential oil amount in the seeds (ml/100g dry seeds),q i the oil

content in the seeds after the period t(ml/100g of dry seeds),b coefficient of the

initial rapid stage of hydrodistillation,k coefficient of the second slower stage of

the hydrodistillation (min1) andt the duration of hydrodistillation (min).

2.4. Gas chromatography/mass spectrometry (GC/MS) analyses

Gas chromatography-mass spectrometry analyses (GC/MS)were performed (in triplicate) according to Radulovicand or devic(2014) on a Hewlett-Packard 6890N gas chromatograph cou-

pled with a 5975B MS detector. A non-polar, low-bleed columnDB-5MS (length 30m, i.d. 0.25mm, film thickness 0.25m, 5%poly(methylphenylsiloxane),AgilentJ&W, USA),programmed from70 C to 290 C at 5 C/min and afterwards held isothermally for10min at 290 C, was used. Injector and interface temperatures

were 250 C and 300 C, respectively. The flow of He was held con-stant at1.0 ml/minstartingfromthe first 30 s afterthe injection.TheEt2O solutions of the essential oil (1 mg/ml) samples (1l) weresplit injected (40:1) in a pulsed mode (Radulovic and or devic,

2014). Theoperationalconditions ofthe MS detector were: electronimpact(EI) energy, 70 eV;ion sourcetemperature,230 C; recordedmass rangem/z35650. The relative (%) oil composition was cal-culated from the total ion current peak areas without correction

factors. Identification of oil components was done as described inRadulovic andor devic (2014).


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2.5. Physicochemical characteristics of dill oil

Physicochemical characteristics (relative density, optical rota-tion, refractive index, and solubility in 90% ethanol,Table 9)of thedill oil were analyzed at 20 C using standard method presented in

Pharmacopoeia Jugoslavica IV (1984).

3. Results and discussion

3.1. The influence of the hydrodistillation hydromodule on the dill

oil yield

The influence of the hydrodistillation hydromodule on the dillseeds oil yield is shown in Table 2. The yield of the essential oil

increasedwith thehydromodule increase,reached a maximum andthen decreased. The highest oil yields of 2.80 ml per 100 g of dryplant material (70.0% of the initial seed content of the oil) wereobtained by the application of the 1: 20 (w/v) hydromodule for

the duration of 180 min. This optimal hydromodule was used insubsequent experiments.

Table 2

The influence of the hydromodule on the yield of the essential oil.

Hydromodule (w/v) Yield of essential oil

ml/100g dry plant material %a

1:10 2.12 53.0

1:15 2.41 60.25

1:20 2.80 70.0

1:25 2.73 68.25

a The initial essential oil yield from dill seeds.

The oil yield increase with the increasing hydromodule is mostlikely a consequence the reduced mass transfer resistance andan ameliorated water-seeds contact, which makes the volatiles

readily available for hydrodistillation. A slight oil yield reduc-tion in the 1:25 (w/v) hydromodule can be probably explained by

solubilization and/or by chemical transformation involving water

molecules of some constituents due to larger quantities of waterpresent during the distillation (Milojevic et al., 2008).

3.2. The influence of the hydrodistillation technique on the yield

of dill volatiles

Fig. 1shows the influence of the hydrodistillation time on the

essential oilyieldin a seriesof fivedistillationat differenthydrodis-tillation techniques(techniquesIIV) and average oil yieldfrom five

hydrodistillation run.Maximal essential oil yield of 2.8 ml/100g dry plant material

(70% in regard to the initial oil content) obtained by technique Iwas achieved after 180 min (Fig. 1a).

In five consecutive hydrodistillation runs by techniques II(Fig. 1b), III(Fig. 1c) and IV (Fig. 1d) the oil yield increased with theincreased number of hydrodistillation runs. In the sixth hydrodis-tillation run themaximum oil yield is nearlythe same as in the fifth

hydrodistillation.Maximal essential oil yield of 2.59 ml/100g dry plant material

(64.75% in regard to the initial oil content) obtained by techniqueII was achieved after 120min in the fifth hydrodistillation run

(Fig. 1b). The yield of oil is lower by 7.5% than the yield achieved bytechnique I. In the case of Clevenger hydrodistillation (techniqueI), the condensate water returns to the process maintaining theoptimal hydromodule (1:20 w/v) approximately constant, while in

the technique II, the liquid phase in a distillation flask is reducedover time. In accordance with the results of hydromodule influ-ence on oil yield investigations, decrease of hydromodule belowoptimal (1:20 w/v) during hydrodistillation, leads to the reduc-

tion of expected maximal oil yield, for hydromodule 1:20 w/v, tothe one corresponding to hydromodule 1:12 m/v (approximately110ml of water, which is about 36% of liquid phase, was elim-inated during the hydrodistillation process). In addition, a part

of oil soluble components (hydrophilic component) and a part ofoil droplets which are finely emulsified (water-insoluble) in the

Fig. 1. Effect of the hydrodistillation time on the oil yield in a series of five distillation (a technique I, b technique II, c technique III, d technique IV).


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Table 3

The influence of the hydrodistillation methodology on the essential oil yield.

Hydrodistillation technique ml/100 g dry plant material %a

Yield of essential oil after

the fifth hydrodistillation

Average yield of essential oil

from five hydrodistillation

Yield of essential oil after

the fifth hydrodistillation

Average yield of essential oil

from five hydrodistillation

Technique I 2.80 2.80 70.0 70.0

Technique II 2.59 2.32 64.75 58.0

Technique III 3.74 3.37 93.5 84.25

Technique IV 2.73 2.47 68.25 61.75

d.p.m. dry plant material.a The initial essential oil yield (in %) from dill seeds.

condensate water were returned to the next hydrodistillation, so

the oil yield increased in a series of five hydrodistillations. Accord-ing toFig. 1b, this was happening up to the fifth hydrodistillation,after which there was probably the highest amount of dissolvedhydrophilic and emulsified hydrophobic components of oil in the

condensate water. A hydromodule decrease during hydrodistilla-tion hada decisive impacton the significant reduction of maximumoil yield obtained by this hydrodistillation methodology.

The maximal yield of 3.74ml of the essential oil per 100g of

seeds (93.5% in regard to the initial oil content) obtained by tech-

nique III was achieved after 180 min in the fifth hydrodistillationrun, for constant, optimal hydromodule of 1:20 w/v (Fig. 1c). About70.5% of the initial content of oil from the dill seeds was achieved

in the first hydrodistillation run by technique III. The oil yieldincreased with the increasing number of hydrodistillation runs.This is probably the consequence of the use of water from thestill flask in the subsequent distillations of a new batch of seeds

(Stanojevic et al., 2011). The oil yields achieved after the fifthhydrodistillation runwas higherby 25.13 and30.75%of theoil yieldachieved by technique I and II, respectively.

The maximal essential oil yield of 2.73 ml/100g dry plant

material (68.25% in regard to the initial oil content) obtained bytechnique IV was achieved after 120 min in the fifth hydrodistilla-tion run, for constant, optimal hydromodule of 1:20 w/v (Fig. 1d).

For obtaining essential oil by technique IV the condensate andresidue still water from previous distillation were combined andmade up with fresh water to 300 ml for the distillation of a newbatch of dill seeds. The condensate water was removed from thehydrodistillation process while reducing the hydromodule of the

initial, optimal 1:20 w/v to 1:12 w/v. Decrease of hydromoduleduring hydrodistillation had a decisive impact on the reductionof maximum essential oil yield obtained by this hydrodistilla-tion technique, as we have seen in the case of technique II.

According to the results presented in Table 3, it can be con-cluded that the oil yield depends on the used hydrodistillationtechnique.

The highest amount of the oil was obtained by technique III for

180 min of hydrodistillation. The difference in the oil yield is the

result of using the residual still water from previous distillationsin the subsequent distillation of fresh batch of seeds. The oil yieldobtained by hydrodistillation technique IV is higher than the yield

obtained by technique II and less than the yield obtained by thetechniqueIII.The highest yieldof essentialoil wasexpectedby tech-nique IV,compared to yieldsachieved by techniquesI, II and III,justusing the condensate water and residue still water from the previ-

ousdistillation forimmersing plant material in thenext distillation.However, the reduction of the essential oil maximum yield due tothe decrease of hydromodule during the process, from 1:20 w/v to1:12 w/v, because of the singling out of condensate water from the

process of hydrodistillation, is considerably higher compared to itsincrease due to use of the condensate and residue still water fromthe previous distillation for immersing plant material in further

distillations.

3.3. Hydrodistillation kinetics

Two hydrodistillation kinetics models were applied in the

case of essential oil from dill seeds: the model of Ponomarev(Ponomarev,1976) (Model A) and a non-stationary diffusionmodel(VeljkovicandMilenovic,2002;Milojevicetal.,2008) (ModelB).Forthe fourmethodologies utilized, in five consecutiveruns, Fig.2(ad)

andFig. 3(ad) show the kinetics of the oil hydrodistillation fromdill seeds and the average oil yields of the corresponding hydrodis-tillations, by kinetics models A and B, respectively.

The models used to described the kinetics of essential oilhydrodistillation from dill seeds were based on a mechanism sim-ilar to the one which relates to the extractive matters extractionfrom plant material (Veljkovic and Milenovic, 2002; Milojevicet al., 2008).

The hydrodistillation curves show that there are two distinctperiods of hydrodistillation (Fig. 2). The volatiles distilled fromthe surface of the seed cells in the initial phase (the fast oilhydrodistillation). In the second phase, a much less rapid oil

hydrodistillation period, a slow molecular diffusion of the essen-tial oil constituents from intracellular compartments occurred. Thecoefficientb, characterizes the fast hydrodistillation period (linearpart of the hydrodistillation curve), while the coefficient k char-

acterizes the slow hydrodistillation period (Eq. (3)). The highest

hydrodistillation level of oil (93.5% in regard to the initial contentof essential oilin plant material) wasobtainedby techniqueIII, after180 min in the fifth hydrodistillation run (Fig. 2).

The non-stationary diffusion model of dill oil hydrodistillationwas shown inFig. 3.This model was also described by Milojevicet al. (2008)for modelling oil hydrodistillation from juniper.

The coefficientsb and k, thetime ofthe fast periodof hydrodistil-

lation (FHT, min) and hydrodistillation levels (HL = 100(q0 qi)/q0)for the essential oil were presented inTables 47.

In the first period (fast hydrodistillation), 61.1% (technique I),57.5% (technique II), 83.1% technique III) and 58.8% (technique IV)

of the oil constituents evaporated with water steam from the outersurface of seed cells (Tables 47).First period is characterized by arapid increase of essential oil. A slow increase of oil yield occurred

in the second, slow period of hydrodistillation.Modelling of the kinetics of essential oil hydrodistillation from

dill seeds was in accordance with hydrodistillation kinetics of oilfrom lavender flowers (Stanojevic et al., 2011), juniper berries(Milojevic et al., 2008) and laurel leaves (Stanisavljevic et al.,

2010).The coefficient k values in kinetics equations of hydrodistilla-

tion in a model of non-stationary diffusion are higher than thoseof coefficientk in Ponomarev kinetics hydrodistillation equations

(Tables 47).Based on the results shown in the mentioned tables,it can be concluded that coefficients b in kinetics equations ofessential oils hydrodistillation, by Ponomarev and non-stationarydiffusion model, are slightly different. The results presented in

Tables 47show that both kinetics models can be used for mod-

elling of essential oil hydrodistillation from dill seeds.


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Fig. 2. Hydrodistillation kinetics of dill seeds essential oils (Model A) in five consecutive hydrodistillation runs by four hydrodistillation techniques (a technique I, b

technique II, c technique III, d technique IV).

Fig. 3. Hydrodistillation kinetics of dill seeds essential oils (Model B) in five consecutive hydrodistillation runs by four hydrodistillation techniques (a technique I, b

technique II, c technique III, d technique IV).


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Table 4

The time of the fast hydrodistillation stage (FHT), the level of hydrodistillation (HL) and the values ofbandkcoefficients from the kinetic equations (technique I).

Hydrodistillation run FHT, min HL, % Model A Model B

b k104, min1 b k103, min1

I-1 45 62.0 0.607 5.74 0.603 1.72

I-2 45 62.0 0.613 5.84 0.610 1.76

I-3 45 62.9 0.615 5.75 0.611 1.77

I-4 45 61.1 0.597 5.74 0.594 1.67

I-5 45 61.1 0.600 5.52 0.597 1.61

Average value 45 61.9 0.607 5.70 0.603 1.70

Table 5

The time of the fast hydrodistillation stage (FHT), the level of hydrodistillation (HL) and the values ofbandkcoefficients from the kinetic equations (technique II).



II-1 30 41.4 0.383 1.11 0.377 2.08II-2 30 45.0 0.432 0.78 0.430 1.53

II-3 30 53.9 0.528 0.58 0.527 1.36

II-4 30 54.7 0.514 1.03 0.508 2.53

II-5 30 57.5 0.558 0.77 0.555 2.0

Average value 30 50.5 0.483 0.86 0.48 1.89

Table 6

The time of the fast hydrodistillation stage (FHT), the level of hydrodistillation (HL) and the values ofbandkcoefficients from the kinetic equations (technique III).



III-1 45 62.0 0.613 5.84 0.610 1.76

III-2 60 66.5 0.678 6.04 0.672 2.85

III-3 45 75.5 0.719 9.52 0.688 5.49

III-4 45 81.8 0.801 7.12 0.778 5.81

III-5 45 83.1 0.806 7.81 0.770 7.34

Average value 45 73.8 0.72 7.56 0.705 3.77

Table 7

The time of the fast hydrodistillation stage (FHT), the level of hydrodistillation (HL) and the values ofbandkcoefficients from the kinetic equations (technique IV).


b k104

, min1

b k103

, min1

IV-1 30 42.3 0.394 1.05 0.389 2.0

IV-2 30 45.0 0.410 1.57 0.396 3.35

IV-3 30 50.4 0.473 1.32 0.463 3.10

IV-4 30 55.7 0.521 1.20 0.512 3.10

IV-5 30 58.8 0.548 1.11 0.538 3.04

Average value 30 50.2 0.468 1.27 0.458 2.91

3.4. Influence of the hydrodistillation techniques on dill oil

composition

Detailed GC/MS analyses enabled the identification of 29components of dill seed essential oil(Table 8). Although alloils con-tained the same 29 constituents, the quantitative composition ofthe essential oilsdepended on the used hydrodistillationtechnique.

GCMS analyses of the essential oils revealed that carvonewas the most abundant component of all investigated oils (85.9,88.8, 89 and 89.3% in the oils obtained by hydrodistillation tech-nique I, II, III and IV, respectively), independent of the applied

hydrodistillation techniques. The content of carvone in the essen-tial oil from dill seeds from various regions was different: 50.1%,from Bulgaria (Jirovetz et al., 2003), 55.2% from India (Singhet al., 2005),75.21% from Romania, 49.5% from Canada (Delaquis

et al., 2002). Alongside carvone, limonene, cis-dihydrocarvone,

trans-dihydrocarvone, cis-carveol and trans-carveol, all other dillseeds oil components were identified in much lower concentra-tions.The content ofcis-dihydrocarvone, trans-dihydrocarvone and

cis-carveol was slightly different in all obtained oils. The contentof limonene was 5.1%, 2.1%, 0.9% and 1.4% in the oils obtained

by hydrodistillation techniques I, II, III and IV, respectively. Otherinvestigators reported a higher content of limonene in dill seeds oil(2050%) (de Carvalho and da Fonseca, 2006; Jirovetz et al., 2003;

Delaquis et al., 2002; Singh et al., 2005) than theonein the dill seedsfrom Serbia. These changes of carvone and limonene content in theessential oil, and changes in the compositions of the oil are proba-blydue to differingenvironmental conditionsand thedifferences in

thegenetic makeup of theutilized seeds (Ghassemi-Golezani et al.,2008; Callan et al., 2007; Faber et al., 1997; Stanojevic et al., 2011).

Especially important is the significantly higher content of car-vone (85.989.3%), a bioactivecomponent with an arrayof different

biological activities (de Carvalho and da Fonseca, 2006; Bailer et al.,2001; Bakkali et al., 2008; Faberet al., 1997). The majorcomponentsare believed to be mainly responsible for the biological activity ofthis particular essential oil (Bakkali et al., 2008;Bailer et al., 2001).

The usage of carvone as a reversible suppressant of sprouting instoredpotatoes orflowerbulbs is probably itsmost importanttech-nical application (Bailer et al., 2001).Based on the results obtainedin ourinvestigation, the essential oilfrom dill seeds from Southeast

Serbia (Svrljig) could be a potential natural sourcefor the industrialproduction of carvone.


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Table 8

The identified constituents of the dill seeds essential oil from four different hydrodistillation methodologies (IIV).

Rt/min RIa Component Hydrodistillation technique IDc

I II III IV

Content, %

5.821 1020 p-Cymene trb tr tr tr a,b,c

5.923 1024 Limonene 5.1 2.1 0.9 1.4 a,b,c

5.923 1025 -Phellandrene tr tr tr tr a,b,c

7.243 1089 p-Cymenene tr tr tr tr a,b7.399 1095 Linalool tr tr 0.2 0.1 a,b,c

7.997 1119 trans-p-Mentha-2,8-dien-1-ol tr tr tr tr a,b

8.263 1132 cis-Limonene oxide tr tr tr tr a,b

8.351 1133 cis-p-Mentha-2,8-dien-1-ol tr tr tr tr a,b

8.361 1137 trans-Limonene oxide tr tr tr tr a,b9.616 1184 Dill ether tr tr tr tr a,b

9.826 1186 -Terpineol tr tr tr tr a,b,c

9.897 1191 cis-Dihydro carvone 3.0 2.6 2.8 2.7 a,b

9.923 1192 Dihydro carveol tr tr tr tr a,b

9.923 1193 neo-Dihydro carveol tr tr tr tr a,b

10.072 1200 trans-Dihydro carvone 2.7 2.5 2.7 2.7 a,b

10.383 1212 iso-Dihydro carveol tr tr tr tr a,b

10.409 1215 trans-Carveol 1.4 1.5 1.6 1.4 a,b

10.736 1226 neoiso-Dihydro carveol tr tr tr tr a,b

10.761 1226 cis-Carveol 1.8 2.3 2.4 2.0 a,b,c

11.134 1239 Carvone 85.9 88.8 89.0 89.3 a,b,c

11.346 1247 p-Anis aldehyde tr tr tr tr a,b,c11.704 1266 Isopiperitenone tr tr tr tr a,b

11.865 1273 trans-Carvone oxide tr tr tr 0.1 a,b

12.127 1282 trans-Anethole tr tr 0.3 0.2 a,b,c

12.183 1289 Thymol tr tr tr tr a,b,c

13.938 1356 cis-Carvyl acetate tr tr tr tr a,b,c

17.967 1517 Myristicin tr tr tr tr a,b,c

20.252 1620 Dill apiole tr tr tr tr a,b

23.087 1722 Neocnidilide (syn. Sedanolide) tr tr tr tr a,b

Total identified: 99.9 99.8 99.9 99.9

a RI= Retention index.b tr = trace amount (


8/8


from dill seeds with maximal yield and high carvone content could

be devised. The results also suggest that the dill seeds essentialoil from Southeast Serbia could be regarded as a potential naturalsource of bioactive carvone.

Acknowledgement

This work was supported under the Project on Development of

Technologynumber TR-34012 by the Ministry of Education,Scienceand Technological Development of the Republic of Serbia.

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