Chemical Compositions of Essential Oil and Crude Oil of Some Fruits belonging to Umbelliferae Family cultivated in Konya Ecological Conditions

Apiaceae, also called Umbelliferae, the parsley family, in the order Apiales, comprising around 300 and 400 genera of plants distributed throughout a wide variety of habitats, principally in the north temperate regions of the world. Most members of Umbelliferae family are aromatic herbs. Species used as herbs and spices include fennel (Foeniculum vulgare), anise (Pimpinella anisum), dill (Anethum graveolens), coriander (Coriandrum sativum), and cumin (Cuminum cyminum). In this study, essential oil and crude oil components were determined in the seeds of dill, fennel, aniseed, cumin and coriander. The yield and components of essential oil and crude oil, main active compounds in the fruit of the plants of dill, fennel, anise, cumin and coriander grown in the ecological conditions of Konya were examined. According to the results, essential oil and crude oil yields were 3.5 % and 5.06 % in dill, 2.25 % and 22.07 % in anise, 2.70 % and 7.34 % in fennel, 1.90 % and 11.26 % in cumin, 0.95 % and 18.48 % in coriander. The main components of dill, fennel, anise, cumin and coriander seed essential oils were carvone (45.221 %), trans-anethole (86.898 %), (Z-)-Anethole (92.478 %), cumin aldehyde (42.900 %) and linalool (87.238 %) respectively. In crude oils, the main component was determined as C18:1 (oleic acid). Research Article Article History Received : 10.12.2019 Accepted : 07.05.2020


INTRODUCTION
Turkey has a rich biodiversity in terms of medicinal and aromatic species due to its different climatic conditions and favourable geographical structure (Hajyzadeh et al., 2017). Medicinal plants in the world and in our country find an increasing range of use especially in the pharmaceutical and food industries, cosmetics, paints, decorative and feed industry. They are consumed as spice in the food industry at the most. Thyme (Thymus vulgaris), rose (Rosa damascena), poppy (Papaver somniferum), aniseed (Pimpinella anisum), fenugreek (Trigonella foenum-graecum), pepper mint (Mentha piperita), black cumin (Nigella sativa) and similar species have a place in cultured medicinal and aromatic plants. In recent years, the demand has increased rapidly both in the foreign and domestic markets as a result of the use of medicinal and aromatic herbal products.
The main factors determining the importance of medicinal and aromatic plants are the active ingredients. These active ingredients in the plants, especially essential and fixed oils, depend on such many factors as primarily the genetic structure of the plant, climate, environmental factors, cultural treatments, the region of growth of the plant, different parts of the plant (morphogenetic variability) (Singh and Randhawa, 1991), development periods of the plant (ontogenetic variability) (Özel, 2000) and temperature changes during the day (diurnal variability) (Kaçar and Özkan, 2005;Uyanık, 2013). It is important to know the amount and distribution of active ingredient in essential oil plants and the plants belonging to the Umbelliferae family, whose herbs and seed are evaluated separately in particular (Ayhan and Özel, 2017).
Both herbs and frit of the plants of dill, fennel, aniseed, cumin and coriander belonging to the Umbelliferae family are used in salads, soups and sauces as spices and vegetables. In addition, all of these plants are commonly used in medicine, alternative medicine and the public especially in the digestive system, common cold and cough.
Konya is one of the provinces with the least annual precipitation in our country. Due to the very hot and dry summers, irrigation problems are often encountered. This increases secondary metabolite production against stress conditions in medicinal and aromatic plants. For this reason, it was aimed to carry out this study in fruits of dill, fennel, anise, cumin and coriander consumed among the people. In this study, essential oil and crude oil yields and chemical compositions of dill, fennel, anise, cumin and coriander plants grown in Konya ecological conditions were investigated.

Plant Materials
The fruits used in the trial, were dill (Anethum graveolens), fennel (Foeniculum vulgare), anise (Pimpinella anisum), cumin (Cuminum cyminum), coriander (Coriandrum sativum). This study was conducted to essential oil yield, crude oil yield and components of the fruits cultivated, Selçuk University, Faculty of Agriculture, Medical Plants Research and Application Experimental Area in Konya ecological conditions. Field trial was carried out in 2018. All the fruits used were populations. Dill, fennel, anise, cumin and coriander fruis were directly planted in the experimental area by hands in the first week of March (05 March). The growing period of plants were reached 150 days. Trial was set up in three repetitions according to the randomized parcels experimental design. In order to determine the soil properties of the trial area on which the experiment was conducted, the physical and chemical analyzes of the soil sample taken from 0-20 cm depth were carried out in Selçuk University, Faculty of Agriculture, Department of Soil Laboratory. Soil analysis was given in Table 1.  Essential Oil Distillation and Analysis The fruits were milled with a grinder (Foss Kniftec 1095, Denmark) to analyse essential oil distillation. Then whole ground fruits (100 g) subjected to hydrodistillation for 3 h using Clevenger type apparatus to produce essential oil. Essential oil is calculated as volume (ml / 100 g). GC-MS instrument was used to determine the essential oil components. The essential oils were stored at -20 0 C until analyzed. GC-MS analysis was performed on a Agilent 6890N Network GC system combined with Agilent 5975 C VL MSD Network Mass Selective Detector. The GC conditions were; column, DB Waxe tr; 60.0m x 0.25mm x 0.25µm; oven temperature programme: The column held initially at 60 0 C for 10 min after injection, then increased to 220 0 C with 4 0 C min -1 heating ramp for 10 min and increased to 240 0 C with 10 0 C min -1 heating ramp without hold; inject or temperature 250 0 C; carrier gas; He; inlet pressure, 9.60 psi; linear gas velocity, 7 cm sec -1 ; initial flow 0.3 ml min -1 ; split ratio,65.0:1; injected volume 1.0 µl. Computer matching against commercial libraries (Wiley GC-MS Library, Adams Library, MassFinder 3 Library) as well as MS literature data was used for the identification of essential oil components(European Pharmacopoeia 7.0).

Isolation and Derivatization of The Fruit Crude Oils
The fruits of dill, fennel, anise, cumin and coriander were independently subjected to continuous extraction technique with diethyl ether for 8 h using Soxhlet apparatus. The organic phases were evaporated in vacuo until dryness to give the crude oils. Prior to GC-MS analysis, trans-methyl derivatives of the crude oils were prepared. Fatty acid profiles were determined as fatty acid methyl esters (FAMEs) and the FAMEs were dissolved in n-hexane for injection and analyzed by GC-MS (European Pharmacopoeia 7.0).

Fruit Crude Oil Analysis by GC-MS
GC-MS analysis was performed on a Agilent 6890N Network GC system combined with Agilent 5975 C VL MSD Network Mass Selective Detector. Determination of the components in the fruit fatty oils of dill, fennel, anise, cumin and coriander were performed by comparison of their mass spectra with Wiley, Famed-23 and Nist GC-MS Libraries and retention indices (RI), relative to n-alkanes as well as corresponding data from relevant literature. The percentages of the components were calculated from the GC peak areas using the normalization method.

Yields of Essential Oil and Crude Oil of the Fruits (%)
Essential oil yields (%) of dill, fennel, aniseed, cumin and coriander fruits were determined in the clevenger apparatus and crude oil yields (%) were determined in the soxhlet apparatus. Accordingly, the essential oil and crude oil yields of the fruits were given in Table  3. Table 3. Essential oil (%) and crude oil (%) yields of some plant fruits belonging to Umbelliferae family Çizelge 3. Umbelliferae familyasına ait bazı bitkilerin meyvelerine ait uçucu yağ ve sabit yağ miktarları (%) The essential oil yields of dill, fennel, aniseed, cumin and coriander fruits were determined as 3.15%, 2.70%, 2.25%, 1.90% and 0.95% respectively. Şanlı et al. (2012), essential oil yields in the fruits of dill, fennel, aniseed, cumin and coriander grown in the ecological conditions of Burdur were respectively determined as 3.02%, 2.74%, 2.68%, 1.82% and 0.32%. In another study reported that average essential oil rates were determined as 3.18% in dill fruit, 2.49% in fennel fruit, 3.33% in aniseed fruit, 1.77% in cumin fruit and 0.42% in coriander fruit in Isparta ecological conditions (Keskin and Baydar, 2016). According to the studies investigated with dill fruits, Charles et al. (1995)  Crude oil yields determined in the fruits were given in Table 3. The crudel oil yields of dill, fennel, aniseed, cumin and coriander fruits were respectively determined as 5.06%, 7.3422.07%, 11.26% and 18.48%. The crude oil yields of coriander genotypes were determined as 18.64%-22.53% (Gökduman and Telci, 2018). In another research, it was reported that coriander's crude oil was 13%-21%, cumin's crude oil was 10%-15% and aniseed's crude oil was 30% (Gruenwald et al., 2004). The results were consistent with other results.
The results of the study revealed that the essential oil and crude oil ratios were in parallel with the other studies.

Essential Oil Compositions of the Fruits
The essential oil components of the dill fruit were given in Table 4. The essential oil components of dill, fennel, aniseed, cumin and coriander determined in the GC-MS. Wiley, Nist-Spectral and Volatile libraries were used to determine components in the GC-MS. , transdihydrocarvone (9.373%), anethole (3.716 %), dillapiole (1.681 %) and dillether (0.107 %). The number of totally determined components was 25 and the total amount was 100 %. Aside from these components, para-anisaldehyde (0.019 %), cisdihydrocarvone (1.598 %), α-phellandrene (0.342 %) were determined. Main components (carvone, limonene, trans-dihydrocarvone, anethole, dillapiole and dillether) constitute 96.007% of the amount of all the components. Carvone was found to be the main component of the fruit essential oil when the studies conducted with dill were examined. Şanlı et al. (2012) found the essential component of the fruit essential oil as D-Carvone (71.80%) and α-fenchene (11.85%) and limonene (9.75%) were other components. In other studies, the rate of carvone was determined as 18.18-81.15% (Charles et al., 1995) (Keskin and Baydar, 2016). Orhan et al. (2013) found that the main component of the dill herb's essential oil is αphellandrene (47.748% in organic dill and 27.940% in culture dill). In our study, the main component was determined as carvone. It was in parallel with other studies. However, the reason for the fact that its quantity was slightly lower than others could be explained as climate, environmental conditions and applied agricultural techniques. It was thought to be effective that it the ecological conditions of Konya was more arid.

Crude Oil Components of the Fruits
Fatty acid methyl esters of the fruit of dill, fennel, aniseed, cumin and coriander were determined in the GC-MS. Wiley, Nist-Spectral and Famed 23 libraries were used to determine the components in the GC-MS. Fatty acid components of dill, fennel, aniseed, cumin and coriander were given in Table 9.
The main fatty acid component of dill, fennel, aniseed, cumin and coriander was oleic acid (6Z-octadecanoic acid-petroselinic acid-C18:1). The highest amount of oleic acid was determined in the dill fruit (%88.296), while the lowest amount of oleic acid was determined in the cumin fruit (66.593%). The amount of oleic acid in fennel, coriander and aniseed was 84.356%, 79.651% and 70.818% respectively. The other major fatty acid component was identified as linoleic acid (C18:2). The highest amount of linoleic acid was 26.464% in the cumin fruit and the lowest was 6.625% in the dill fruit. As seen, the amounts of oleic acid and linoleic acid were inversely proportional. Other determined unsaturated fatty acids are palmitoleic acid (C16:1), linolenic acid (C18:3) and gadoleic (9-eicosenic acid-C20:1) acid. Palmitic acid (C16:0) and arachidic acid (C20:0) were determined as saturated fatty acids. The highest amount of palmitic acid was determined in coriander (5.057%) and the lowest amount was determined in cumin (4.338%). Arachidic acid was found only in coriander (0.954%) and cumin (2.017%). The crude oils of some species belonging to the Umbelliferae family such as parsley, fennel, dill, aniseed, cumin, coriander, are very rich (55-90%) in petroselinic acid (C18:1, cis 6), which is not found in the oil of other plants, and can be used both as food and industrial oil. In a study conducted in the conditions of Isparta, the main fatty acid component of aniseed, dill, fennel, cumin and coriander was determined as petroselinic acid (55.44%-87.28%) (Keskin and Baydar, 2016). In our study, the main fatty acid component was also determined as petroselinic acid.