Physicochemical Analysis Using Gas Chromatogrphy Mass Spectrophotometer (GCMS) on the Quality of Citronella Oil (Cymbopogon nardus L.)

Indonesia is known as a country that has biological forests which can be used as a source of essential oils. The levels of chemical compounds that make up citronella oil are not fixed and depend on several factors such as distillation. Distillation using traditional methods is a production process that has been identical for generations used by farmers, usually this distillation uses wood fuel and takes 5 hours. Meanwhile, distillation with electrical energy only takes 4-5 hours. This research was conducted at the Laboratory of Chemical Analysis, Faculty of Mathematics and Natural Sciences, Syiah Kuala University, Banda Aceh. This research was conducted from January 2023 to June 2023. The results showed that distillation using the traditional method had 15 chemical compounds and consisted of 3 active ingredients, namely citronellal (42.48%), geraniol (17.60%) and citronellol ( 13.67%) while the results of the distillation by the electric method have 21 compounds and also consist of 3 active ingredient components, namely citronellal (40.87%), geraniol (16.53%) and citronellol (17.68%).


Introduction
Indonesia is known as a country that has biological forests which can be used as a source of essential oils.Essential oil is one of the commodities generating foreign exchange.Therefore, in recent years, essential oilshave received considerable attention from the Indonesian government.Currently, Indonesia can produce nine types of essential oils, namely: clove oil, ylang oil, patchouli oil, fragrant root oil, nutmeg oil, eucalyptus oil, cinnamon oil and citronella oil.There are six types of essential oils that are most prominent in Indonesia,namely: nutmeg oil, patchouli oil, eucalyptus oil, ylang ylang oil, clove oil and citronella oil [1].Increasing production of citronella essensial oil this can be seen from the many modern products that have been circulating, such as cosmetics and aromatherapy, which are produced from this oil.The components or content of citronella essential oil are quite complex,but the most important components are citronellal, citronellol and geraniol.These three components determine the intensity of the fragrance as well as the value and price of citronella oil.The levels of chemical compounds that make up citronella oil are not fixed and depend on several factors such as proper harvesting age, sufficientwithering, normal steam pressure and clean distillers [2].However, apart from these problems, it turns out that the distillation method also affects the quality of the oil produced.From the results of a survey in the distillation field with traditional methods it takes longer to run than electricity, this is of course the physicochemistry of citronella essential oil is also predicted to be 1297 (2024) 012011 IOP Publishing doi:10.1088/1755-1315/1297/1/012011 2 different.Distillation using traditional methods is a production process that has been identical for generations used by farmers.Usually this distillation uses wood fuel with a time of 5 hours, while distillation with electrical energy only takes 4-5 hours and during the refining process, try not to have any obstacles so that the citronella oil produced has maximum quality [3].From this problem the authors are very interested in conducting research on the effect of the traditional distillation method and the electric method on the quality of citronella essential oil which later becomes a referencebased on SNI 06-3953-1995 as shown in Table 1.To determine the quality of citronella essential oil produced from the two distillation methods, accurate technologyis needed and of course it can analyze the component of the citronella essential oil.GCMS is a reliable, simultaneous and predictable method multiple parameters simultaneously.According to the results of previous studies, it was stated that GCMS is atool that is very accurate in determining the quality of samples that have been subjected analysis [4].

Materials and methods
The Materials used _ in this research is the Mahapengiri type from distillation or the latest production, filter paper and duct tape.The tools used in this study were GCMS with Gas Chromatography and Mass types Spectromete, distillers, test tubes, refractometers,thermometers, pycnometers, pipettes, 10 and 100 ml measuring cups, and analytical balances.This research was conducted in January-June 2023 at the Chemical Analysis Laboratory, Faculty of Mathematics and Natural Sciences, Syiah Kuala University, Banda Aceh.
A B Figure 1.Distillation process using traditional (A) and Electric (B) methods

Sample Preparation and Preparation
The sample used was citronella (Cymbopogun nardus L.) which was harvested from Rerebe Village, Tripe Jaya District, Gayo Lues Regency.Before the distillation process is carried out, the harvest is the initial stage which is carried out at theage of 4 months and is not the first harvest after planting, before the fragrant citronella is distilled, of course the fragrant citronella is first dried, the purpose of this drying is to reduce the water content in the material because in this process evaporation of waterwill occur, the release of water from the material results in the rupture of the oil cells making it easier to extract oil during the refining process.Next is the distillation stage, this is the final stage for obtaining citronella essential oil, where the oil sample consists of two distillation methods, namely traditional and electric distillation results, the more precise the distillationprocess, the better the quality produced.

Acquisition of GCMS
GCMS consists of Gas Chromatography and Mass Spectrometer using a capillary column which depends on the dimensions of the column (length, diameter or thickness).Essential oil dripped as much as 1 drop on a piece of filter paperand allowed to stand.Then it was injected into the GCMS which was operatedusing a glass column 25 mm long, 0.25 mmin diameter and 0.25 µm thick with the stationary phase CP-Sil 5CB with the oven temperature programmed between 70-271ºC/minute with a temperature rise rate of 10ºC/minute, gas Helium carrier pressure of 12kPa, total rate of 30 ml/minand Split ratio of 1: 50 [5].

Data analysis
The data obtained from this study will be in the form of a chromatogram with peaks , retention time (tR) and peak areas which are then calculated to validate the method and concentration of citronella essential oil compounds.The concentrationof the chemical compound obtained by means of the peak area of the specimen is plotted in the standard linear regressionequation.The linear test was carried out by making a linear regression equation based on concentration and area.The data was then tested using simple linear regression statistics using IBM SPSS statistics 20 software.

GC-MS Chromatrogram Analysis Results Figure 3 and 4
Figures 3 and 4 show that the most chemical compounds in citronella essential oil are presentat the highest peak.There are 3 most important active components in citronella essential oil, namely citronella, geranioland citronella both from traditional and electric distillations.The results of research using the traditional distillation method showed a citronellal content of 42.48% at a retention time of 13,921 minutes, a geraniol content of 17.60% at a retention time of 16,768 minutes and a citronellol content of 13.67% with a retention time of 16,033 minutes.While the distillation using the electric method the content of citronella, geraniol and citronellol produced was lower than traditional distillation, namely the citronellal content of 40.87% at a retention time of 13,952 minutes, a geraniol content of 16.53% at a retention time of 16,775 minutes and a citronellol content of 17.68% at retention time of 16,050 minutes.From the GCMS results, compounds that have a low boiling point will come out first to the detector, this is because the low boilingpoint causes the compound to evaporate more 4 Samples of Fragrant Citronella Essential Oil Results of Distillation with Traditional Methods easily, so the retention time is faster.Each chemical compound has a different boiling point which causes different peaks on the spectrum.This research is supported by previous research which stated that the difference in retention time of the physicochemical compounds of citronella essential oil could be caused by the interaction process of the compound with the stationary phase, in this case the column used in this study is non-polar so that polar compounds will come out.first and those that are nonpolar will be retained longer in the column.The greater the percentage of a component in a sample, the greater the percentage of a component in the sample, the higher the resulting peak will be [6].   2 and 3   .The two types of terpenoids have differences in the resulting boiling points so that the peak, retention, % area are also not the same.The types of chemical compounds detected in citronella essential oil are needed in the raw material, pharmaceutical, perfume and food industries.This research is also supported by previous studies which stated that the GCMS physicochemical analysis of citronella essential oil samples had the highest peaks in the content of citronella, geraniol and citronellol where these compounds greatly determine the selling price of the product [7].

Components of citronella oil analyzed using traditional and electrical methods in table
Citronella compounds are the highest compounds in essential oils produced from traditional and electric distillation, where these compounds are included in the monoterpene compounds which have a distinctive aroma and are able to inhibit bacterial activity including P. aces and Sreptococcus mutans.According to the results of previous research on the concentration of citronella essential oil application on the diameter of the inhibition zone of P. aces bacteria with the lowest concentration of 10% and 11.7 mm inhibition which has a strong interpretation, thus it can be concluded that the small concentration of compounds from citronella essential oil proven to inhibit the growth of P. aces, Streptococcus mutans [8].In the GCMS results it can also be seen that the chemical components detected are different from the amount of compounds produced.In the traditional citronella distillation analysis data, there are 15 peaks or compounds produced, while the distillation results using the electric method are able to produce 21 compounds contained in the oil.It is suspected that the traditional distillation process takes longer than electricity so that the physicochemical compounds of the essential oils are not all retained and will evaporate at higher temperatures.
In the analysis of distillation data using the electrical method, the number of peaks is 21, which means that there are 21 compounds in the oil.It can also be predicted that the distillation by this electric method has a normal fire temperature so that the physico-chemistry of the oil does not burn or evaporate much.This was corroborated by previous research which stated that the components of citronella essential oil that undergo polymerization are non-oxygenated hydrocarbon compounds suchas terpenes and sesquiterpenes and usually occur due to heating.Apart from the polymerization process, the increase in total solids is also dissolved in the oil because it is caused by a smallamount of the heavy fraction being distilled in the oil during the refining process [9].

Comparison of the results of the GCMS analysis with the standard export value (SNI) of citronella essential oil
In the table above you can see a comparison of the results of the GCMS analysis between the research results and the data Indonesian standard export.If we look at the results of research on traditional and electric distillation, it can be concluded that the highest levels of citronella from each of the distillation methods are found.In the results of this study the levels of citronellaland citronellol produced from the two distillation methods were in accordance with the provisions of the SNI, namely citronella 35% and citronellol at least 10%.As for the geraniol content, it can be seen that the traditional distillation is 17.60% higher compared to the distillation using electric power with a geraniol content of 16.53%, this occurs because the distillation factor in the traditional way requires longer time to reach its maximum limit.
Besides the process of refining the cultivation factor alsodetermines the physicochemistry of the oil produced.The results of the GCMS analysis of the two distillation methods have not reached the geraniol content in accordance with the SNI requirements where the geraniol content must be above 80-85%.
From this it can be concluded that the geraniol content so far has not complied with the provisions of the SNI, namely the minimum geraniol level 85%.According to the results of previous research that total citronella and geraniol is a form of determining the purity of citronella oil, the more citronellal and geraniol content, the purer the oil is [10].
The effect of distillation time is also able to produce citronella essential oil with maximum levels of citronella and geraniol, therefore too long distillation will not significantly increase the levels of these two substances.The use of high heat temperatures can increase the geraniol content in citronella essential oil, but conversely the levels of citronella in the oil will decrease with the use of higher temperatures [11].This research was also corroborated by previous researchers who stated that harvesting time and distillation time greatlyaffect the quality of citronella oil, especially according to SNI No. 06-3995-1995 because in this case it certainly greatly influences the selling price of the final product [12].The results of the research show that the components of citronella essential oil from both traditional and electric distillation methods for the active compound citronella are in accordance with the minimum standards stipulated in SNI.

Figure 3 .
Figure 3.The citronella oil compound produced from traditional distillation.

Figure 4 .
Figure 4.The resulting citronella oil compound from electricity distillation.

Figure 5 .
Figure 5.Comparison from traditional results distillation, electricity And SNI

Table 2 .
. Components of citronella oil produced using traditional distillation methods

Table 3 .
Components of citronella oil produced using the electric distillation method

Table 2
and 3 show that the dominant compound contained in citronella essential oil as a result of traditional distillationand electrical methods is the terpenoid group.The most abundant terpenoids in oil are monoterpenes with C10 and sesquiterpenes with C15