CHAPTER 1

PRELIMINARY

1.1 Background

Aromatic hydrocarbons policyiklik often called PAHs (polycyclic

aromatic hydrocarbons) Is a class of organic compounds that have two or more

aromatic rings, Usually resulting from incomplete combustion as fossil fuels,

wood, or during the processing of foods such as burning and fumigation.

Polycyclic aromatic hydrocarbons (PAH) or also known as polycyclic organic

matter (POM) is an aromatic molecule consisting of two or more molecules of

aromatic rings are composed by carbon and hydrogen atoms (Scott, 2015).

PAH in this regard include indole, quinoline, and benzothiophene which

has a biological function in living organisms Although the reaction

mechanisms of PAH formation is not known with certainty, experts

estimate that PAH can be formed by free radicals, intra-molecular

adductsor polymerization of small molecules.Polycyclic aromatic hydrocarbons

contained in coal which is a byproduct of coal-heated convection without air.

Aromatic hydrocarbons policyiklik can be analyzed using gas chromatography or

mass spectroscopy called "GC-MS". GC-MS is a separation method using an

organic compound that is a compound of two analytical methods of gas

chromatography (GC) to quantitatively analyze the amount of compounds and

mass spectrometry (MS) to analyze the molecular structure of the analyte

compound. Therefore, the above underlying this paper that contains PAH analysis

using GC-MS (Scott, 2015).

1.2 Formulation of the problem

The formulation of the problem of this paper are:

1. What is the purpose of the polycyclic aromatic hydrocarbon compounds?

2. What is a gas chromatography mass spectroscopy instruments?

3. How does the analysis of polycyclic hydrocarbons aromatrik using Gc-

Ms?

1.3 Purpose

The purpose of this paper is:

1. To find out what is the purpose of the polycyclic aromatic hydrocarbon

compounds.

2. To find out what it is gas chromatography mass spectroscopy instruments

3. To find out How aromatrik polycyclic hydrocarbon analysis using the Gc-

Ms.
 CHAPTER II

DISCUSSION

2.1 Polycyclic Aromatic Hydrocarbons

Polynuclear Aromatic Hydrocarbons (PAH) is one of the main groups of

persistent organic pollutants to the environment. PAHalso known as

polycyclic aromatic hydrocarbons arrives widespread and detected in a variety of

media, including air, water, food, soil, sediment, industrial waste, animal or

human tissue. PAH is composed of two or more benzene rings in a linear array or

cluster, with complex chemicals including carbon and hydrogen.Generally, PAH

exist as a solid yellow-green, white or pale with a distinctive odor. PAH formed

due to a complex mix, resulting from natural or synthesized. Based on the

mechanism of formation, PAHs are divided into two different categories. The

categories are pyrolitic and petrogenic form. Petrogenic PAH is their natural

shape while pyrolitic PAHs originate from incomplete combustion or pyrolysis of

organic materials, crude oil and its products (Arowojolu et al., 2018).

Polycyclic aromatic hydrocarbons and some derivatives are naturally in

nature and can also be formed during incomplete combustion processes

(temperature 500-800 ° C) or when the heating of organic material at a

temperature of 200-300 ° C. Naturally PAH can be in the air, surface water,

ground, coal mining, and the volcanic area. Another source of PAH are non-

smoking. Cigarettes contain tar levels are quite high and burning tar molecules

known to trigger the formation of carcinogenic PAH PAH especially types

(Arowojolu et al., 2018).

 The mechanism of formation of PAH molecules occurs through cracking

reactions of organic material into simple fragments (pyrolysis) and the formation

of aromatic compounds of such fragments (pirosintetik). In addition through the

mechanism of high temperature (200-800 ° C), known PAH molecules can be

formed at a relatively low temperature, about 100-150 ° C, but with a much longer

time than the pyrolysis and pirosintesis. PAH is generally very hydrophobic

nature due to its structure which has many aromatic rings which are nonpolar

(Mauro, 2014).

Naturally with low molecular weight PAHs contained in the atmosphere in

low enough concentrations, whereas high molecular weight PAHs are generally

formed by the roasting process. However, PAH contamination of the environment

occurs only in invertebrate sea creatures such as mussels and oysters that are

unable to metabolize PAHs. While on vertebrate animals, such as cows, chickens,

and fish, PAH molecules in very low concentrations, it can be metabolized further

so as not to contaminate the meat derived from these animals (Mauro, 2014).

Polycyclic aromatic hydrocarbons (PAHs) are included in the EU and the

US Environmental Protection Agency's list of priority pollutants for PAH are the

largest group of compounds that are mutagenic, carcinogenic and teratogenic.

They can also pose a potential threat to the marine environment. The effects of

PAHs are usually extensive and permanent in the environment. Most PAH have

high hydrophobicity, and can be absorbed strongly by organic particles and

inorganic waterborne. Then may eventually be taken to the bottom sediments as

sinks in aquatic systems. PAHs found in sediment bacteria resistant to degradation

in anoxic environments. Even under favorable conditions, PAH absorbed will be

brought to the water as the source of which threaten aquatic ecosystems through

bioaccumulation in the food chain. Therefore,

2.2 Gas Chromatography Mass Spectroscopy (GC-MS)

Gas Chromatography (GC), is a type of chromatography in which the

phase of motion is usually in the form of an inert gas such as helium or un-

reactive gas such as nitrogen, and the stationary phase is a microscopic layer of

liquid or polymer which is inert and solid, in a glass or metal tube called a column

, Capillary column containing a solid stationary phase is coated with a volatile

liquid. Sample flow or berjalanan through a column with a stream of helium gas.

The components in the sample are separated from each other for some time longer

to pass through the column than others. Mass Spectrometry (MS) is used as a

detector for GC. Samples out of the GC column is fragmented by ionization and

fragments are sorted by mass to form a pattern of fragmentation. Such as retention

time (RT) so that the fragmentation pattern will be formed for a specific

component in the sample that is different and it is a characteristic to identify a

component. It is very specific that is often referred to as a molecular fingerprint.

Gas chromatography-mass spectrometry (GC-MS) is an analytical method which

combines the features of gas-liquid chromatography and mass spectrometry to

identify different substances in a sample components. GC can separate stable and

semi-volatile compounds with great resolution, but can not identify it. MS can

provide detailed information about the structure of most of the compounds so that

the components in the sample can be identified correctly, but can not easily

separate them (Syed and Maqbool, 2014).

2.2.1 Principles of GC-MS

Gas chromatography (GC) and Mass Spectrometry (MS) is a different

analysis technique, used to analyze organic compounds and complex

biochemistry. GC-MS instrument consists of two main components. Sections gas

chromatography separates different compounds in a sample of pure chemicals into

pulses based on its volatility, then by flowing inert gas (mobile phase), which

carries the sample through the stationary phase column. So that would be

generated chromatogram of the compound or the components contained in the

sample. These spectra are collected as they exit the column read by the detector

and mass spectroscopy (MS) to identify and quantify chemical compounds by

mass ratio (m / z). This spectrum can then be stored on a computer and analyzed

form kromatogramnya (Syed and Maqbool, 2014).

GC-MS consists of two parts, namely gas chromatography (GC) and mass

spectrometry (MS), each of which has a different function. GC serves to separate

the compounds in the sample. Separation occurs in the column. The principle of

separation is based on differences in the level of volatility of the compound as

well as based on interactions with the stationary phase. In the column enacted and

holding the temperature gradient to optimize the process pemishan these

compounds. Compounds that have been separated on the GC column, will enter

the MS. MS consists of three parts, namely the ion source, mass analyzer and

detector. Compounds that enter the MS will undergo ionization and fragmentation

into fragment ions. Ionization occurs because the electrons originating from the

ion source (Syed and Maqbool, 2014).

Fragment ions to enter the mass analyzer and will be split based on the

value of m / z her. Fragment ions having m / z values smaller quicker detector will

enter dibandingakan fragment ions having m / z values are great. The output of
the detector in the form of a diagram the relationship between the value of m / z

with the relative intensities of the fragment ions of a compound. Each compound

has a pattern of m / z different, so as to identify a compound by comparing the

spectra patterns that exist in the library (Syed and Maqbool, 2014).

2.2.2 Instrumentation

Here is a picture of the schematic diagram of a gas chromatography mass

spectroscopy (Syed and Maqbool, 2014):

Picture 1. Schematic drawing of GC-MS

1. gas transporter

Carrier gas or gas suppliers are placed in high-pressure cylinders.

Typically the pressure of cylinder of 150 atm. Gas transporter must qualify that

should be inert, does not react with a trailer (trailer solvent and the material in the

column), pure, readily available, relatively cheap, appropriate or suitable to the

detector, and the need to reduce gas diffusion. The gas that is often used is helium,

aargon, nitrogen, carbon dioxide, and hydrogen. Helium and argon is very good,

is not flammable, but very expensive. So sometimes gas that is often used is

however highly flammable hydrogen gas that had to be careful.

 Selection of the carrier gas is determined by the detector to be used. The

carrier gas tube is equipped with output pressure regulator and pressure gauge.

Before getting into the chromatograph, there are accelerometers, gas and

molecular filter system for separating water and other gaseous impurities.

basically regulated gas flow rate through the pressure regulator.

2. injection site

In gas chromatography trailer should be in the form of a vapor phase. Gas

and steam can be entered directly. However, most organic compounds and solid

form of a solution. Thereby compounds in the form of liquids and solids are first

vaporized Hars, this requires heating before entering the column.

Injection site is always set temperature. The first rule for setting this

temperature is that the temperature of the injection site is about 50 ° C higher than

the boiling point of the mixture of footage which has a high boiling point. Footage

entered into the column by injecting through the injection site. This can be done

by using a hypodermic needle which is often called "a gas tight syringe".

3. Column

There are two types of columns used in GC are boxed column and

capillary column. Column container in the form of a tube made of glass or inert

solids steinnstless suatau berisis packaged neatly. This column has a length of 1.5

to 10 m with a diameter of 2.2 to 4 nm. While the capillary columns are typically

made of silica with a layer of polyamide. Columns of this type usually has a

length of 20-26 m uuran with a very small diameter.

4. column oven
 The column is located inside an oven in the instrument. Oven temperature

should be set and slightly below the boiling point of the sample. If the temperature

is too high, liquid stationary phase can be evaporated, too little sample can be

dissolved in a high temperature and can flow too fast in the column.

5. ion source

In the ion source, the product will be ionized prior to analysis in the mass

spectrometer. Ion source will change into a sample of gas phase ions.

6. mass analyzer

Mass analyzer function choose berddasarkan mass ions using

electromagnetic fields.

7. Detector

The detector will detect ion beam emerging from the mass analyzer and

converted into a signal that can be used. The detector is an important element of

mass spectroscopy which produces a signal from ions that are reinforced by

secondary electrons or by inducing currents.

2.3 PAH Analysis Using GC-MS

1. Determination of Polycyclic Aromatic Hydrocarbons in Industrial Harbor

Sediment by GC-MS.

Analysis of 16 polycyclic aromatic hydrocarbons (PAHs) from the list of

priority pollutants to the US Environmental Protection Agency performed on

sediment samples from the industrial port in southern Taiwan's Kaohsiung Harbor

of which should be widely contaminated by industrial waste disposal.

Determination and quantification of PAHs in sediment samples done using gas

chromatography coupled to mass spectrometry (GC-MS) with the aid of an

internal standard and deuterated PAH standard replacement. Total concentration

of 16 PAH vary. PAH concentration is relatively high in the area of the river

mouth, and gradually decreases towards the harbor area. Diagnostic ratios indicate

that the likely source of PAHs in the industrial port area could come from the

burning of coal. Compared with the US Sediment Quality Guidelines (SQGs)

various levels of PAHs exceed the observed effects range median (ERM), and

thus can cause acute biological damage. The results can be used for regular

monitoring, and prevention of future pollution so as to reduce pollution from

various industries.

 Sampling

surface sediment samples were collected at 14 stations located in the

southern industrial port of Kaohsiung Harbor in January 2007) with Ekman

Dredge fishing with a boat ride. Immediately after collection, the samples were

scooped into a glass bottle, which was washed with n-hexane and stored in the

refrigerator. Then the samples were transported to the laboratory for analysis. In

the laboratory, the samples were freeze-dried for 72 hours, the soil, filter 0.5 mm

and completely homogenized. Dried sediment was placed in a temperature of 20 °

C in glass bottles that had been washed with n-hexane and covered with

aluminum foil until analyzed.

The 16 PAHs standard that is in use is naphthalene (NA), acenaphthylene

(ACY), acenaphthene (ACE), fluoren (FL), phenantrene (PH), anthracene (AN),

fluoranthen (FLU), pyrene (PY), benzo [ a] anthracene (BAA), Chrysene (CH),

benzo [b] fluoranthen (BBF), benzo [k] fluoranthen (BKF), benzo [a] pyrene

(BAP), indeno [1,2,3-cd] pyrene (IP), dibenzo [a, h] anthracene (DA), and benzo
[g, h, i] perylene (BP) in a mixed solution of 80 mg / L obtained from

"AccuStandard Chem. Co. (New Haven, CT, USA) ". Deuterated internal standard

solution of PAH (naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10-d

Chrysene 12, and perylene-d 12) at 4,000 mg / L and the replacement standard

solution (2-fluorobiphenyl and 4-terphenyl- d 14) at 2.000 mg / L obtained from

AccuStandard Chem.

 sample preparation

One gram of dry sediment samples and homogeneously incorporated into

clean centrifuge tubes, and added a 1: 1 (v / v) acetone / n hexane as much (5 mL).

Then added a mixture of replacement standard (2-fluorobiphenyl and 4-terphenyl-

d 14) solution. Prepared empty tube following the same procedure without adding

sediment samples. Created the standard used for quality control by adding

standard solution into 5 mL of acetone / n hexane 1: 1 (v / v), then in the vortex

until homogenised for 1 minute. PAH used for the extraction of ultrasonic

equipment for 15 minutes. Sample tubes were then centrifuged at 2000 rpm for 10

minutes. After centrifugation, the organic layer containing the extracted

compounds were sucked out with a Pasteur pipette, and the sediment was re-

extracted twice with 1: 1 (v / v) acetone / n hexane (5 mL). All extracts were

collected together, and active copper added to the combined extracts to

desulfurization. Then a mixture of internal standards (naphthalene-d 8,

acenaphthene-d 10, phenanthrene-d 10, Chrysene-d 12, and perylene-d 12) was

added to the extract which was then analyzed using gas chromatography with

selective detection mass (GC-MS).

 Samples were injected in split mode at an injection temperature of 300 ° C.

Transfer line and ion source temperature of 280 ° C and 200 ° C. The column

temperature was initially held at 40 ° C for 1 min, in raising to 120 ° C at 25 ° C /

min, then to 160 ° C at a rate of 10 ° C / min, and finally to 300 ° C at a rate of 5 °

C / minute, for 15 minutes. Detector temperature kept at 280 ° C. Helium was

used as carrier gas at a constant flow rate of 1 mL / min. Ionisasielektron acquired

using a mass spectrometry (EI) and selective ion monitoring mode (SIM). The

following table picture of the ion monitoring GC-MS conditions at the scheduled

time:
Figure 2. Ion monitoring on GC-MS
  result

Figure 3. (A) GC-MS total ion chromatogram of sixteen PAHs, (b)

chromatogram ion selected from the five internal standard, namely naphthalene-d
8 (IS1), acenaphthened 10 (is2), phenanthrene-d 10 (iS3), Chrysene-d 12 (IS4),
and perylene-d 12 (is5), (c) two replacement standard, 2-fluorobiphenyl (SS1) and
4-terphenyl-d 14 (SS2).
 Before analyzing the samples, the efficiency of GC-MS for the analysis of

target compounds were tested with the standard mix of 16 PAH. Figure 3a shows

the total ion chromatogram for this analysis. Identity 16 PAH is confirmed by

retention time and abundance ion quantification / confirmation in an authentic

PAH standards. Because the 16 PAHs have significantly different chemical

properties and the retention time, five internal standard isotope used to monitor

the 16 PAHs. Naphthalene-d8 with a retention time of 7.021 minutes used for NA.

Acenaphthene-d10 with a retention time of 10.495 min is used to ACY, ACE, and

FL in the retention time window 9,45-13.50 min. Phenanthrene-d10 with a

retention time of 15.250 minutes used for PAH in the retention time range 13,50-

21.50 min. Chrysene-D12 is used for CH and baa. Perylene-D12 is used for the

remaining PAH. Figure 3 (b, c) shows the selected ion chromatogram illustrating

how internal standards and standards effective replacement cover 16 PAHs. The

separation and quantitation of PAHs in sediment samples were achieved using

GC-MS conditions same as the standard.

 CHAPTER III

CLOSING

3.1 Conclusion

1. Polycyclic aromatic hydrocarbons (PAH) or also known as polycyclic

organic matter (POM) is an aromatic molecule consisting of two or more

molecules of aromatic rings are composed by carbon and hydrogen atoms

2. Gas chromatography (GC) and Mass Spectrometry (MS) is teknik different

analysis, used to analyze organic compounds and complex biochemistry.

3. One example of PAH analysis using GC-MS is "Analysis of Polycyclic

Aromatic Hydrocarbons in Industrial Harbor Sediment by GC-MS"

3.2 Suggestion

Suggestions for further manufacture of paper so that the material comes

from sources more reliable material. And the reader is expected to provide input

that are build.