QUALITATIVE AND QUANTITATIVE ANALYSIS

OF AIR SAMPLE USING GCXGC-10FMS

Raquel Tejero Oliva

Arantxa Garcia Torre
Yingqi Fan
Mariana Sánchez Campos
Clara Toledo Arribas

AIR PURIFICATION TECHNOLOGIES

2018-2019

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 1. INTRODUCTION

1.1 The gerstel tenax ta tube (Yingqi Fan)

Figure 3.1.1 the picture of the tenax ta tube Figure 3.1.2 the structure of the tenax ta tube

Tenax® TA is a traditional sorbent (porous polymer) for trapping medium to high boiling
compounds; it is especially useful for low concentrations because of its low background. Tenax
TA is hydrophobic and is suitable for use in EPA Method TO-17 or IP-1B and other thermal
desorption applications. After the collection of the air, it can be preserved for 1 week in the
refrigerator in 4 ℃ .

As it is shown in the figure 3.1.2, the tube is consisted of many parts. Such as high- purity
glass wool, sealing caps, glass tube, sorbent layer, backup sorbent layer, foam separator and
precision- sealed tips.

1.2 GSS air sampler from Gerstel (Yingqi Fan)

1.2.1 Reliable collection of air samples

The Gas Sampling System (GSS) is an active sampling system based on pumped sampling
of air onto one or two adsorbent tubes, which are then analyzed by thermal desorption
combined with MPS. The two flow channels may be used as independent as it is shown in the
figure 3.2.1, for Distributed Volume Pair samples or as identical channels for critical and unique
samples.

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 Figure 3.2.1 the picture of the GSS air sampler

1.2.2 Dual channel system- for improved safety

The GSS is equipped with mass flow controllers as well as mass flow sensors with Flow
Tamer™ Technology. The GERSTEL GSS is compatible with all standard TD-tubes used for
thermal desorption. All collection parameters are independently recorded on both channels
and may be sent to an external data device. Sampling may be started using a pre-programmed
time schedule or on-demand from the built-in touch screen.

1.2.3 GERSTEL GSS Features

 Parallel sampling onto two adsorbent tubes

 Sample volumes can be specified independently for each channel
 Sampling flow can be set independently for each channel
 Duplicate samples or Distributed Volume Pairs can be collected
 Simple sampling including back-up sample
 Compatible with all standard adsorbent tube types
 Sampling using a programmed sequence or manual operation
 Two independent flow channels with separate integrated pumps
 Constant flow sampling or intermittent sampling
 Low flow sampling for time weighted average (TWA) operation
 Battery operation for independent and flexible field sampling
 Rugged housing ideal for field operation
 Reliable and accurate sampling
 Reliable and accurate sampling for accurate results
 Full documentation and traceability

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 1.3 The experimental data of the GSS air sampler (Yingqi Fan)

During the experiment, it takes 20 mins to collect the air sample out of the organic laboratory.
It collected the air 75 mL/min, so that the total volume of the air is 1.5 L. One thing during the
experiment need to be paid attention is that the sampler need to be placed vertically.

1.4 Thermal desorption system from Gerstel (Mariana Sánchez and Clara Toledo )

Is a flexible automated solution for thermal desorption and thermal extraction. The TDU 2fits
on top of any modern GC without the need for additional bench space and it is perfectly suited
for the analysis of gaseous, liquid and solid samples.

 It incorporates the latest advances in thermal desorption technology. Intelligently

designed and based on a “Liner-in-Liner” concept it has no valves or transfer lines.

1. Is connected directly to the GERSTEL Cooled Injection System (CIS), which

serves both as a cryo-focusing trap and as a temperature programmable GC
inlet.

2. Active sites are eliminated, reducing the risk of analyte loss, discrimination and
memory effects to an absolute minimum.

3. Can be operated in split or true splitless mode enabling it to cover the widest
range of concentrations, to protect the column from water and contamination
and to achieve the lowest possible detection limits.
4. The pneumatics provide improved flexibility and performance. For extreme
sensitivity, the multi-desorption mode can be selected in MAESTRO.

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Several techniques are supported by the TDU:

1. Stir Bar Sorptive Extraction (SBSE) using the GERSTEL Twister®

2. Dynamic Headspace (DHS) based on standard headspace vials
3. DHS Large based on sample containers up to 1 L volume
4. Thermal desorption of adsorbent tubes used for air sampling
5. Thermal extraction of solid samples placed in fritted TDU tubes
6. Thermal extraction of liquids placed in µ-vials inside the TDU 2
7. Direct introduction and thermal extraction of liquids such as standards
8. Automated Pyrolysis of liquid and solid samples using the PYRO module
9. The TDU 2 supports manual operation and it can be removed in seconds to enable
direct liquid sample introduction into the GERSTEL Cooled Injection System (CIS), a
PTV-type universal GC inlet.

When configured with the GERSTEL MultiPurpose Sampler (MPS), up to 40 samples are stored
per TDU tray in individually sealed sample positions. The system can easily be scaled up by
using up to three TDU trays per tray holder. The number of tray holders depends on size and
configuration of the MPS.

Samples can be analyzed in one automated sequence using one or more methods. The
MAESTRO software combined with the Agilent ChemStation controls the complete process
from sample introduction through thermal desorption to GC/MS analysis with one method and
one sequence table ensuring efficient and error-free operation.

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 1.5 The Agilent 7890A gas chromatograph (Mariana Sánchez and Clara Toledo)

Chromatography is the separation of a mixture of compounds into individual components.

The Agilent 7890A gas chromatograph includes advanced separation capabilities, powerful
new productivity features, and real-time intelligent instrumental self-monitoring.

There are three major steps involved with separating and identifying components of a mixture
using a GC:

 Injecting a simple into the GC. This takes place at the inlet.
 Separating the simple into individual components.
 Detecting what compounds were in the simple.

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During this process, status messages from the Agilent 7890A GC are displayed, and user
changes to parameter settings can be made through the operating panel.

-The front view

-The back view

-The inlets

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Inlets are where samples are injected into the GC. This machine has two inlets, Fron Inlet and
Back Inlet. The type of inlet chosen is base don the type of analysis being done, the type of
simple being analyzed, and the colum being used.

-The Gc Column and Oven

GC columns are located inside a temperature- controlled oven. Generally, one end of the
column is attached to the inlet, while the other end is attached to the detector.

Columns vary in length, diameter, and internal coating. Each column is designed for use with
different compounds.

The purpose of the column and the oven is to separate the injected sample into individual
compounds as it travels through the column. To aid this process, the GC oven can be
programmed to speed the sample flow through the column.

-Detectors

Detectors identify the presence of compounds as they exit the column. As each compound
enters the detector, an electrical signal proportional to the amount of compound detected is
generated. This signal is generally sent to a data analysis system where it shows up as a peak
on a chromatogram.

-The display

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It shows information of what is happening at that moment and allows to make changes in the
parameters when it is necessary.

-Status indicators

Status indicators provide basic information with a glimpse of what is happening at the
moment.

-The keypad

All of the parameters required to operate the Agilent 7890A GC can be entered through the
GC’s keypad. Normally, however, most of these parameters are controlled using an attached
data system.

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1.6 Two-dimensional gas chromatograph coupled with time of flight mass spectrometer and
cis-cruo injection system from Gerstel. (Arantxa Garcia)

1.6.1 Cis-cruo injection system from Gerstel

CIS-2-940×1302 (4.1)

From guide.

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Is the most widely sold PTV-type universal inlet in the world. The CIS combines high
performance with unique flexibility for various compounds.

The CIS is easily controlled through GERSTEL MAESTRO Software in stand-alone mode or
integrated with the Agilent Technologies MassHunter or ChemStation software. All data entry
fields have pop-up information windows available that provide valid parameters ranges as well
as practical tip. in combination with the GERSTEL MAESTRO Software, integrated in the
Agilent® Technologies ChemStation Software or operated in stand-alone mode only one
method for the complete system including GC/MS when integrated in ChemStation software.

Gas chromatographic analysis is now more versatile, reproducible and has lower detection
limits than other versions, this is due to temperature programmed (is performed reliably up to
650 °C) sample injection using GERSTEL Cooled Injection System.

Parts of CIS (4.2)

From guide.

Two main system-functions:

1. Universal injection system for all injection techniques: split, splitless, on-column and
large-volume up to 1000 µl.
2. Cryotrap enrichment system in combination with sample preparation systems, i.e. the
GERSTEL Thermal Desorption System TDS, the GERSTEL Dynamic Headspace DHS, the
GERSTEL Thermal Desorption Unit TDU or the GERSTEL Multipurpose Sampler MPS.

Gas inlet liners: 3 x 2 x 71 mm (OD x ID x L)

1. 3 x 1 x 71 mm (OD x ID x L) only for CIS4.

2. Straight or baffled.
3. Empty or packed.
4. Made of quartz or borosilicate glass.
5. Standard or deactivated.
6. Separate liner flyer (provides more detailed information).

Main Features and Advantages

 Universal inlet – 7 different modes of injection.

 Peltier or LN2 cooling.
 Eliminates thermal discrimination.
 Reduces decomposition of thermally labile compounds.
 Lowers detection limits.
 Efficient cold trap.

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There are three different versions of the CIS:

 CIS 4 for Agilent Technologies 6850/6890/7890 GCs.

 CIS 6 for high temperature (650ºC) applications using Agilent Technologies
6850/6890/7890 GCs.
 CIS 3 for HP 5890 GC as well as for all other types of GCs.

Versions of CIS (4.3)

From guide.

1.6.2 Two-dimensional gas chromatograph coupled with time of flight mass spectrometer
(Arantxa García)

It combines gas chromatography and mass spectrometry to identify and quantify substances.
The process begins with the substance under study being diluted with a gas or liquid and
introduced into the machine. The GCMS separates the substance into components to be
identified by a computer.

The gradual increase in temperature causes the compound to break down into its component
parts, leave the chamber, and move at variable rates in the detector. Electrically charged, the
particles activate an electronic signal. The higher the particle concentration, stronger the signal
created.

These signals are then analysed by the software. The programme produces (a chart)
chromatogram with peaks that indicate the retention times and the signal intensities of the
compounds. Knowing the retention times of several chemical compounds allows to identify.

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Additional analysis occurs in the mass spectrometer. Once compounds enter the spectrometer,
they hit a series of electrons or gas. Ionization occurs, breaking the compound into fragments,
each with a specific atomic mass. These fragments are subjected to analysis by compiling a
mass fragment under load, or M/Z.

This information founded passes to the gas chromatograph mass spectrometer computer that
formulates a graph with M/Z based peaks vs signal strength. The software includes a database
of known ratios and signal strengths for different chemicals. The gas chromatograph mass
spectrometer can complete each phase of the analysis individually or simultaneously.
Depending on the level of detail desired, completing the process can take minutes or hours.

This technique has been used for the analysis of several complex mixtures such as jet fuels,
environmental samples (Environmental agencies use technology to analyse air, soil, or water
samples to detect potential contaminants.), drug screening (Police officers use a mass
spectrometer gas chromatograph when they suspect the presence of illegal drugs or poisonous
substances) Health professionals use a GCMS in urine samples to detect chemical compounds
found in people with certain metabolic disorders, cigarette smoke condensate and pesticides.

The major advantage of a time-of-flight mass spectrometer (TOFMS) over other GCxGC
detectors is its ability to aid in the identification of many compounds in very complex mixtures.
Obtaining useful information from the analysis of these mixtures, which may contain many
different compounds, requires a reliable and relatively rapid procedure to identify compounds
of interest and to deconvolute any overlapping mass spectra to yield pure chromatographic
peak profiles for accurate quantification. Offers the best separation efficiency combined with
accurate mass measurements over a wide mass range.

Characterization of serum metabolic fingerprints of neonatal

13(4.5)
calves

https://www.journalofdairyscience.org/article/S0022
-0302(17)30282-5/pdf
GC×GC-MS Analysis

It has many systems to analyse but with a system containing an Agilent 7890 GC (Agilent
Technologies, Santa Clara, CA) with a Gerstel MPS2 autosampler (Gerstel, Mülheim an der
Ruhr, Germany) interfaced with a LECO Pegasus 4D time-of-flight MS (LECO Corp., St. Joseph,
MI).

It has 2 columns, the primary column, 30-m DB-5MS (0.25 mm i.d. × 0.25 μm df, Agilent
Technologies), and the secondary column, 1.5-m RTX-200 (0.18 mm i.d. × 0.25 μm df, Restek
Corp., Bellefonte, PA).

The columns can be placed one inside the other due to the modulator of nitrogen. The carrier
gas is helium. The primary column temperature must be chosen. The secondary column
temperature program can be set in at a parallel ramp putting few more degrees.

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15
 2. EXPERIMENTAL PART (Raquel Tejero Oliva)

The purpose of this experiment was the collection and analysis of air samples from the
University Politechnika of Gdánska.

As we can see in table 2.2 the compounds we have found were toluene, ethylbenzene, p-
xylene and o-xylene.

2.1 INFORMATION ABOUT THE COMPOUNDS (Raquel Tejero Oliva)

2.1.1 Toluene

TOLUENE (fig 2.1) is a clear colorless liquid with a characteristic aromatic odor. Flash point
40°F. Less dense than water (7.2 lb / gal) and insoluble in water. Hence floats on water. Vapors
heavier than air. May be toxic by inhalation, ingestion or skin contact. Used in aviation and
automotive fuels, as a solvent, and to make other chemicals.

GHS Hazard statements

H225: Highly Flammable liquid and vapor [Danger Flammable liquids]

H304: May be fatal if swallowed and enters airways [Danger Aspiration hazard]
H315: Causes skin irritation [Warning Skin corrosion/irritation]
H336: May cause drowsiness or dizziness [Warning Specific target organ toxicity, single
exposure; Narcotic effects]
H361d ***: Suspected of damaging the unborn child [Warning Reproductive toxicity]
H373 **: Causes damage to organs through prolonged or repeated exposure [Warning Specific
target organ toxicity, repeated exposure]

Fig 2.1 Toluene

2.1.2 Ethylbenzene

ETHYLBENZENE (Fig 2.2) is a clear colorless liquid with an aromatic odor. Flash point 59°F. Less
dense than water (at 7.2 lb / gal) and insoluble in water. Hence floats on water. Vapors heavier
than air. Used as a solvent and to make other chemicals.

GHS Hazard statements

H225: Highly Flammable liquid and vapor [Danger Flammable liquids]

H304: May be fatal if swallowed and enters airways [Danger Aspiration hazard]
H332: Harmful if inhaled [Warning Acute toxicity, inhalation]

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H373: Causes damage to organs through prolonged or repeated exposure [Warning Specific
target organ toxicity, repeated exposure]

Fig 2.2 Ethylbenzene

2.1.3 p-xylene

P-XYLENE (Fig 2.3) is a colorless watery liquid with a sweet odor. Less dense than water.
Insoluble in water. Irritating vapor. Freezing point is 56°F. (USCG, 1999).

GHS Hazard statements

Aggregated GHS information provided by 964 companies from 21 notifications to the ECHA
C&L Inventory. Each notification may be associated with multiple companies.
H226 (100%): Flammable liquid and vapor [Warning Flammable liquids]
H304 (10.89%): May be fatal if swallowed and enters airways [Danger Aspiration hazard]
H312 (99.79%): Harmful in contact with skin [Warning Acute toxicity, dermal]
H315 (100%): Causes skin irritation [Warning Skin corrosion/irritation]
H319 (48.03%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]
H332 (100%): Harmful if inhaled [Warning Acute toxicity, inhalation]
H335 (11.1%): May cause respiratory irritation [Warning Specific target organ toxicity, single
exposure; Respiratory tract irritation]
H412 (16.08%): Harmful to aquatic life with long lasting effects [Hazardous to the aquatic
environment, long-term hazard]
Information may vary between notifications depending on impurities, additives, and other
factors. The percentage value in parenthesis indicates the notified classification ratio from
companies that provide hazard codes. Only hazard codes with percentage values above 10%
are shown.

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Fig 2.3 p-xylene

2.1.4 o-xylene

O-XYLENE (Fig 2.4) is a colorless watery liquid with a sweet odor. Less dense than water.
Insoluble in water. Irritating vapor. (USCG, 1999).

GHS Hazard statements

Aggregated GHS information provided by 1175 companies from 22 notifications to the ECHA
C&L Inventory. Each notification may be associated with multiple companies.
H225 (30.21%): Highly Flammable liquid and vapor [Danger Flammable liquids]
H226 (69.79%): Flammable liquid and vapor [Warning Flammable liquids]
H304 (15.49%): May be fatal if swallowed and enters airways [Danger Aspiration hazard]
H312+H332 (30.3%): Harmful in contact with skin or if inhaled [Warning Acute toxicity, dermal;
acute toxicity, inhalation]
H312 (99.91%): Harmful in contact with skin [Warning Acute toxicity, dermal]
H315 (100%): Causes skin irritation [Warning Skin corrosion/irritation]
H319 (45.87%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]
H332 (99.91%): Harmful if inhaled [Warning Acute toxicity, inhalation]
H335 (15.57%): May cause respiratory irritation [Warning Specific target organ toxicity, single
exposure; Respiratory tract irritation]
Information may vary between notifications depending on impurities, additives, and other
factors. The percentage value in parenthesis indicates the notified classification ratio from
companies that provide hazard codes. Only hazard codes with percentage values above 10%
are shown.

Fig 2.4 o-xylene

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 2.2 TABLES AND GRAPHS (Raquel Tejero Oliva)

Name Time retention Similarity Height 1:50 (20 ppb)

(s)
Toluene 612 932 217709 691080
Ethylbenzene 877 807 85636 516544
p-xylene 914 928 144869 411633
o-xylene 1008 800 54034 402589

Name 1:100 (10 ppb) 1:200 (5 ppb) 1:500 (2 ppb) 1:1000 (1 ppb)
Toluene 370360 187801 77372 35846
Ethylbenzene 267280 130591 53522 26695
p-xylene 209206 101621 41549 21707
o-xylene 199527 97239 39193 20710

Table 2.2

2.2.1 TOLUENE

Concentration (ppb) Height

1 35846
2 77372
5 187801
10 370360
20 691080

Table 2.2.1

Toluene
800000
700000
f(x) = 34651.69 x + 7615.82
600000 R² = 1
500000
Height

400000
300000
200000
100000
0
0 5 10 15 20 25
Concentration (ppb)
Graph 2.2.1

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With the formula and the first height, we can recalculate the concentration.

y=34652 x+ 7615,8=¿ 297709

x = 8.34 ppb

2.2.2 ETHYLBENZENE

Concentration (ppb) Height

1 26695
2 53522
5 130591
10 267280
20 516544

Table 2.2.2

Ethylbenzene
600000

500000 f(x) = 25890.68 x + 1797.67

R² = 1
400000
Height

300000

200000

100000

0
0 5 10 15 20 25
Concentration (ppb)

Graph 2.2.2

With the formula and the first height, we can recalculate the concentration.

y = 25891x + 1797,7 = 85636

x= 3.23 ppb

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 2.2.3 p-xylene

Concentration (ppb) Height

1 21707
2 41549
5 101621
10 209206
20 411633

Table 2.2.3

p-xylene
450000
400000 f(x) = 20604.02 x + 460.56
350000 R² = 1
300000
250000
Height

200000
150000
100000
50000
0
0 5 10 15 20 25
Composition (ppb)

Graph 2.2.3

With the formula and the first height, we can recalculate the concentration.

y = 20604x + 460,56 = 144869

x= 7.009 pbb

2.2.4 o-xylene

Concentration (ppb) Height

1 20710
2 39193
5 97239
10 199527
20 402589

Table 2.2.4

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 o-xylene
450000
400000
f(x) = 20128.02 x − 934.46
350000 R² = 1
300000
250000
Height

200000
150000
100000
50000
0
0 5 10 15 20 25
Concentration (ppb)

Graph 2.2.4

With the formula and the first height, we can recalculate the concentration.

y = 20128x - 934,46= 94034

x= 4.718 pbb

3. CONCLUSION (Raquel Tejero Oliva and Arantxa García Torre)

Requeriments to do the calibration

LOD ≥ 3 → S/ N ≥3
LOQ ≥ 10→ S/ N ≥10
OUR S/N at 1 compound S/N= 350

The reagents found in the air of the Chemia A building of the Politechnika Gdánska University
are not dangerous to health in the concentrations found (ppb).

In the long term, the concentrations of these substances could increase, and they would begin
to be harmful to the health of students and teachers.

We must be aware of the importance of air purification, since this could lead to a mixture with
particulate matter and would be very harmful to health and more complicated to purify.

We have been surprised by the presence of dioxins, since these are usually only found in large
industries, and they are also very directly related to cancer and malformations of fetuses.

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