Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

1. OBJECTIVE...................................................................................................................................... 2
2. PRINCIPLE.......................................................................................................................................2
3. INTERFERENCES ...........................................................................................................................2
4. EQUIPMENTS AND REAGENTS ..................................................................................................... 2
5. GLASSWARE CLEANING ................................................................................................................2
6. PREPARATION OF REAGENTS AND STANDARD SOLUTION ...................................................... 2
7. GRINDING OF SAMPLES ................................................................................................................5
8. GC METHOD.................................................................................................................................... 6
9. HEAD-SPACE METHOD FOR ACETALDEHYDE / SOLID SAMPLE : 30MIN 150°C ....................... 6
10. HEAD-SPACE METHOD FOR ACETALDEHYDE / CALIBRATION &CONTROL SOLUTIONS : 5
MIN 150°C................................................................................................................................................ 6
11. HEAD-SPACE METHOD FOR BENZENE/ SOLID SAMPLE : 30 MIN 200°C ................................... 7
12. HEAD-SPACE METHOD FOR BENZENE / CALIBRATION AND CONTROL SOLUTIONS : 5 MIN
200°C .......................................................................................................................................................7
13. QUALITY CONTROLS......................................................................................................................7
 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

1. OBJECTIVE
The objective of this method is to achieve a quantitative analysis of benzene (b) and Acetaldehyde (AA) in PET or
rPET materials (pellets, preforms, bottle necks), within the range of concentrations mentioned in the following table.

Calibration scale for 1g of Limit of Quantification for 1g of

Analyte CAS
sample sample
Acetaldehyde 75-07-0 0,150 -50 mg/kg 0,150 mg/kg
Benzene 71-43-2 0,025-2 mg/Kg 0,025 mg/kg

2. PRINCIPLE
Samples are grinded and placed in headspace vials (sample volume/air volume is fixed). The vials are placed in a
thermostatically controlled oven to reach determined equilibrium conditions, allowing the transfer of molecules of
interest present in the sample to the gas phase.

The chromatographic analysis of a part of the gas phase is carried out using a capillary column and the appropriate
detector.

3. INTERFERENCES
It is possible to generate acetaldehyde during the grinding of the PET material, that is why it is necessary to cool the
material before and during grinding with liquid nitrogen.

4. EQUIPMENTS AND REAGENTS

 Head-space / Gas chromatography with column VF-624ms 30m, 0.25mm, 1.40μm, Agilent
CP9102 or equivalent
 Commercial solution Benzene in MeOH at 2.5 μg / μl kept in the freezer: 2 different lots
 AA commercial solution in water at 100 μg / μl kept in the freezer: 2 different lots
 Analytical Grade Methanol
 Ultrapure water of quality 1 according to ISO 3696
 Ultra centrifuge grinder
 Blade grinder

5. GLASSWARE CLEANING
All reusable glassware is cleaned in the dishwasher.
The clean glassware is placed in an oven at 60 ° C until it is used. It must be taken out before use so that it comes
back to room temperature.

6. PREPARATION OF REAGENTS AND STANDARD SOLUTION

PREPARATION OF ACETALDEHYDE CALIBRATION SOLUTIONS

From the commercial solution at 100 μg/μL, prepare an intermediate solution at 10 μg/μL and then a second
solution at 1 μg/μL. To do this, in a 1,5mL vial with an insert, place the necessary ultrapure water volume using the
pipette and top up the vial. Take the volumes described using the appropriate syringe and place them in the vial
through the septum of the cap.
Reproduce this preparation for all calibration solutions from the intermediate solutions and the commercial solution
as described in the following tables.
 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

Preparation of AA intermediate solution at 10 µg/µL Volume

AA commercial solution in water at 100 µg/µl 25 µL

Ultrapure water 225 µL

Preparation of AA intermediate solution at 1µg/µL Volume

AA intermediate solution in water at 10µg/µl 25 µL

Ultrapure water 225 µL

Volume to be Ultrapure water

Solutions prepared Solution to be taken
taken volume

AA commercial solution in water at

Dilute solution 9 at 5 µg/µL 50 µL 950 µL
100 µg/µl

AA commercial solution in water at

Dilute solution 8 at 2 µg/µL 20 µL 980 µL
100 µg/µl

AA commercial solution in water at

Dilute solution 7 at 1 µg/µL 10 µL 990 µL
100 µg/µl

Dilute solution 6 at 0,500 µg/µL Intermediate solution at 10 µg/L 50 µL 950 µL

Dilute solution 5 at 0,200 µg/µL Intermediate solution at 10 µg/L 20 µL 980 µL

Dilute solution 4 at 0,100 µg/µL Intermediate solution at 10 µg/L 10 µL 990 µL

Dilute solution 3 at 0,050 µg/µL Intermediate solution at 1 µg/L 50 µL 950 µL

Dilute solution 2 at 0,030 µg/µL Intermediate solution at 1 µg/L 30 µL 970 µL

Dilute solution 1 at 0,015 µg/µL Intermediate solution at 1 µg/L 15 µL 985 µL

Use these dilute solutions to make a calibration in Head Space vial by introducing the same volume in each vial.
Each vial must be previously crimped and placed in the freezer so that it is cold. Arrange the 10μL of each dilute
solution through the septum on the wall of each vial following the below table.

Volume to be
collected and Number of vials
Solutions prepared Solution to be taken injected in a cold per standard to
vial through the be prepared
septum

Standard 9 (50 µg AA into the vial) Dilute solution 9 at 5 µg/µL 10 µL 3

Standard 8 (20 µg AA into the vial) Dilute solution 8 at 2 µg/µL 10 µL 3

Standard 7 (10 µg AA into the vial) Dilute solution 7 at 1 µg/µL 10 µL 3

 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

Standard 6 (5 µg AA into the vial) Dilute solution 6 at 0,500 µg/µL 10 µL 3

Standard 5 (2 µg AA into the vial) Dilute solution 5 at 0,200 µg/µL 10 µL 3

Standard (1 µg AA into the vial) Dilute solution 4 at 0,100 µg/µL 10 µL 3

Standard (0,5 µg AA into the vial) Dilute solution 3 at 0,050 µg/µL 10 µL 3

Standard 2 (0,3 µg AA into the vial) Dilute solution 2 at 0,030 µg/µL 10 µL 3

Standard 1 (0,15 µg AA into the vial) Dilute solution 1 at 0,015 µg/µL 10 µL 3

PREPARATION OF BENZENE CALIBRATION SOLUTIONS

From the commercial solution at 2,5 μg/µL, prepare an intermediate solution at 0,25 μg/μL. To do this, in a vial of
1,5 mL arrange the necessary volume of methanol using the pipette and re-seal the vial. Take the volumes
described using the appropriate syringe and place them in the vial through the septum of the cap.
Reproduce this preparation for all calibration solutions from the intermediate solutions and the commercial solution
as described in the following tables.

Preparation of Benzene intermediate solution at 0,25µg/µL Volume

Benzene commercial solution in MeOH at 2,5 µg/µl 25 µL

Methanol 225 µL

Volume to be
Solutions prepared Solution to be taken Methanol volume
taken

Benzene commercial solution in

Dilute solution 9 at 0,2 µg/µL 80 µL 920 µL
MeOH at 2,5µg/µl

Benzene commercial solution in

Dilute solution 8 at 0,1 µg/µL 40 µL 960 µL
MeOH at 2,5µg/µL

Benzene commercial solution in

Dilute solution 7 at 0,05 µg/µL 20 µL 980 µL
MeOH at 2,5µg/µL

Dilute solution 6 at 0,0375 Benzene commercial solution in

15 µL 985 µL
µg/µL MeOH at 2,5µg/µL

Dilute solution 5 at 0,0250 Benzene commercial solution in

10 µL 990 µL
µg/µL MeOH at 2,5µg/µL

Dilute solution 4 at 0,0150

Dilute solution at 0,25 µg/µL 60 µL 940 µL
µg/µL

Dilute solution 3 at 0,0100

Dilute solution at 0,25 µg/µL 40 µL 960 µL
µg/µL

Dilute solution 2 at 0,0050

Dilute solution at 0,25 µg/µL 20 µL 980 µL
µg/µL

Dilute solution 1 at 0,0025

Dilute solution at 0,25 µg/µL 10 µL 990 µL
µg/µL
 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

Use these dilute solutions to make a calibration in Head Space by introducing the same volume in each vial. Each
vial must be previously crimped and placed in the freezer so that it is cold. Arrange the 10μL of each dilute solution
through the septum into each vial according to the chart below.

Volume to be
collected and Number of vials
Solutions prepared Solution to be taken injected in a cold per standard to
vial through the be prepared
septum

Standard 9 (2 µg Benzene into

Dilute solution 9 at 5 µg/µL 10 µL 3
the vial)

Standard 8 (1 µg Benzene into

Dilute solution 8 at 2 µg/µL 10 µL 3
the vial)

Standard 7 (0,5 µg Benzène

Dilute solution 7 at 1 µg/µL 10 µL 3
dans vial)

Standard 6 (0,375 µg Benzene

Dilute solution 6 at 0,500 µg/µL 10 µL 3
into the vial)

Standard 5 (0,250 µg Benzène

Dilute solution 5 at 0,200 µg/µL 10 µL 3
dans vial)

Standard 4 (0,150 µg Benzene

Dilute solution 4 at 0,100 µg/µL 10 µL 3
into the vial)

Standard 3 (0,100 µg Benzene

Dilute solution 3 at 0,050 µg/µL 10 µL 3
into the vial)

Standard 2 (0,050 µg Benzene

Dilute solution 2 at 0,030 µg/µL 10 µL 3
into the vial)

Standard 1 (0,025 µg Benzene

Dilute solution 1 at 0,015 µg/µL 10 µL 3
into the vial)

7. GRINDING OF SAMPLES
It is key to cold down the samples before and during the grinding with liquid nitrogen, in order to prevent generation
of AA and b.

In case of preforms or bottle necks, the samples must be first reduced in small pieces with the blade grinder. Then
use the ultra centrifuge grinder.

In each vial, arrange 1 g of sample at +/- 0,01 g using the spatula and crimp. Record the precise weight.
 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

8. GC METHOD

9. HEAD-SPACE METHOD FOR ACETALDEHYDE / SOLID SAMPLE : 30MIN 150°C

10. HEAD-SPACE METHOD FOR ACETALDEHYDE / CALIBRATION &CONTROL SOLUTIONS : 5

MIN 150°C
Settings are the same except the incubation time (Thermostat) which is only 5 minutes. Indeed all the molecules are
already as steam in the gas phase, so incubation is not necessary.
 Benzene and Acetaldehyde quantification in PET/rPET materials by HS-GC

11. HEAD-SPACE METHOD FOR BENZENE/ SOLID SAMPLE : 30 MIN 200°C

12. HEAD-SPACE METHOD FOR BENZENE / CALIBRATION AND CONTROL SOLUTIONS : 5 MIN
200°C
Settings are the same except the incubation time (Thermostat) which is only 5 minutes. Indeed all the molecules are
already as steam in the gas phase, so incubation is not necessary.

13. QUALITY CONTROLS

It is important to have a quality system allowing to make sure that the results are reliable:

- Set criteria to validate the calibration curve (linear regression, accuracy…)

- Each day of analysis verify the calibration of the equipment by analyzing control solutions prepared from
commercial solutions different from the ones used for the calibration solutions
- Make sure that the preparation of the samples doesn’t lead to over or under estimation
- …