Application Gas Chromatography Mass Spectrometry

News
Analysis of Mixed Polymer Sample as Microplastics
using Pyrolysis GC/MS
No. M298
Fine plastic particles with sizes of several μm to about 5 mm
are called microplastics (MPs), and their effect on pollution
„ Sample and Analysis Conditions
Fig. 1 shows the Py-GC/MS system (GCMS-QP2020 NX and
and ecosystems in marine environments is a serious concern. EGA/PY-3030D pyrolyzer) used in the analysis.
It has been pointed out that bioaccumulation may occur by a
process of adsorption of harmful substances on MPs, and Approximately 0.05 mg each of fragments of four types of
ingestion of those MPs by marine organisms in marine commercially-available standard polymer sample materials
environments. Due to that, many surveys of the actual (polyethylene (PE), polypropylene (PP), polystyrene (PS), and
condition of MPs and evaluation of their toxicity are being polyvinyl chloride (PVC)) were introduced into a sample cup,
conducted. and about 1 mg of wool was placed in the cup to prevent
scattering. This sample was then set in the auto-shot sampler
As analytical instruments, the Fourier transform infrared of the pyrolyzer.
spectrometer (FTIR) is used in qualitative analysis of
comparatively large MPs, while the FTIR microscope Table 1 shows the instruments and the analytical conditions.
employing an infrared microscope is mainly used for fine MPs According to References (1) and (2), the contents of the
which cannot be analyzed by the attenuated total reflectance polymers were judged by detecting the pyrolysis products
(ATR) method of FTIR. The FTIR microscope enables highly shown in Table 2 (however, some of these compounds were
sensitive analysis of fine MPs with a size of approximately selected independently).
10 μm. However, in cases where it is difficult to distinguish
the MPs containing multiple types of fine particles, it has Table 2 Pyrolysis Products and Analytical Conditions Used in
been reported that the pyrolysis gas chromatography/mass Detection of Polymers
spectrometry (Py-GC/MS) method is effective. SIM
Retention
Using Py-GC/MS method, qualitative analysis of individual Polymer Pyrolysis product monitoring
time (min)
ion
polymers contained in mixed samples is possible by highly C20, alkane 20.937 99, 85
sensitive detection of the distinctive pyrolysis products of each PE C20, Į-alkene 20.879 97, 83
polymer. This article reports the results of a qualitative analysis C20, Į, Ȧ-alkene 20.817 95, 82
of a sample, prepared by mixing multiple polymers to simulate 2,4-dimethylhept-1-ene 5.231 126, 70
2,4,6,8-tetramethyl-1-undecene 12.908 111, 69
MPs, using Py-GC/MS method. PP
2,4,6,8-tetramethyl-1-undecene 13.027 111, 69
Y. Kudo, Y. Ikezawa, Y. Aoyama 2,4,6,8-tetramethyl-1-undecene 13.145 111, 69
Styrene 6.17 104, 78
PS 3-butene-1,3-diyldibenzene 18.136 208, 91
5-hexene-1,3,5-triyltribenzene 25.032 312, 207
Benzene 2.498 78, 51
1-Chloroindan 8.874 116, 115
PVC
Dihydronaphthalene 10.835 130, 115
Azulene 11.145 128, 102

Fig. 1 Appearance of Py-GC/MS System

Table 1 Analytical Conditions

Instruments
Pyrolyzer : EGA/PY-3030D multi-shot pyrolyzer, AS-1020E auto-shot sampler (Frontier Laboratories Ltd.)
GC-MS : GCMS-QP™2020 NX
Column : UA-5 (MS/HT)-30M-0.25 (Length 30 m, I.D. 0.25 mm, df = 0.25 μm) (Frontier Laboratories Ltd.)

Pyrolyzer conditions
Pyrolyzer furnace temp. : 600 °C
Interface temp. : 300 °C (manual)

GC conditions MS conditions
Vaporizing chamber temp. : 300 °C Interface temp. : 300 °C
Column oven temp. : 40 °C (2 min) o 10 °C/min o 320 °C (16 min) Ion source temp. : 230 °C
Carrier gas : Helium Ionization method : El
Control mode : Constant linear velocity Measurement mode : Scan/SIM (m/z 29 - 700)
Injection mode : Split (1 : 50) Scan event time : 0.3 s
Linear velocity : 36.1 cm/min SIM event time : 0.15 s
Purge flow rate : 3 mL/min
Application No. M298
News

„ Simultaneous Analysis of Polymers in Mixed it was difficult to specify the individual polymers contained in
the sample from this chromatogram alone.
Polymer Sample
Fig. 2 shows the total ion current chromatogram (TIC Fig. 3 shows the SIM chromatograms of the pyrolysis
chromatogram) obtained by analyzing the mixed sample products of the respective polymers. By tracing the
containing multiple polymers. Since the result of this analysis distinctive pyrolysis products of the respective polymers, the
takes the form of a complex chromatogram in which the contents of the polymers could be specified accurately, even
pyrolysis products of the respective polymers are intermixed, multiple polymers were intermixed in a sample.

(x1,000,000)
7.0 1:TIC (1.00)
6.0

5.0
4.0

3.0

2.0

1.0

5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 min

Fig. 2 TIC Chromatogram Obtained by Analysis of Mixed Polymer Sample by Py-GC/MS Method
C20, alkane C20, α-alkene C20, α,ω-alkene
(x10,000)
2.25 (x10,000) (x10,000)
99 7.0
85 97 3.5 95
2.00 83 82
1.75 6.0 3.0

1.50 5.0 2.5

Pyrolysis products of PE 1.25

1.00
4.0 2.0

3.0 1.5
0.75
0.50 2.0 1.0

0.25 1.0 0.5

20.50 20.75 21.00 21.25

20.50 20.75 21.00 21.25 20.50 20.75 21.00 21.25

2,4-dimethylhept-1-ene 2,4,6,8-tetramethyl-1-undecene 2,4,6,8-tetramethyl-1-undecene 2,4,6,8-tetramethyl-1-undecene

(x100,000) (x100,000) (x100,000) (x100,000)
6.0 70 69 69 69
1.2 1.2 111 1.2 111
126 111
5.0 1.0 1.0
1.0

4.0 0.8 0.8 0.8

Pyrolysis products of PP 3.0 0.6 0.6 0.6

2.0 0.4 0.4 0.4

1.0 0.2 0.2 0.2

0.0 12.50 12.75 13.00 13.25

4.75 5.00 5.25 5.50 12.25 12.50 12.75 13.00 12.75 13.00 13.25 13.50

Styrene 3-butene-1,3-diyldibenzene 5-hexene-1,3,5-triyltribenzene

(x1,000,000) (x1,000,000) (x100,000)
7.0 104
208 312
78 1.25 2.50 207
6.0 91

5.0 1.00 2.00

4.0
Pyrolysis products of PS 0.75 1.50
3.0
0.50 1.00
2.0
0.25 0.50
1.0

0.00
5.75 6.00 6.25 6.50 17.75 18.00 18.25 18.50 24.75 25.00 25.25 25.50

Benzene 1-Chloroindan Dihydronaphthalene Azulene

(x1,000,000) (x100,000) (x10,000)
(x100,000)
78 130 4.5
1.75 116 128
51 8.0 115
2.50 115 4.0 102
1.50 7.0
3.5
2.00 1.25 6.0
3.0
5.0
1.50 1.00 2.5
Pyrolysis products of PVC 0.75
4.0
2.0
1.00 3.0
1.5
0.50
2.0
0.50 1.0
0.25 1.0 0.5

2.00 2.25 2.50 2.75 8.50 8.75 9.00 9.25 10.50 10.75 11.00 11.25 10.75 11.00 11.25 11.50

Fig. 3 SIM Chromatograms of Pyrolysis Products of Polymers in Mixed Polymer Sample

„ Conclusion
In this experiment, it was found that qualitative analysis of <References>
various polymers is possible, even the sample contains (1) M. Fisher and B. M. Scholz-Böttcher, Environ. Sci. Technol.,
multiple polymers, by monitoring the pyrolysis products of 51,5052-5060 (2017)
the respective polymers using the Py-GC/MS method. (2) S. Tsuge, H. Ohtani, C. Watanabe: Pyrolysis-GC/MS Data Book of
Synthetic Polymers -Pyrograms, Thermorgams and MS of
Although the object of analysis in this experiment consisted
Pyrolyzers-,1st Edition, Elsevier, 420 (2011)
of four substances (polymers), it is thought that this
technique is also applicable to larger numbers of polymers.
Thus, this technique is expected as a new analysis method of
MPs.

GCMS-QP is a trademark of Shimadzu Corporation in Japan and/or other countries.

Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not
they are used with trademark symbol “TM” or “£”.
First Edition: Jun. 2020

For Research Use Only. Not for use in diagnostic procedures.

This publication may contain references to products that are not available in your country. Please contact us to check the availability of these
products in your country.

The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.
Shimadzu disclaims any proprietary interest in trademarks and trade names used in this publication other than its own.
See http://www.shimadzu.com/about/trademarks/index.html for details.

www.shimadzu.com/an/ The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
to change without notice.
© Shimadzu Corporation, 2020