Professional Documents
Culture Documents
spectrometry
Institute for Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky
Supplement content: 15 pages (cover page included), 4 tables, 9 figures, and 2 text sections
Table S2 (page S-3) Table of all plastic standards used for data base and calibration
Table S3 (page S-12) Calibration related data for the investigated polymer types
Figures S1- S8 (pages S-4 – S-11) Pyrograms (direct and TMAH), additional information and
selected mass spectra of all synthetic polymer types used
S-1
Pyrolysis-GCMS/Thermochemolysis
Table S1 Conditions for Pyrolysis-GCMS measurements
S-2
Polymer Standards
Table S2 Table of all plastic standards used for data base and calibration
Abbre-
Polymer standard Source of supply
viation
Polyamide 6 (K891)
PA6 Ter Hell GmbH, Hamburg, Germany
Akulon® K222-D
Polycarbonate (K883)
PC Ter Hell GmbH, Hamburg, Germany
XANTAR® 18 SR FD
Polyethylene MG7547 HDPE Borealis, Austria
Polyethylene, Lupolene® 6031 M HDPE LyondellBasell, The Netherlands
Polyethylene HDPE Commercially available packaging foil
Polyethylene terephthalate (K896) PET Ter Hell GmbH, Hamburg, Germany
Poly(methyl methacrylate) (K964)
PMMA Ter Hell GmbH, Hamburg, Germany
PLEXIGLAS® 7N
Polypropylene
PP LyondellBasell, The Netherlands
Purell HP570M, isotactic
Polypropylene, isotactic PP Commercially available packaging foil
Polystyrene (K834) Ter Hell GmbH, Hamburg, Germany
PS
TOTAL PS impact 7240
Polystyrene, Bycolene® 158K NR2 PS BASF, Germany
Polystyrene 143 E PS BASF, Germany
Commercially available black pond foil
Polyvinylchloride, plasticized* PVC
(1 mm) (DIY store)
Polyvinylchloride
PVC Granulat GmbH, Germany
Troilit® VB 537-HE
* The content of plasticizers in the pond foil was analytically determined (29.4 %, average of a
quintuplicate) and subtracted for calibration purposes. The additive content of all the other standards is
about 1-2% as it is reported for such common thermoplastic materials. The additive content of Troilit®
was analytically determined with 1.3%. These contents were ignored regarding the calibration.
Identification
In the following, characteristic pyrograms of the polymers analyzed are shown (Figures S1-
S8). Each subsection contains:
a) The pyrogram after direct pyrolysis, represented by the total ion current (TIC) and the ion
chromatogram of selected indicator compounds. The amount pyrolyzed is given in the right
upper corner for selected polymers.
S-3
b) The pyrogram after thermochemolysis (TMAH addition), represented by the total ion
current (TIC) and the ion chromatogram of selected indicator compounds. The amount
pyrolyzed is given in the right upper corner for selected polymers.
Additionally the structure of the selected indicator ions is given in the respective ion traces.
In most of the pyrograms after thermochemolysis silyl artifacts are present. In the respective
pyrograms they are indicated with *1 (2,2,4,4,6,6-Hexamethyl-1,3,5,2,4,6-trioxatrisilinane)
and *2 (2,2,4,4,6,6,8,8-Octamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane) and are not included
in the individual tables of the polymers separately. The TMAH treated samples start with a
broad signal mainly refers to trimethyl amine indicated with a triangle.
o P3 4.56E4
TIC MS PE02C
TIC
50
P1 o 110 µg
Relative Abundance
0 NL:
100
a) 50
5.46E3
m/z=
82.50-83.50+
84.50-85.50 MS
0 PE02C
100 NL:
7.80E4
TIC MS PE_TT5
1.9*104 o 50
0
100 NL:
9.58E3
m/z 83+85
RT: 49.65 - 52.56 m/z=
Intensity
Time (min)
0 NL:
100
5.46E3
0 50
m/z=
82.50-83.50+
Δ
84.50-85.50 MS
o 0 P2 P3 PE02C
5.2*105
100 NL:
7.80E4 TIC
50 P1 TIC MS PE_TT5
240 µg
0
100 o NL:
9.58E3
m/z=
50 82.50-83.50+
84.50-85.50 MS
0 PE_TT5
50.0 50.5 51.0 51.5 52.0 52.5
Time (min)
0
0 20 40 60 80
Time (min)
peak
c) characteristic pyrolysis products m/z
notation
P1 n-alkadienes 82
P2 n-alkenes 83
P3 n-Alkanes 85
o Non PE-derived
d)
P1 – n-C20 alkadiene P2 – n-C20 alkene P3 – n-C20 alkane
55 83 57
100 100 100
82
111 85
50 97 50 280 50 282
125 99 127
123 152 139 281 283
250 278
0 0 0
100 200 300 100 200 300 100 200 300
m/z m/z m/z
S-4
2.2*107 TIC
a)
3.6*106 P1 m/z 70
8.3*105 P2 m/z 69
Intensity
2.2*107 Δ TIC
50 µg
*2
3.6*106 P1 m/z 70
8.3*105 P2 m/z 69
b)
0 20 40 60 80
Time (min)
c) peak
characteristic pyrolysis products m/z
notation
P1 2,4-Dimethyl-1-heptene 70 + 126
P2 2,4,6,8-Tetramethyl-1-undecenes (3 isomers) 69 + 111
d)
P2 - 2,4,6,8-Tetramethyl-1-undecenes (3 isomers)
69 69 69
100 100 100 85 111
83 111 85 111
50 50 50
0
125 154
210
0
125 154
210
0
cv 154 210
100 200 100 200 100 200
m/z m/z m/z
P1 - 2,4-Dimethyl-1-heptene
70
100
55
50 56 83 126
79 97 111
0
50 100
m/z
S-5
3.5*107 TIC
a)
5.0*106 P2 P3 m/z 91
Intensity
TIC
3.5*107
m/z 104
9.0*106 P1
b)
m/z 91
5.0*106 P2 P3
0 20 40 60 80
Time (min)
peak
c) characteristic pyrolysis products m/z
notation
P1 styrene 104
P2 3-butene-1,3-diyldibenzene (styrene dimer) 91
P3 5-hexene-1,3,5-triyltribenzene (styrene trimer) 91
d)
P1 - styrene P2 - 3-butene-1,3-diyldibenzene P3 - 5-hexene-1,3,5-triyltribenzene
104 91 91
100 100 100
S-6
* TIC
2.2*107
a) *
*
6.0*106 m/z 78
P1
P2
Intensity
2.2*107 Δ TIC
* *
* *
*
*
6.0*106 m/z 78
b) P1
P2
0 20 40 60 80
Time (min)
peak
c) characteristic pyrolysis products m/z
notation
P1 benzene 78
P2 chlorobenzene 112
* additives or additive derived
d)
P1 - benzene P2 - chlorobenzene
78 112
100 100
50 50 77 114
51 56 77 55 67 81 95 96
74 79 115
0 0
60 80 50 100
m/z m/z
S-7
TIC
100
a)
0
100 m/z 113
Relative Abundance
P1
0
100 Δ TIC
0
100 m/z 113
P1
b)
0
100 T1 m/z 127
0
0 10 20 30 40 50 60 70 80
Time (min)
c) peak
characteristic pyrolysis products m/z
notation
P1 ε-Caprolactam 113
T1 N-Methyl caprolactam 113 + 127
S-8
1.7*107 TIC
a)
3.6*106 P2 m/z 100
8.0*105 m/z 55
P1
Intensity
TIC
1.7*107
Δ
*1 *2
3.6*106 P2 m/z 100
b)
8.0*105 m/z 55
P1
0 20 40 60 80
Time (min)
peak
c) characteristic pyrolysis products m/z
notation
P1 Methyl acrylate 55 + 85 +86
P2 Methyl methacrylate 69 + 100
d)
P1 - Methyl acrylate P2 - Methyl methacrylate
55 69
100 100
100
50 50
58 85 59 85
68 86
0 0
60 80 60 80 100
m/z m/z
S-9
D3
8.0*106 TIC
a) D2
1024 µg
0
Intensity
Δ TIC
8.0*106
*2 7 µg
*1
2.0*105 T1 m/z 163
b)
0
0 20 40 60 80
Time (min)
c) peak
characteristic pyrolysis products m/z
notation
D1 Benzoic acid 105 + 122
D2 Ethan-1,2-diyldibenzoate 105 + 227
D3 2-(benzoyloxy)ethyl vinyl terephthalate 297
T1 Dimethyl terephthalate 163 + 194
d) D3 – 2-(benzoyloxy)ethyl
D1 – Benzoic acid D2 – Ethan-1,2-diyldibenzoate vinyl terephthalate
T1 – Dimethyl terephthalate
163
100
50 194
76 103 135
0
50 100 150 200
m/z
Figure S7. Polyethylene terephthalate (PET). To detect the volatile products of PET via direct
pyrolysis a comparatively high amount of polymer has to be pyrolyzed (cf. amounts given).
S-10
1.9*107 TIC
a)
D1 15 µg PC
1.9*107 Δ
TIC
Intensity
11 µg PC
T1
1.9*107 m/z 241
T2
b)
0 20 40 60 80
Time (min)
Peak
c) Characteristic pyrolysis products m/z
notation
D1 Triphenylphosphine oxide 277 + 278
T1 p-Methoxy-tert-butylbenzene 149 + 164
T2 2,2-Bis(4'-methoxyphenyl)propane 241 + 256
d) T2 –
D1 - Triphenylphosphine oxide T1 - p-Methoxy-tert-butylbenzene 2,2-Bis(4'-methoxyphenyl)propane
50 50 121 50
164 256
77 152 199 77 133 165
0 0 0
100 200 50 100 150 100 200
m/z m/z m/z
Figure S8. Polycarbonate (PC). In the pyrogram after direct pyrolysis (a) triphenylphosphine oxide
(flame retardant) was the only detectable signal due to the small amount used for pyrolysis.
S-11
Potential gas-phase polymerization of styrene
transferline (300°C). Since no further chromatographic separation occurs in the transline any
spontaneous polymerization product should show up in the mass spectrum of the styrene
monomer signal of the PS pyrogram. Even at higher PS concentrations (570 µg) neither m/z
208 (dimer) nor m/z 312 (trimer) was detectable. On m/z 91, the base peak of both oligomers,
only a slightly increased background noise level was detected. From these observations, one
may conclude, that spontaneous gas phase polymerization (back reaction) does not occur
Indicator
Polymer ion(s) for
Range (µg) N Calibration functions r²
type integration
m/z
PE 83 + 85 4 - 600 11 y=5.45*104+2.09*103*x 0.96
S-12
Fish sample Clean-up
The method was adopted and optimized after the method of M. Löder (pers. communication)
All solvents used were membrane filtered (0.45 µm) prior to use. One to five fish stomachs
(pelagic fishes) or GI-tracts (flat fishes), depending on fish sizes (<12 cm standard length
(SL), 5 stomachs/GI-tracts; <20 cm SL, 2-3 stomachs/ GI-tracts; >20 cm SL, 1stomach/ GI-
tract) were placed in a sintered glass crucible (D4), positioned in a glass beaker. The beaker
was covered with alumina foil that was only lifted for the addition of solutions and kept
closed during all other steps. After addition of 40 ml sodium dodecyl sulfate solution (5%,
Applichem, Germany) the sample was sonicated for 5 min and kept at 50°C for 3 h. The
crucible was placed on a vacuum filtration assembly, supernatant was vacuumed off and
residue was rinsed with water intensely. Following the addition of 40 ml Protease (AO-1, EC
3.4.21.62, ASA Spezialenzyme GmbH, Wolfenbüttel, Germany) and PBS-buffer (pH 9, Carl
Roth GmbH, Germany) mixture (1:5) sample was sonicated and incubated 24 h at 50°C.
Again supernatant was vacuumed off and residue rinsed with water. This was followed by
addition of 40 ml H2O2 (30%, VWR International, Germany). The mixture was kept at 50°C
for 3 h, sucked and washed. In case of a high chitin load this step was affiliated by addition of
PBS buffer (pH 5.6, Carl Roth GmbH, Germany) mixture (1:20) and an incubation for 48 h at
37°C. If necessary the H2O2 treatment was repeated. In case of visible grease contents the
residue was vacuum dried beforehand, treated with some milliliter portions of petrol ether
(40/60, Fisher Scientific, UK) and vacuum dried again. To remove sand particles, if
necessary, the residue was transferred into a separation funnel containing 50 ml sodium iodide
solution (density 1.6 g ml-1); sand particles were removed by dumping it together with 2/3 of
the fluid through the bottom outlet of the funnel. The treated sample was transferred
S-13
completely on an Anodisc® filter ( 13 mm, 0.2 µm, Watman, UK) narrowed to a 6 mm
radius under rigorous washing with ethanoic solution (10% in water) and pure ethanol (Fisher
Scientific, UK). Analogous the remaining density fluid and floating particles were washed as
well as rinsed directly on the Anodisc® filter. The stamped out filter section ( 6 mm) was
milled in a miniature agate bullet mortar and directly transferred into the pyrolysis targets. To
samples 10 µl of TMAH (25 % in water, Fluka, Germany) were added just before
0 20 40 60 80
1.4*104 1.2*103
Intensity
1.4*104 1.2*103
m/z 104 m/z 91
Standard
6 7 8 9 62 64 66
Time (min)
Figure S9: Pyrogram (TMAH) of chitin and opposed ion-chromatogram sections of styrene
monomer (m/z 104) and styrene trimer (m/z 91), and a PS standard equals 10 µg.
S-14
Table S4 Potential interferences of different biogenic polymers with polymer indicator
ions
methoxyphenyl)
ε-Caprolactame
alkenes/alkanes
Styrene Trimer
2,4,6,8-Tetra-
terephthalate
methacrylate
& N-Methyl
caprolactam
resp.
2,2-Bis(4'-
methyl-1-
monomer
undecene
Dimethyl
Benzene
Weight
propane
Styrene
Methyl
[µg]
Chitin
10 yes yes no no yes no no yes no
(Copepods)
Chitin
(Copepods 10 no yes no no no no no no no
digested)
Chitin (picked
1 piece no yes no no no no no no no
from sample)
Cellulose 8.6 no ? no no no no no no no
Wood 78.7 no ? no no no no no no no
Cotton fiber 9.9 no ? no no no no no no no
Wool fiber 6.3 yes yes no no no no no no no
? = detected in traces, possible contamination
S-15