Sorolla-Rosario, Débora; Llorca-Porcel, Julio; Lozano-Castelló, Dolores et al.

Working Paper
Microplastics’ Analysis in Water : Easy Handling of Samples by a
New Thermal Extraction Desorption-Gas Chromatography-Mass
Spectrometry (Ted-Gc/Ms) Methodology

Provided in Cooperation with:

Social Science Research Network (SSRN)

Reference: Sorolla-Rosario, Débora/Llorca-Porcel, Julio et. al. (2022). Microplastics’

Analysis in Water : Easy Handling of Samples by a New Thermal Extraction Desorption-Gas
Chromatography-Mass Spectrometry (Ted-Gc/Ms) Methodology. [S.l.] : SSRN.
https://ssrn.com/abstract=3992614.

This Version is available at:

http://hdl.handle.net/11159/495402

Kontakt/Contact
ZBW – Leibniz-Informationszentrum Wirtschaft/Leibniz Information Centre for Economics
Düsternbrooker Weg 120
24105 Kiel (Germany)
E-Mail: rights[at]zbw.eu
https://www.zbw.eu/econis-archiv/

Standard-Nutzungsbedingungen: Terms of use:

Dieses Dokument darf zu eigenen wissenschaftlichen Zwecken
und zum Privatgebrauch gespeichert und kopiert werden. Sie
dürfen dieses Dokument nicht für öffentliche oder kommerzielle
Zwecke vervielfältigen, öffentlich ausstellen, aufführen, vertreiben
oder anderweitig nutzen. Sofern für das Dokument eine Open-
Content-Lizenz verwendet wurde, so gelten abweichend von diesen
Nutzungsbedingungen die in der Lizenz gewährten Nutzungsrechte.
https://zbw.eu/econis-archiv/termsofuse
This document may be saved and copied for your personal
and scholarly purposes. You are not to copy it for public or
commercial purposes, to exhibit the document in public, to
perform, distribute or otherwise use the document in public. If
the document is made available under a Creative Commons
Licence you may exercise further usage rights as specified in
the licence.
1 Microplastics’ analysis in water: Easy handling of
2 samples by a new Thermal Extraction Desorption-
3 Gas Chromatography-Mass Spectrometry (TED-
4 GC/MS) methodology
5
6 Débora Sorolla-Rosario1*, Julio Llorca-Porcel1, Mónica Pérez-Martínez2, Dolores Lozano-
7 Castelló3, Agustín Bueno-López3.
8 1 Labaqua, S.A. C/ Dracma 16-18 Pol. Industrial Las Atalayas 03114 Alicante, Spain.
9 2 Interlab
laboratorios, S.L.U. C/ Aureliano Ibarra, 16 03009 Alicante, Spain
10 3 Department of Inorganic Chemistry, University of Alicante, Carretera de San Vicente s/n, E03080, Alicante, Spain

11
12 Abstract
13 Thermal Extraction-Desorption (TED) using a thermobalance coupled to a gas chromatograph
14 (GC) with mass spectrometer (MS) detector is an extended method for polymers identification
15 in complex matrixes. A new TED-GC/MS method for microplastics identification is developed in
16 this study, where the whole filter with solids collected from water is thermal treated in a furnace,
17 instead of using a small portion in a TGA device, avoiding sample handling. Pyrolyzing the whole
18 filter in a tubular furnace has advantages with respect to the standard procedure of using a TGA
19 with a small crucible in TED-GC/MS.
20 The main advantage is the easy manipulation of the sample, since the filter does not have to be
21 manipulated to extract the sample or cut some portions, avoiding sample losses during handling
22 and ensuring that inhomogeneity on the filter surface is not a problem.
23 Furthermore, there are no limitations on the weight of the sample beyond the adsorbent´s
24 ability to trap decomposition compounds without becoming saturated, so high intensity signals
25 can be obtained in order to avoid confuse signals with noise, false negatives or values so close
26 of the quantification limit.
27
28 Key words
29 Microplastic, TED-GC/MS, thermodecomposition, polymer, filter.

Electronic copy available at: https://ssrn.com/abstract=3992614

30 1.- INTRODUCTION.

31 Microplastics (MPs) are currently causing a growing interest both at the

32 scientific and social level. Those bits of plastic material, smaller than 5 mm, are observed nearly

33 everywhere in the water environments although most of the environmental samples are not

34 studied enough yet. One of the major handicaps to achieve scientific advances is the lack of

35 standardization when studying these MPs.

36 Spectroscopic technics, such as FTIR or Raman spectroscopies, are commonly used for

37 the MPs characterization, which can give information about particle number, size and identity

38 of the polymer1–4 but are time-consuming and require complicated sample preparation being

39 not suitable for particles smaller than 10 μm 5.

40 Thermal technics can offer identity and mass information across the entire MP size

41 range6 . Gas chromatography-mass spectrometry (GC/MS) is a very powerful tool to identify and

42 quantify volatile compounds upon thermal treatment of MP-containing samples, since each

43 compound in a complex mixture can be separated. Another very important advantage of

44 Thermal Extraction Desorption (TED) techniques coupled to GC/MS is that the released volatile

45 compounds can be retained on a selective adsorbent , and only the compounds retained in the

46 adsorbent are introduced into the chromatographic system afterwards, avoiding other

47 compounds that may be present in the matrix of the samples and the heavier compounds that

48 may arrive to obstruct the pipes and columns of the GC equipment, which results in high

49 maintenance costs7–10.

50 In order to determine microplastics using the TED-GC/MS techniques, they must first be

51 broken down into molecules with low boiling temperatures. For this purpose, subjecting the

52 polymers to a temperature program that causes thermal decomposition is a good solution, being

53 able to obtain structural information and a global vision of the changes produced in the polymers

Electronic copy available at: https://ssrn.com/abstract=3992614

54 during the increase in temperature. Furthermore, each polymer has characteristic degradation

55 products that can be used for their identification and/or quantification11, in addition to

56 presenting the advantage that these techniques can analyze both the polymer and additives in

57 the same experiment12.

58 Regarding the techniques based on Thermal Extraction-Desorption (TED), some studies

59 have been carried out where the sample is subjected to a temperature program in a

60 thermogravimetry equipment with an inert atmosphere, and the gases released are trapped in

61 a solid phase sorbent. The decomposition products are subsequently thermal desorbed and

62 analyzed in a Gas Chromatography-Mass Spectrometry (GC/MS) system8,10,13,14. In the

63 chromatographic column the compounds are separated and analyzed by means of a selective

64 mass detector. This method provides a chromatogram of the products generated during

65 pyrolysis with additional information from the mass spectrum that can be compared with a

66 known reference library to identify the polymer, being the identification of the compounds in

67 which the polymer has degraded simple and unequivocal, being able to analyze samples with

68 complex matrices.

69 Using thermogravimetric equipment has the advantage that mass loss information is

70 obtained, but it has multiple disadvantages. On the one hand, once the solid residue is filtered

71 from the water to be analyzed, the sample must be manipulated to be placed in the TGA crucible,

72 and during this process, some of the mass may be lost or the smallest particles may remain in

73 the filter. On the other hand, TGA crucible is too small to fit the entire filter, so only a fraction

74 must be cut and inserted into the TGA, and this small sample could not be representative of the

75 whole solid collected in the filter.

76 The main goal of this study is to develop a new Thermal Extraction-Desorption

77 methodology for microplastics identification, where the whole filter with solids collected from

78 water is thermal treated, instead of using a small piece, as it is usually done in the standard

Electronic copy available at: https://ssrn.com/abstract=3992614

79 procedures in TGA devices with a small crucible. In the new methodology developed in this

80 study, after filtering the microplastic-containing solids from water, the whole filter is dried and

81 placed into a reactor, pyrolyzing the complete solid waste together with the filter, avoiding

82 sample handling. This new procedure has been named TED-GC/MS (Thermal Extraction

83 Desorption-Gas Chromatography-Mass Spectrometry).

84

85 2.- MATERIALS AND METHODS.

86 2.1. Reference Materials.

87 Reference microplastic materials were chosen covering the most abundant types in

88 freshwater systems. The set of reference plastics studied include Polyethylene (PE), Polystyrene

89 (PS), Polyamide (PA), Polyethylene terephthalate (PET) (30% glass particles as reinforce),

90 Polypropylene (PP) and Polyvinylchloride (PVC), and were purchased from Sigma-Aldrich.

91 Water suspensions of 1 mg of each polymer studied were made separately using 200 ml

92 of ultrapure water.

93 2.2. Filtration

94 To isolate microplastic particles, the water suspensions were filtered in a vacuum

95 filtration system using quartz wool filters grade QMA (Whatman). Quartz filters are advisable

96 for this purpose, because they withstand the high temperatures reached in the furnace during

97 the pyrolysis process without generating compounds that can interfere with the analysis.

98 To avoid moisture, the microplastic-containing filters were dried at room temperature

99 in a silica desiccator at least for 48 hours.

100

Electronic copy available at: https://ssrn.com/abstract=3992614

101 2.3. Extraction.

102 The microplastic-containing filters, once dried, were introduced into a 2 cm internal

103 diameter tubular quartz reactor, which is placed horizontally inside a ceramic tubular furnace to

104 pyrolyze the complete solid waste together with the filter, avoiding sample handling. This is the

105 key step in TED-GC/MS process, where polymer molecules are thermally degraded and the

106 decomposition products are trapped in a solid phase sorbent. The temperature was raised from

107 25 to 600°C, with a heating rate of 10°C/min, in a nitrogen flow rate of 90 ml/min at the gas

108 outlet. It was previously confirmed by thermogravimetry that this maximum temperature is high

109 enough for total decomposition of all polymers.

110 A diagram of the pyrolysis setup using the tubular furnace is exposed in Figure 1.

111

112 Figure 1.- Pyrolysis setup diagram.

113

114 A solid sorbent (Polydimethylsiloxane-PDMS stir bar purchased to Gerstel) is fitted

115 downstream the reactor to collect the gas compounds released upon microplastics thermal

116 decomposition.

117 To prove the advantages of pyrolyzing the whole filter, analysis of a portion of 10 % of

118 the filter has been carried out in a TGA equipment model TGA/STA 449 F5 Jupiter from NETZSCH.

119 The temperature was raised from 25 to 600°C, with a heating rate of 10°C/min, in a nitrogen

120 flow rate of 90 ml/min at the gas outlet as with the tubular furnace.

121

Electronic copy available at: https://ssrn.com/abstract=3992614

122 2.3. Desorption-Gas chromatography/Mass spectrometry.

123 Once the decomposition products have been trapped in the solid sorbent, it is

124 introduced into a commercial thermodesorption unit (TDU), mounted on a cooling injection

125 system (CIS 4. Gerstel) used as a cryotrap and coupled to a gas chromatograph (GC) with mass

126 spectrometry (MS) detection.

127 Desorption occurs in two stages. In the first stage, the analytes are released in the TDU

128 from 70 to 300°C maintaining this temperature for 8 minutes for complete desorption of all

129 analytes from the solid phase and transferred through a heated capillary to the cryogenic trap.

130 This transfer capillary should always be at a temperature higher than the highest TDU

131 temperature (preferably above 20-30 °C) to ensure complete transfer of all analytes to the

132 cryogenic trap.

133 Once all the analytes have been adequately desorbed from the solid sorbent, the cryo-

134 focuser is cooled to -50 °C to retain all the compounds. After cooling, the temperature rises

135 rapidly, heating with a ramp of 12 ºC/s to 300 °C and maintaining this temperature for 8 minutes,

136 to transfer all the analytes to the GC column with minimal loss of sample. With this technique

137 99 % of the analytes are desorbed during the first seconds.

138 The GC/MS system was a 6890N GC (Agilent) coupled to a 5973 MSD (Agilent), and mass

139 spectrometry data acquisition was performed in scan mode, recording mass/charge (m/z) ratio

140 in two differentiated windows to optimize the detection of the most volatile compounds in the

141 shortest retention times. The first acquisition window covers the first 7 minutes where m/z

142 ratios were recorder from 35 to 100, and the second window, which covers from minute 7 to

143 the end of the chromatogram, where m/z ratios were reordered from 40 to 380.

144 Data analysis was performed with MassHunter Workstation (Qualitative Analysis)

145 version 10.0 software from Agilent Technologies.

Electronic copy available at: https://ssrn.com/abstract=3992614

146 The identification of the compounds was carried out considering the retention time (Tr)

147 and the characteristic ions (m/z) of each compound. The identification was completed with a fit

148 ≥80% in NIST14 and/or Wiley 11th Edition/NIST 2017 (W11N17).

149

150

151 3.- RESULTS AND DISCUSSION.

152 The different microplastics have been analysed by TED-GC/MS. Mass spectroscopy

153 signals have been used to obtain the characteristic m/z fingerprint of each material, and the best

154 m/z descriptors have been identified. In a further step, the selected m/z signals have been used

155 for a quantitative analysis of the different microplastics.

156 3.1. Qualitative identification of microplastic.

157 Each polymer has characteristic thermal decomposition compounds that depend on

158 their chemical structure. Finding those compounds in a chromatogram indicates the presence

159 of that polymer.

160 Figure 2 compiles the chromatogram of each studied polymer, showing their main

161 characteristic thermo decomposition compounds, as well as the most intense ions of the mixture

162 and their retention times.

163
Tr Tr
Polymer Peak Compound m/z Polymer Peak Compound m/z
(min) (min)
PVC 1 Naphthalene 27.3 128 PA 1 Caprolactam 29.1 113

164

Electronic copy available at: https://ssrn.com/abstract=3992614

 Tr Tr
Polymer Peak Compound m/z Polymer Peak Compound m/z
(min) (min)
2,4-Dimethyl-1-decene
PP 1 23.4 43 PE C11 Undecane 21.7 57
(propylene tetramer)
2,4,6,8-Tetramethyl-1- 29.6
PP 2 undecene (propylene 29.9 43 PE C12 Dodecane 23.7 57
pentamer) (3 isomers) 30.2
PE C13 Tridecane 25.9 57

PE C14 Tetradecane 28.6 57

165

166

167
Tr Tr
Polymer Peak Compound m/z Polymer Peak Compound m/z
(min) (min)
PS 1 Styrene 18.4 104 * Siloxane compound 20.7 191
1,3-Dimethyl-1-butene
PS 2 48.4 115 PET 1 2,4-Ditertbutylphenol 37.2 191
(Styrene dimer)
168
169 Figure 2. Chromatogram of each studied polymer, indicating their main thermo decomposition
170 product, including their retention time and the major ion in the mass spectra.

171

172 It is concluded from results in Figure 2 that the main ions obtained upon thermal

173 degradation of the studied polymers are unique for each polymer and can be used for proper

Electronic copy available at: https://ssrn.com/abstract=3992614

174 identification without interference the remaining polymers in case of multi-polymers samples.

175 However, in the real environmental samples, hydrocarbons and polyaromatic compounds can

176 be present in the matrix, so for a suitable identification of microplastics is advisable to identify

177 two or more of the characteristic m/z signals.

178 In summary, in the Table 1, the identification product together with some proposed

179 verification products are shown.

180

181 Table 1. Summary of the thermodecomposition compounds to analyse and verify the
182 identification of the studied polymers.

Polymer Identification compound (m/z) Verification compound (m/z)

PVC Naphthalene (128) Xylene (91)
Benzoic acid (105)
HCl (36)
Styrene (104)
PS 1,3-Diphenyl-1-butene (115) Styrene (104)
Methyl ethylbenzene (118)
PA Caprolactam (113)
PET 2,4-Ditertbutylphenol (191) Benzoic acid (105)
Diethyl phthalate (149)
2,4,6,8-Tetramethyl-1-undecene
PP 2,4-Dimetil-1-decene (43)
(3 isomers) (43)
PE Tetradecane (57) Decane (57)
Undecane (57)
Dodecane (57)

183

184 3.2. Quantitative results of microplastics concentrations.

185 To compare the results obtained with a Tubular furnace-GC/MS vs TGA-GC/MS, two

186 suspensions with 2 mg of polyethylene (PE) were filtered in quartz filters. The first filter was

187 completely pyrolyzed in the tubular furnace and the other one was processed in a TGA, where

188 only a portion of the filter was introduced in the crucible. The portion of the second filter

189 corresponds approximately to the 10% of the total filter, trying to introduce small portions that

Electronic copy available at: https://ssrn.com/abstract=3992614

190 are representative of the total filter, and the decomposition products were collected in a PDMS

191 Gerstel stir bar in the same conditions for both procedures.

192 The results of the chromatograms of the PDMS Gerstel stir bar are compared in Figure

193 3 for TGA and tubular furnaces desorption, where the signal of the characteristic decomposition

194 products for Polyethylene is much intense in the case of the tubular furnace than in the case of

195 the TGA.

x10 6 + TIC Scan PATRON.D

x10 7
2,1 1 1
2
8
1,9
1,8
1,7
7
1,6 2 mg PE (Tubular furnace/GC-MS)
1,5
6
1,4
1,3
1,2
5
1,1
1 2 mg PE (TGA/GC-MS)
4
0,9
0,8
3
0,7
0,6
0,5
2
0,4
0,3
1
0,2
0,1
00
28,4 28,45 28,5
5 10 15 20 28,55
25 28,6
30 28,6535 28,740 28,75
Counts 45 28,8Time
vs. Acquisition 5028,85 5528,9 60
28,95
6529 29,05 29,1 29,15 29,2
Counts vs. Acquisition Time (min) (min)

196

197 Figure 3. Comparation of the chromatograms of 2 mg of pure PE pyrolyzed by a tubular

198 furnace and a TGA.

199

200 Comparing the signals is evident that using a tubular furnace and pyrolyzing the filter

201 completely, the intensity is significatively increased. In the case of TGA-GCGC/MS, by having

202 such low intensities, there is a risk of being close the limit of quantification (LQ), which could

203 cause false negatives, avoiding it by increasing the intensity in the signal that gives us higher

204 concentrations.

205 Another aspect to consider is the homogeneity in the filter. Table 2 shows the area under

206 the curve of the peaks by both methods, where the area obtained experimentally of the 10% of

207 the filter with the TGA-GC/MS and the area that should have been obtained if we consider that

10

Electronic copy available at: https://ssrn.com/abstract=3992614

208 the microplastic particles are evenly distributed on the filter surface, as well as the peak area in

209 the case of effectively 100% pyrolyzed filter with the Tubular furnace-GC/MS.

210 As can be seen, the estimated tetradecane area for the complete filter pyrolyzed with

211 the TGA-GC/MS is more than four times less than the peak given for the filter effectively 100%

212 pyrolyzed. By means of this observation, it can be affirmed that the distribution of the particles

213 on the surface of the filter cannot be consider homogeneous, as well as the possibility of analyte

214 losses may have occurred during handling.

215

216 Table 2. Comparation of the peak area for both methods, considering portion analysed and the
217 total of the filter.
218 Tetradecane
10% filter pyrolyzed 100% filter pyrolyzed
Method
(peak area/ a.u.) (peak area/ a.u.)
219
TGA-GC/MS 163279 1632790*
Tubular furnace-GC/MS 6644975

220 * Estimation.

221 To evaluate the behaviour of the different polymer in both techniques, suspensions with

222 different amounts of each polymer studied were prepared and pyrolyzed in a TGA equipment

223 and in the tubular furnace. For both methods, the linearity in the results as well as the presence

224 of a larger area when the filters are completely pyrolyzed in the oven are considered.

225 Figure 4 plots the area of the main CG/MS signal for each polymer as a function of the

226 mass of polymer used in the preparation of each water suspension. The results obtained show

227 that, for all polymers, the filters pyrolyzed in the furnace present a much larger area than those

228 pyrolyzed in the TGA and have a greater slope, which is indicative of greater sensitivity. In

229 addition, as a general rule, data obtained with filters pyrolyzed in the TGA crucibles present

11

Electronic copy available at: https://ssrn.com/abstract=3992614

230 lower regression coefficients than those obtained with the whole filter thermal treated in a

231 furnace, which is indicative of low homogeneity of microplastics in the filter after filtration.

232

233

234

235 Figure 4. Comparation of the results pyrolyzing the filter in the tubular furnace (blue) and in a
236 TGA crucible (grey).

237

12

Electronic copy available at: https://ssrn.com/abstract=3992614

238 As a summary, this quantitative analysis allows concluding that the novel method

239 proposed in this study, based on the pyrolysis of the entire filters used for microplastics filtration

240 in water samples, yields values between 2 and 10 times more intense than those obtained in a

241 conventional TGA-based approach, being more convenient for identification of microplastics in

242 low concentration-samples.

243

244 4. CONCLUSIONS

245

246 A new Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (TED-

247 GC/MS) methodology is proposed in this study for microplastics identification in water samples,

248 where the whole filter used to collect the microplastics is pyrolyzed in a reactor instead of a

249 portion being thermal threated in a thermobalance, as usually done in TED-based techniques.

250 Pyrolyzing the whole filter in a tubular furnace has advantages with respect to use a TGA with a

251 small crucible in TED-GC/MS, being the main ones

252  Easy manipulation of the sample, since the filter does not have to be manipulated to

253 extract the sample or cut some portions, avoiding sample losses.

254  No limitations on the weight of the sample, so high intensity signals can be obtained in

255 order to avoid confuse signals with noise, false negatives or values so close of the LQ.

256  The furnace significantly increases the sensitivity with regard to TGA, represented by a

257 greater slope of the line when comparing samples with different polymer masses,

258 obtaining signals between 2 and 10 times more intense.

259  After filtering the samples containing microplastics, these particles are not distributed

260 homogeneously on the surface of the filter, so when taking a portion of the filter the result

261 is less representative, proven by observing a lower linearity in the results of known

262 masses.

13

Electronic copy available at: https://ssrn.com/abstract=3992614

263 Acknowledgements

264 Authors thank the funding from Vice-Rector for Research and Knowledge Transfer of the
265 University of Alicante (Project UAIND19-02), Labaqua and Interlab for funding the Industrial
266 Doctorate.

267

268 REFERENCES

269 1. Tagg, A. S., Sapp, M., Harrison, J. P. & Ojeda, J. J. Identification and Quantification of
270 Microplastics in Wastewater Using Focal Plane Array-Based Reflectance Micro-FT-IR
271 Imaging. Anal. Chem. 87, 6032–6040 (2015).

272 2. Hendrickson, E., Minor, E. C. & Schreiner, K. Microplastic Abundance and Composition in
273 Western Lake Superior As Determined via Microscopy, Pyr-GC/MS, and FTIR. Environ. Sci.
274 Technol. 52, 1787–1796 (2018).

275 3. Käppler, A. et al. Analysis of environmental microplastics by vibrational

276 microspectroscopy: FTIR, Raman or both? Anal. Bioanal. Chem. 408, 8377–8391 (2016).

277 4. Hendrickson, E., Minor, E. C. & Schreiner, K. Microplastic Abundance and Composition in
278 Western Lake Superior As Determined via Microscopy, Pyr-GC/MS, and FTIR. Environ. Sci.
279 Technol. 52, 1787–1796 (2018).

280 5. Peters, C. A. et al. Pyr-GC/MS analysis of microplastics extracted from the stomach
281 content of benthivore fish from the Texas Gulf Coast. Mar. Pollut. Bull. 137, 91–95 (2018).

282 6. Mintenig, S. M., Bäuerlein, P. S., Koelmans, A. A., Dekker, S. C. & Van Wezel, A. P. Closing
283 the gap between small and smaller: towards a framework to analyse nano- and
284 microplastics in aqueous environmental samples. Environ. Sci. Nano 5, 1640–1649
285 (2018).

286 7. Bitter, H. & Lackner, S. Fast and easy quantification of semi-crystalline microplastics in
287 exemplary environmental matrices by differential scanning calorimetry (DSC). Chem.
288 Eng. J. 423, 129941 (2021).

289 8. Dümichen, E. et al. Fast identification of microplastics in complex environmental samples

290 by a thermal degradation method. 174, 572–584 (2017).

291 9. Dehaut, A. et al. Microplastics in seafood: Benchmark protocol for their extraction and
292 characterization. Environ. Pollut. 215, 223–233 (2016).

293 10. Arroyo-manzanares, N., Ignacio, L. & Hern, M. Chemosphere An overview of

294 microplastics characterization by thermal analysis. 242, (2020).

295 11. Fischer, M. & Scholz-Böttcher, B. M. Simultaneous Trace Identification and Quantification
296 of Common Types of Microplastics in Environmental Samples by Pyrolysis-Gas
297 Chromatography–Mass Spectrometry. Environ. Sci. Technol. 51, 5052–5060 (2017).

298 12. Herrera, M., Matuschek, G. & Kettrup, A. Fast identification of polymer additives by
299 pyrolysis-gas chromatography/mass spectrometry. J. Anal. Appl. Pyrolysis 70, 35–42
300 (2003).

14

Electronic copy available at: https://ssrn.com/abstract=3992614

301 13. Dümichen, E. et al. Analysis of polyethylene microplastics in environmental samples ,
302 using a thermal decomposition method. Water Res. 85, 451–457 (2015).

303 14. Duemichen, E., Eisentraut, P., Celina, M. & Braun, U. Automated thermal extraction-
304 desorption gas chromatography mass spectrometry: A multifunctional tool for
305 comprehensive characterization of polymers and their degradation products. J.
306 Chromatogr. A 1592, 133–142 (2019).

307

308

15

Electronic copy available at: https://ssrn.com/abstract=3992614