Mass spectrometry in support of the environment, food, and health interaction and desease Antwerpen 2018 Identification and quantification of plastics and water soluble polymers in sewage and surface waters based on pyrolysis-GC/MS J an Schwarzbauer Institute of Geology and Geochemistry of Petroleum and Coal RWTH Aachen University
Polymers in the Environment Waste Beaches Kamilo-Beach at Hawai (waste removal rate: 52 tons per year) Very small (down to microscopic scale) plastic particles can account for up to 25% of weight in beach sands Waste in Los Angeles River collected after a storm event
Polymers in the Environment The 5 biggest oceanic gyres Oceanic Garbage Patches • Great Pacific Garbage Patch (Pacific Trash Vortex): Area of 7000.000 to 1.500.00 km 2 , contains 100 M io. tons of dominantly plastic waste • According to an UNEP-study the average particle frequency on the oceans surface is approx. 18.000 plastic particles/ km 2 • A rough calculation indicated a particle frequency on the oceans floor of approx. 11.000 plastic particles/ km 2 • Plastic parts in oceanic travel with approx. 7cm/ s for ca. 16 years resulrting in a distance of ca. 10.000 km (circulation time 2 - 4 years for one round)
Polymers in the Environment Impact on marine organism
Structural diversity of synthetic polymers Polypropylene PP Polymer Applications Wide application: plastic Polyethylene (PE) wrap, bin liner … n Polypropylene (PP) Ropes, helmets … Polyvinylchloride PVC Polystyrene (PS) Insulant, packaging … Polyethylene terephthalate Cl Cl Cl Bottles, textile fibers … (PET) n Polyvinylchloride (PVC) Tubes, flooring … Polymethyl methacrylate Plexiglas, transparent Polyamides PA (PMMA) plates .. O O Polyamide (PA) Stockings, fibres …. R R O N N O n H H Polyurethane (PUR) Foams, membranes Polyacrylamide (PAA) Flocculants, absorbers .. Polyethylene terephthalate PET O O O O O O n O O
Plastic class Acronym Specific Density Main Use (g/cm³) Foamed polystyrene XPS 0.028-0.045 House building, floats, foam cups Polypropylene PP 0.905 Folders, fod packaging, car bumper etc. will float on water, available for Low-density polyethylene LDPE 0.92 Films for food packaging, reusable bags, etc uptake by filter feeders or High-density HDPE 0.96 Toys, milk bottles, and pipes planktivorous polyethylene Polyvinyl chloride PVC 1.35-1.39 Window frames, flooring and pipes, clothes, etc. Density Polyurethane PUR 1.2 Mattresses and insulation panels Polystyrene PS 1.05-0.07 Spectacle frames, plastic cups, packaging, etc. Polyethylene PET 0.96-1.45 (av. Plastic beverage bottles and packaging ? terephthalate 1.38-1.41) Acrylonitrile butadiene ABS 1.01-1.08 Pipe systems, automotive components, styrene medical devices, musical instruments, etc. Polyamide (nylon) PA 1.02-1.06 Textile, automotive applications, carpets and sportswear, etc. Polycarbonate PC 1.20-1.22 Electronic components, construction materials, dates storage, automotive components, etc. Polymethyl methacrylate PMMA 1.09-1.20 Transparent glass substitute, medical will sink, (acrylic) technologies and implants, etc. accumulation in sediments Polytetrafluoroethylene PTFE 2.1-2.3 Industrial applications, coating on kitchen (teflon) saucepans, frying Pans
Analytical approaches .... for detecting/determining microplastic in particulate matter samples (soils & sediments) Spectroscopy Pyrolytic analyses µFTIR, µRaman Pyrolysis-GC/MS • Non-destructive method • Destructive method • Specific absorption bands • Specific pyrolyses products are needed are needed • 'Eliminates' matrix • Quantification using external calibration • Fast measurement • Matrix interfere • No quantification • Particle separation/isolation • Extensive sample is partly needed (pre)treatment Complementary approaches with individual Pro's and Con's
µFTIR as analytical alternative sand Resin resin Sand particle Resin PVC PET
A Artificial sand samples PE in sand sample (3.7%) B A B µFTIR as analytical alternative
Motivation Polymer analysis needs identification and quantification The environment is not only affected by insoluble plastics but also by water soluble polymers Py-GC/ M S Pyrolysis GC/ M S – specificty of Pyrolysis GC/ M S – quantification pyolytic products Polyvinylpyrrolidone - Chemically modified Chemically modified PVP Polyacrylamide - P AbF cellulose - CEC, HEC M unicipal sewage Flocculants in S TP Drilling fluids effluents Soils and aquatic M arine water and Surface water sediments sediments
Pyrolysis-GC/MS approach Polymer Identification pyrolysis-GC/MS Specific Py-products Quantification external calibration with marker Concentrations
'History' Polystyrene in polluted sediments, Po river, Italy: R R Comparison with reference material (styrene) Signal linearity of styrene vs polystyrene content Quantitative results: 1.0 to 3.9 mg/g (Fabbri, Trombini, Vassura, J Chromat Sci 1998)
Pyrolysis-GC/MS approach on-line Py-GC/MS off-line continous flow pyrolysis TMAH Thermochemolysis Closed off-line pyrolysis
Identification of specific pyrolysis products ☹ ️ PS PMMA → MMA � O 41 69 O 39 100 40 50 60 70 80 90 100 m/z
Identification of specific pyrolysis products 77 103 100 50 39 63 74 89 49 79 65 53 98 101 87 106 110 44 93 115 119 123 127 131 139 152 165 0 43 84 89 97 39 63 74 51 50 78 Styren (Monomer) 100 104 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 C omponent at scan 475 (9.278 m in) [Model = +77u] in D:\ DESKT Head to Tail MF=543 RMF=544 Styrene 115 103 100 78 51 91 39 50 63 65 50 57 52 74 76 89 62 38 40 79 53 61 64 87 90 92 49 66 73 43 45 80 98 108 113 123 126 129 0 43 49 55 86 92 98 38 40 52 74 76 79 89 58 65 50 63 91 115 39 51 78 50 α -Methylstyrene 103 polystyrene pyrolysis 100 118 30 40 50 60 70 80 90 100 110 120 130 140 C omponent at scan 848 (13.429 min) [Model = +117u] in D:\ DESKT Head to Tail MF=861 RMF=864 α- Methylstyrene 115 130 208 100 193 178 91 165 50 77 89 51 39 63 82 152 94 103 139 2.68 41 69 97 202 57 219 0 70 82 95 139 152 39 51 65 103 77 89 165 130 178 91 50 Dimer 100 193 208 115 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 C omponent at scan 3832 (46.602 min) [Model = +193u] in D:\ DESK Head to Tail MF=842 RMF=854 Benzene, 1,1'-(3-methyl-1-propene-1,3-diyl)bis- 23.59 40.85 m/z: 104 Monomer Relative Abundance m/z: 104 Dimer m/z: 208 m/z: 208 Trimer m/z: 312 m/z: 312 Time (min)
Identification of specific pyrolysis products 203 Terephthalic acid 3-dibutenylester 100 polyethyleneterephthalate pyrolysis 149 50 76 104 65 38 121 55 49 80 93 0 50 132 39 80 93 65 76 121 104 OH H 3 C 54 149 CH 3 50 100 CH 3 95 100 203 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 90 85 H 3 C CH 3 80 CH 3 75 2,4-Di-tert-butylphenol 70 65 CH 2 OH H 3 C 60 O O O 55 Undecanoic acid O 50 O O 45 40 Terephthalic acid 3-dibutenylester H 2 C 35 Benzaldehyde 30 25 20 15 10 5 0 0 10 20 30 40 50 60 70 80 90 100 110
Identification of specific pyrolysis products 1 2 R R n Cl Cl Cl Cl Cl Pyrolysis products of PVC naphthalene m/z 128 Relative Abundance 1- and 2-methylnaphthalenes m/z 142 fluorene m/z 166 anthracene m/z 178 Time (min)
Formation of pyrolysis products of PVC 1 2 R R Molecular structure of PVC n Cl Cl Cl Cl Cl 1 2 R R 1 CH + 2 2+ + + R + R - + H C CH CH + + 5 Cl + H 2 C CH 2 CH 3 Cl Cl Cl Cl Cl Potential cleavage Reactive species 2+ H C + + CH CH 2+ + + - H C CH CH + + - + 3 + + 3 + 3 Cl CH H 3 Cl H Cl CH 2 + + CH CH 2+ H C formation of monocyclic structures and hydrochloric acid - stabilisation Formation of polycyclic aromatic compounds
Variation of pyrolysis temperatures 423 °C polystyrene pyrolysis 590 °C Relative Abundance 764 °C Time (min)
Reproducibility 7,84 11,70 25,71 11,23 20,13 7,84 11,70 25,74 20,16 7,62 Relative Abundance Polyvinylchloride pyrolysis 11,75 25,43 19,86 7,63 Retention time Compound 11,00 (min) 25,42 19,86 7 Naphthalin 7,61 11 1- and 2- Methylnaphthalene 10,98 20 Fluorene 25,41 19,85 25 Antracene Time (min)
Pittfalls polystyrene pyrolysis 2,26 pyrolysate without rinsing glass ware 25,30 Relative Abundance 42,77 rinsed from glass ware 2,25 2,68 combination 23,59 40,85 Time (min)
Polyvinylpyrrolidone PVP • Hygroskopic (soluble in water and polar organic solvents) • M w of 2.500 to 2.500.00 Dalton Example 1 • High production rate • Wide application PVP-Iodine disinfectant Contact lense cleaner Shampoos Hair spray Ink transfer inhibitor in washing agents Binder in tablets Blood plasma expander M embranes in drinking water filtration Food additive E1201 • High environmental stability (Trimpin et al. 2001) • No information avalaible about environmental behaviour
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