[PPT] - Mass spectrometry in support of the environment, food, and health PowerPoint Presentation

SLIDE 1

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

f Petroleum and Coal

RWTH Aachen University

Mass spectrometry in support of the environment, food, and health interaction and desease Antwerpen 2018

SLIDE 2

Waste in Los Angeles River collected after a storm event 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

Polymers in the Environment

SLIDE 3

Great Pacific Garbage Patch (Pacific Trash Vortex): Area of

7000.000 to 1.500.00 km2, 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/ km2

A rough calculation indicated a particle frequency on the
ceans floor of approx. 11.000 plastic particles/ km2
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)

The 5 biggest oceanic gyres

Oceanic Garbage Patches

Polymers in the Environment

SLIDE 4

Polymers in the Environment Impact on marine

rganism

SLIDE 5

Polymer Applications Polyethylene (PE) Wide application: plastic wrap, bin liner … Polypropylene (PP) Ropes, helmets … Polystyrene (PS) Insulant, packaging … Polyethylene terephthalate (PET) Bottles, textile fibers … Polyvinylchloride (PVC) Tubes, flooring … Polymethyl methacrylate (PMMA) Plexiglas, transparent plates .. Polyamide (PA) Stockings, fibres …. Polyurethane (PUR) Foams, membranes Polyacrylamide (PAA) Flocculants, absorbers ..

O O O O O O O O

n

Polyethylene terephthalate PET

R O O N H R N H O O n

Polyamides PA

n

Polypropylene PP Polyvinylchloride PVC

Cl Cl Cl n

Structural diversity of synthetic polymers

SLIDE 6

Plastic class Acronym Specific Density (g/cm³) Main Use Foamed polystyrene XPS 0.028-0.045 House building, floats, foam cups Polypropylene PP 0.905 Folders, fod packaging, car bumper etc. Low-density polyethylene LDPE 0.92 Films for food packaging, reusable bags, etc High-density polyethylene HDPE 0.96 Toys, milk bottles, and pipes Polyvinyl chloride PVC 1.35-1.39 Window frames, flooring and pipes, clothes, etc. Polyurethane PUR 1.2 Mattresses and insulation panels Polystyrene PS 1.05-0.07 Spectacle frames, plastic cups, packaging, etc. Polyethylene terephthalate PET 0.96-1.45 (av. 1.38-1.41) Plastic beverage bottles and packaging Acrylonitrile butadiene styrene ABS 1.01-1.08 Pipe systems, automotive components, 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 (acrylic) PMMA 1.09-1.20 Transparent glass substitute, medical technologies and implants, etc. Polytetrafluoroethylene (teflon) PTFE 2.1-2.3 Industrial applications, coating on kitchen saucepans, frying Pans

Density

will sink, accumulation in sediments will float on water, available for uptake by filter feeders or planktivorous

?

SLIDE 7

Pyrolytic analyses Pyrolysis-GC/MS

Destructive method
Specific pyrolyses products

are needed

Quantification using

external calibration

Matrix interfere
Particle separation/isolation

is partly needed Spectroscopy µFTIR, µRaman

Non-destructive method
Specific absorption bands

are needed

'Eliminates' matrix
Fast measurement
No quantification
Extensive sample

(pre)treatment

Complementary approaches with individual Pro's and Con's

.... for detecting/determining microplastic in particulate matter samples (soils & sediments) Analytical approaches

SLIDE 8

sand resin

PET Resin Sand particle Resin PVC µFTIR as analytical alternative

SLIDE 9

PE in sand sample (3.7%)

A B A B

Artificial sand samples µFTIR as analytical alternative

SLIDE 10

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

Motivation

Chemically modified Polyacrylamide - P AbF Polyvinylpyrrolidone - PVP Chemically modified cellulose - CEC, HEC Flocculants in S TP Soils and aquatic sediments M unicipal sewage effluents Drilling fluids Surface water M arine water and sediments Pyrolysis GC/ M S – specificty of pyolytic products Pyrolysis GC/ M S – quantification

SLIDE 11

Pyrolysis-GC/MS approach

Polymer Specific Py-products Concentrations Identification pyrolysis-GC/MS Quantification external calibration with marker

SLIDE 12

Polystyrene in polluted sediments, Po river, Italy: 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)

R R 'History'

SLIDE 13

TMAH Thermochemolysis Closed off-line pyrolysis

ff-line continous flow

pyrolysis

Pyrolysis-GC/MS approach

n-line Py-GC/MS

SLIDE 14

40 50 60 70 80 90 100 m/z

39 41 69 100

O O

PMMA → MMA PS

Identification of specific pyrolysis products

☹️

SLIDE 15

Time (min) Relative Abundance

2.68 23.59 40.85

Monomer m/z: 104 Dimer m/z: 208 Trimer m/z: 312

m/z: 104 m/z: 208 m/z: 312

C

mponent at scan 3832 (46.602 min) [Model = +193u] in D:\ DESK

Benzene, 1,1'-(3-methyl-1-propene-1,3-diyl)bis- Head to Tail MF=842 RMF=854 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 50 100 50 100 39 39 41 51 51 57 63 65 69 70 77 77 82 82 89 89 91 91 94 95 97 103 103 115 115 130 130 139 139 152 152 165 165 178 178 193 193 202 208 208 219

Dimer

C

mponent at scan 848 (13.429 min) [Model = +117u] in D:\ DESKT

α-Methylstyrene Head to Tail MF=861 RMF=864 30 40 50 60 70 80 90 100 110 120 130 140 50 100 50 100 38 38 39 39 40 40 43 43 45 49 49 50 50 51 51 52 52 53 55 57 58 61 62 63 63 64 65 65 66 73 74 74 76 76 78 78 79 79 80 86 87 89 89 90 91 91 92 92 98 98 103 103 108 113 115 115 118 123 126 129

α-Methylstyrene

C

mponent at scan 475 (9.278 m

in) [Model = +77u] in D:\ DESKT Styrene Head to Tail MF=543 RMF=544 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 50 100 50 100 39 39 43 44 49 51 53 63 63 65 74 74 77 78 79 84 87 89 89 93 97 98 101 103 104 106 110 115 119 123 127 131 139 152 165

Styren (Monomer)

polystyrene pyrolysis

Identification of specific pyrolysis products

SLIDE 16

polyethyleneterephthalate pyrolysis

10 20 30 40 50 60 70 80 90 100 110 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 50 100 50 100 38 39 49 50 54 55 65 65 76 76 80 80 93 93 104 104 121 121 132 149 149 203 203

O O O O CH2 C H2

Terephthalic acid 3-dibutenylester

Benzaldehyde

O

2,4-Di-tert-butylphenol OH C H3 CH3 CH3 C H3 CH3 CH3

C H3 OH O

Undecanoic acid

Identification of specific pyrolysis products

SLIDE 17

naphthalene m/z 128 1- and 2-methylnaphthalenes m/z 142 fluorene m/z 166 anthracene m/z 178 Time (min) Relative Abundance

Pyrolysis products of PVC

R

1

Cl Cl Cl Cl R

2

Cl n

Identification of specific pyrolysis products

SLIDE 18

R

1

Cl Cl Cl Cl R

2

Cl n

Molecular structure of PVC

R

1

Cl Cl Cl Cl R

2

Cl

Potential cleavage

R

1 CH +

CH3



+

C H

2+

CH

+

CH

+

CH2

+

C H2

+ R 2

+ + 5 Cl

Reactive species

C H

2+

CH

+

CH

+

CH2

+

3 Cl

CH

+

C H

2+

CH

+

CH

+

CH

+

CH

+

C H

2+

+ 3

3 Cl

+

H

+

+ 3

Cl H

formation of monocyclic structures and hydrochloric acid - stabilisation Formation of polycyclic aromatic compounds

Formation of pyrolysis products of PVC

SLIDE 19

Time (min) 423 °C 590 °C 764 °C Relative Abundance

polystyrene pyrolysis

Variation of pyrolysis temperatures

SLIDE 20

Time (min) Relative Abundance 7,84 11,70 25,71 11,23 20,13 7,84 11,70 25,74 20,16 7,62 11,75 25,43 19,86 7,63 11,00 25,42 19,86 7,61 10,98 25,41 19,85 Retention time (min) Compound 7 Naphthalin 11 1- and 2- Methylnaphthalene 20 Fluorene 25 Antracene

Polyvinylchloride pyrolysis

Reproducibility

SLIDE 21

pyrolysate without rinsing glass ware

Time (min) Relative Abundance

2,26 25,30 42,77 2,25 2,68 23,59 40,85

polystyrene pyrolysis

rinsed from glass ware combination

Pittfalls

SLIDE 22

Hygroskopic (soluble in water and polar organic solvents)
M w of 2.500 to 2.500.00 Dalton
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

Polyvinylpyrrolidone PVP Example 1

SLIDE 23

Analytical problems in detecting PVP in environmental samples:

Isolation from water matrices
Low concentration level

S Trimpin, P Eichhorn, H J Räder, K M üllen, T P Knepper Recalcitrance of poly(vinylpyrrolidone): evidence through matrix- assisted laser desorption- ionisation time-of-flight mass spectrometry Journal of Chromatography A 938, 67-77

N O N O Pyrolysis

Py-GC/ FID (1990) M embranes: ~ 1.0 µg/ g Py-GC/ M S (1998) Washing agents: LOD 0.05%

Polyvinylpyrrolidone PVP

SLIDE 24

nline-pyrolysis

5.0 3.5 2.5 1.5 1.0 0.5

Amount of PVP in µg

N O N O N H O

T = 750°C; t = 5s PVP K30 (Sigma-Aldrich) M w 55.000 g/ mol

+

Polyvinylpyrrolidone PVP

1 2 3 4 5

R2 = 0.998 Area NVP µg PVP

Good reproducibility

SLIDE 25

Continous-flow offline-pyrolysis

12 14 16 18 20 22 24

125 g PVP

12 14 16 18 20 22 24

Retention time

20 g PVP

12 14 16 18 20 22 24

NVP

1000 g PVP

pyrrolidone

Relative increase of pyrrolidone vs NVP with decreasing amount

f pyrolysis educt



Adsorption of PVP on ceramic surfaces shifts pyrolysis yields as

bserved

V M Bogatyrev, N V Borisenko, V A Pokrovskii (2001) Thermal Degradation of Polyvinylpyrrolidone on the Surface

f Pyrogenic Silica

Russian Journal of Applied Chemistry 74, 839-844.

Polyvinylpyrrolidone PVP

SLIDE 26

200 400 600 800 1000 25 50 75 100 125 R2 = 0.9966 µg NVP µg PVP

Recovery rates determined by spiked waste water samples (n=6, PVP ca. 100µg): 92.3 % - 96.5 %; average: 94.6 % ± 1.5 % (abs.) Pyrolysis yield (n=3) PVP NVP [µg] 1000 9.4 % ± 0.2 750 9.6 % ± 0.1 500 8.5 % ± 0.8 250 10.1 % ± 0.7 125 8.4 % ± 0.3 50 9.2 % ± 0.1 20 9.2 % ± 0.1

Reproducibility

Polyvinylpyrrolidone PVP

Continous-flow offline-pyrolysis

SLIDE 27

9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Time (min)

CPVP = 7.1 mgL

56 68 82 111

: 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Time (min)

M unicipal waste water Aachen Waste water Pancevo CPVP = 2.9 mgL

N O

Surrogate standard

N O

Polyvinylpyrrolidone PVP

Continous-flow offline-pyrolysis

Surrogate standard

SLIDE 28

Polyacrylamide based flocculants (PAbF) are mainly used in sewage treatment

for clarification of industrial and municipial waste

water

for the removal of solids during the primary settling

step

for sludge thickening

Polyacrylamide based flocculants PAbF Example 2

SLIDE 29

Chemical properties

CO CO CO CO NH2 NH2 NH2 NH2

n

cationic-modified anionic-modified

Molecular mass : 105 to 107 Da
Stable below 210 ° C
Soluble in water, formamide, morpholine,

DMSO, ethylene glycol etc.

CO CO CO CO NH NH2 NH2 N H NMe3 + Me3N+

n

COO- CO CO COO- NH2 NH2

n

Polyacrylamide based flocculants PAbF

SLIDE 30

Economical aspects World wide production of polyacrylamides :

approx. 100.000 to 200.000 t/a

Polyacrylamides used as flocculants: approx. 50% Geographically distribution of polyacrylamides usage : 40% USA 30% Europe 30% Japan Consumption in Germany :

approx. 10.000 to 20.000 t per year

Polyacrylamide based flocculants PAbF

SLIDE 31

Release of PAbF to the pedosphere Sewage slugdes are used for fertilisation in agriculture ( Germany : approx. 35% , 15 M io t/a) Restrictions by law (Germany): Within 3 years a maximum of 5 to 10 tons (dry matter) sewage slugde per 10.000 m2 can be discharged on agricultural soils To a minor extend polyacrylamide based thikening agents mixed with pesticides are used to aid in reducing spray drift Polyacrylamide based flocculants PAbF

SLIDE 32

PAbF are known to show

a high environmental stabilitity
high geoaccumulation rates
no bioaccumulation
no significant biotic degradation
ecotoxicological effects in the aquatic environment

Organismn LD50 / EC

50 (mg/ L)

cationic P AbF (dispers) Bacteria 0.9 -7500 Algae 0.2 - 7500 Fishes 0.06 - 1000

Environmantal aspects of PAbF

Canadian diamond mine effluents : Cationic DADM AC 48h median lethal concentrations (LC50) for Ceriodaphnia dubia 0.3 to 0.7 mg/ L

NH2 R R +

Rosemund, Liber (2004) Environ Toxicol Chem

SLIDE 33

No data are reported concerning the ecotoxicological

effects of PAbF in the pedosphere

No analytical methods are known for identification and

quantification of PAbF in environmental samples Although high amounts of PAbF are released to the environment no information about the distribution, fate and ecotoxicological effects in soils are available or can be aquired.

Polyacrylamide based flocculants PAbF State-of-the-Art

SLIDE 34

25 50 75 100 7 14 21 28 35 42 time (d) Inhibition (%)

AN 234 K6-60 PK55H

Respiration activity in soil spiked with PAbF ( 250 to 500 mg / kg )

Ecotoxicological Effects

SLIDE 35

Assumptions:

5 t sewage sludge (dry matter) applied on 10.000 m2
Content of PBaF in sewage sludges: 10 kg/ t (dry matter)
Soil density: 1.5 - 1.8 g/cm3
Depth of agricultural treatment: 0.3 - 0.5 m

5 - 10 mg / kg soil

r 1 - 3 mg / kg per year

Estimated maximal concentrations in soils

SLIDE 36

Products of TM AH thermochemolysis

N O O N O O N O O TIC 127 141 155

R' R HN R' HN OC CO R' CO HN NH CO R' R'

SLIDE 37

Polyacrylamide based flocculants PAbF

with TMAH without TMAH

SLIDE 38

SLIDE 39

Synthesis of reference substances

N O O O OH O H O N N N N N O O

+ +

H3PO4 / >200°C K2CO3 + MeI / PTK

1,3-Dimethylglutarimide Polyacrylamide based flocculants PAbF

SLIDE 40

time temperature On-line

(TMAH)

T 400 °C 30 min 650 °C 2.5 s

Optimization of pyrolysis

T

t t

Off-line

(TMAH)

35 40 45 min On-line pyrolysis (650°C, 2.5 s) 25 µg of a cationic P AbF

reproducibility

SLIDE 41

Linearity / Sensitivity

R

2 = 0.99

R

2 = 0.99

2 4 6 8 10 12 µg

N O O N O O

Peakarea

Optimization of pyrolysis

SLIDE 42

Sewage sludge sample

113 127 139 141 153 TIC 113 127 139 141 153 TIC 113 127 139 141 153 TIC

?

Cationic PAbF Sewage slugde Sewage slugde

(preextracted with acidic M eOH)

Detection of PAbF in a complex matrix

SLIDE 43

Soil sample spiked with PAbF

TIC TIC m/z 139 m/z 127 m/z 127 m/z 153 m/z 153 m/z 141 m/z 141 m/z 113 m/z 113

Polyacrylamide based flocculants PAbF

SLIDE 44

Soil sample affected by sewage slugde

TIC 113 127 139 141 153 TIC 113 127 139 141 153

approx. 70 µg/g

Polyacrylamide based flocculants PAbF

SLIDE 45

M ass spectrometic identification

42 55 70 83 101 127 55 70 98 127 42 55 83 101 127 42 98 98 70

m/z

Cationic PAbF Soil sample spiked with PAbF Soil sample affected by sewage slugde

N O O

98 70

Polyacrylamide based flocculants PAbF

SLIDE 46

Polymers in drilling fluids

Drilling fluids are important additives for exploration and production drilling in terrestrial and marine environments. Up to 95% of all exploration and production wells used water-based muds. These are mixed with clays and polymers, in order to meet subsurface requirements like stabilization of the borehole and regulation

f the flow and filtration properties

Harmful effects are described e.g. by Khodja et al. (2010), Dijkstra et al. (2013), Trannum et al. (2011), Bechmann et al. (2006) Their usage is not a strictly closed system application, hence continuous emission of drilling fluids towards ecosystems are evident. (Apaleke et al. 2012) Detection and quantitation of drilling emissions are highly relevant

Example 3

SLIDE 47

Polymers in drilling fluids

Preparation and

execution of drilling

Handling of drilling

mud Storage and disposal

f drilling mud

Transport of drilling mud Execution of drilling

In average 25% of drilling cuttings are released during off-shore drilling

Water-based drilling cuttings are allowed to be discharged offshore Current amount of in-situ cutting piles: Central North Sea 700,000 m3

SLIDE 48

Carboxymethyl-cellulose (CMC) Hydroxyethyl-cellulose (HEC)

Further components: Xanthan, Bentonite, Barite, etc.

Polyacrylamide (PAA)

Chemical structures of common drilling additive polymers

Drill cutting – 4300 times enlarged

Detection of drilling activities in marine environment Identification of characteristic pyrolysis products of polymers used as main compounds in drilling fluids Proof of ability if these specific substances can act as drill cutting indicators

Polymers in drilling fluids

SLIDE 49

Carboxymethylcellulose (CMC) Polymers in drilling fluids

SLIDE 50

Polymers in drilling fluids

SLIDE 51

Hydroxyethylcellulose (HEC) Polymers in drilling fluids

SLIDE 52

SLIDE 53

Reproducibility Influence of pyrolysis temperature

Polymers in drilling fluids

SLIDE 54

< 1 mg DF/g Quantity/LOQ

Polymers in drilling fluids

SLIDE 55

Cellulose based drilling fluids < 1 mg DF/g

Polymers in drilling fluids

SLIDE 56