mass spectrometry in support of the environment, food, and ... · pyrolysis-gc/ms jan schwarzbauer...

Identification and quantification of plasticsand water soluble polymers in sewage andsurface waters based on pyrolysis-GC/MS

Jan SchwarzbauerInstitute of Geology and Geochemistryof Petroleum and CoalRWTH Aachen University

Mass spectrometry in support of theenvironment, food, and health interaction and desease

Antwerpen 2018

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 particlescan account for up to 25% of weight in beach sands

Polymers in the Environment

• Great Pacific Garbage Patch (Pacific Trash Vortex): Area of7000.000 to 1.500.00 km2, contains 100 Mio. tons ofdominantly 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 theoceans 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



Impact on marine organism

Polymer Applications

Polyethylene (PE) Wide application: plasticwrap, 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

OO

OO

O OO

n

Polyethylene terephthalate PET

R O

O

NH

RNH

O

O

n

Polyamides PA

n

Polypropylene PP

Polyvinylchloride PVC

Cl Cl Cl

n

Structural diversity of synthetic polymers

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 butadienestyrene

ABS 1.01-1.08 Pipe systems, automotive components, medical devices, musicalinstruments, 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, medicaltechnologies 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

?

Pyrolytic analysesPyrolysis-GC/MS

• Destructive method• Specific pyrolyses products

are needed• Quantification using

external calibration• Matrix interfere• Particle separation/isolation

is partly needed

SpectroscopyµFTIR, 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

sand

resin

PET

Resin

Sand particle

Resin

PVC

µFTIR as analytical alternative

PE in sand sample(3.7%)

A

B

A

B

Artificial sand samples

µFTIR as analytical alternative

Polymer analysis needs identification and quantificationThe environment is not only affected by insoluble plastics but also by watersoluble polymers

Py-GC/MS

Motivation

Chemically modifiedPolyacrylamide - PAbF

Polyvinylpyrrolidone -PVP

Chemically modifiedcellulose - CEC, HEC

Flocculants in STP

Soils and aquaticsediments

Municipal sewageeffluents Drilling fluids

Surface water Marine water andsediments

Pyrolysis GC/MS – specificty ofpyolytic products

Pyrolysis GC/MS – quantification

Pyrolysis-GC/MS approach

Polymer

SpecificPy-products

Concentrations

Identification pyrolysis-GC/MS

Quantification external calibrationwith marker

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)

RR

'History'

TMAH ThermochemolysisClosed off-line pyrolysis

off-line continous flowpyrolysis

Pyrolysis-GC/MS approach

on-line Py-GC/MS

40 50 60 70 80 90 100 m/z

39

4169

100

O

O

PMMA → MMAPS

Identification of specific pyrolysis products

☹️

Time (min)

Rel

ativ

e Ab

unda

nce

2.68

23.59 40.85

Monomerm/z: 104

Dimerm/z: 208

Trimerm/z: 312

m/z: 104

m/z: 208

m/z: 312

Component at scan 3832 (46.602 min) [Model = +193u] in D:\ DESKTOP\ AKTUELLER POLYMERORDNER\ ONLINE_PYROLYSE_MESSUNG\ PS_P5_590.RAWBenzene, 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

0

50

100

50

100

39

39

41

51

51

57

63

65

69

70

77

77

82

82

89

89

91

91

94

95

97103

103

115

115

130

130

139

139

152

152

165

165

178

178

193

193

202

208

208

219

Dimer

Component at scan 848 (13.429 min) [Model = +117u] in D:\ DESKTOP\ AKTUELLER POLYMERORDNER\ ONLINE_PYROLYSE_MESSUNG\ PS_P5_590.RAWα-MethylstyreneHead to Tail MF=861 RMF=864

30 40 50 60 70 80 90 100 110 120 130 140

0

50

100

50

100

38

38

39

39

40

40

4343

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

8086

87

89

89

90

91

91

92

92

9898

103

103

108 113

115

115

118

123 126 129

α-Methylstyrene

Component at scan 475 (9.278 min) [Model = +77u] in D:\ DESKTOP\ AKTUELLER POLYMERORDNER\ ONLINE_PYROLYSE_MESSUNG\ PS_P5_590.RAW StyreneHead to Tail MF=543 RMF=544

30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180

0

50

100

50

100

39

394344

49

51

53

63

63

6574

74

77

78

79

84

87

89

8993

97

98 101

103

104

106 110 115 119 123 127 131 139 152 165

Styren (Monomer)

polystyrene pyrolysis


polyethyleneterephthalate pyrolysis

0 10 20 30 40 50 60 70 80 90 100 1100

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

0

50

100

50

100

38

39

49

5054

5565

65

76

76

80

80

93

93

104

104

121

121 132

149

149

203

203

O

O O

O

CH2

CH2 Terephthalic acid 3-dibutenylester

Terephthalic acid 3-dibutenylester

Benzaldehyde

O

2,4-Di-tert-butylphenol

OH CH3

CH3

CH3

CH3 CH3

CH3

CH3OH

OUndecanoic acid


naphthalene

m/z 128

1- and 2-methylnaphthalenesm/z 142

fluorenem/z 166

anthracenem/z 178

Time (min)

Rel

ativ

e Ab

unda

nce

Pyrolysis products of PVC

R1

Cl Cl Cl Cl

R2

Cln


R1

Cl Cl Cl Cl

R2

Cln Molecular structure of PVC

R1

Cl Cl Cl Cl

R2

Cl

Potential cleavage

R1

CH+

CH3

+ CH

2+CH

+CH

+

CH2+ CH2

+ R2

+ + 5 Cl-

Reactive species

CH2+

CH+

CH+

CH2+ 3 Cl

-CH+

CH2+

CH+

CH+

CH+CH+

CH2+

+ 3 3 Cl-+H

+ + 3 ClH

formation of monocyclicstructures and hydrochloricacid - stabilisation

Formation of polycyclic aromaticcompounds

Formation of pyrolysis products of PVC

Time (min)

423 °C

590 °C

764 °C

Rel

ativ

e Ab

unda

nce


Variation of pyrolysis temperatures

Time (min)

Rel

ativ

e A

bund

ance

7,84

11,70 25,7111,2320,13

7,84

11,7025,7420,16

7,62

11,75 25,4319,86

7,63

11,00 25,4219,86

7,61

10,9825,4119,85

Retention time (min)

Compound

7 Naphthalin

11 1- and 2-Methylnaphthalene

20 Fluorene

25 Antracene

Polyvinylchloride pyrolysis

Reproducibility

pyrolysate without rinsing glass ware

Time (min)

Rel

ativ

e A

bund

ance

2,26

25,30

42,77

2,25

2,68

23,59 40,85


rinsed from glass ware

combination

Pittfalls

• Hygroskopic (soluble in water and polar organic solvents)• Mw of 2.500 to 2.500.00 Dalton• High production rate • Wide application

PVP-Iodine disinfectantContact lense cleanerShampoosHair sprayInk transfer inhibitor in

washing agentsBinder in tabletsBlood plasma expanderMembranes in drinking water filtrationFood additive E1201

• High environmental stability (Trimpin et al. 2001)• No information avalaible about environmental behaviour

Polyvinylpyrrolidone PVP

Example 1

Analytical problems in detecting PVP in environmental samples:

• Isolation from water matrices

• Low concentration level

S Trimpin, P Eichhorn, H J Räder, K Müllen, T P KnepperRecalcitrance of poly(vinylpyrrolidone): evidence through matrix-assisted laser desorption- ionisation time-of-flight mass spectrometryJournal of Chromatography A 938, 67-77

NO NOPyrolysis

Py-GC/FID (1990)Membranes: ~ 1.0 µg/g

Py-GC/MS (1998)Washing agents: LOD 0.05%


online-pyrolysis

5.0

3.5

2.5

1.5

1.0

0.5

Amount ofPVP in µg

NO NONH

O

T = 750°C; t = 5s

PVP K30 (Sigma-Aldrich) Mw 55.000 g/mol

+


1 2 3 4 5

R2 = 0.998

Area

NVP

µg PVP

Good reproducibility

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

pyrrolidoneRelative increase of pyrrolidonevs NVP with decreasing amount of pyrolysis educt

Adsorption of PVP on ceramicsurfaces shifts pyrolysis yields asobserved

V M Bogatyrev, N V Borisenko, V A Pokrovskii (2001) Thermal Degradation of Polyvinylpyrrolidone on the Surface of Pyrogenic SilicaRussian Journal of Applied Chemistry 74, 839-844.


0 200 400 600 800 1000

0

25

50

75

100

125

R2 = 0.9966

µg N

VP

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 % ± 0.2750 9.6 % ± 0.1500 8.5 % ± 0.8250 10.1 % ± 0.7125 8.4 % ± 0.350 9.2 % ± 0.120 9.2 % ± 0.1

Reproducibility



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

CPVP = 7.1 mgL

56

68 82

111

:

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

Municipal waste water Aachen Waste water Pancevo

CPVP = 2.9 mgL

NO

Surrogate standard

NO



Surrogate standard

Polyacrylamide based flocculants (PAbF) are mainlyused in sewage treatment

• for clarification of industrial and municipial wastewater

• for the removal of solids during the primary settlingstep

• for sludge thickening

Polyacrylamide based flocculants PAbF

Example 2

Chemical properties

COCO COCO

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.

COCO COCO

NH NH2 NH2 NH

NMe3+ Me3N+

n

COO-CO COCOO-

NH2 NH

2n


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


Release of PAbF to the pedosphere

Sewage slugdes are used for fertilisation in agriculture( Germany : approx. 35% , 15 Mio t/a)

Restrictions by law (Germany):

Within 3 years a maximum of 5 to 10 tons (dry matter) sewageslugde per 10.000 m2 can be discharged on agricultural soils

To a minor extend polyacrylamide based thikening agents mixedwith pesticides are used to aid in reducing spray drift


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 / EC50 (mg/L)cationic PAbF (dispers)

Bacteria 0.9 -7500Algae 0.2 - 7500Fishes 0.06 - 1000

Environmantal aspects of PAbF

Canadian diamond mine effluents :

Cationic DADMAC

48h median lethal concentrations(LC50) for Ceriodaphnia dubia

0.3 to 0.7 mg/L

NH2

RR

+

Rosemund, Liber(2004) Environ

ToxicolChem

• No data are reported concerning the ecotoxicologicaleffects of PAbF in the pedosphere

• No analytical methods are known for identification andquantification of PAbF in environmental samples

Although high amounts of PAbF are released tothe environment no information about thedistribution, fate and ecotoxicological effects in soils are available or can be aquired.


State-of-the-Art

25

50

75

100

7 14 21 28 35 42 time (d)

Inhi

bitio

n (%

)

AN 234

K6-60

PK55H

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

Ecotoxicological Effects

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

or 1 - 3 mg / kg per year

Estimated maximal concentrations in soils

Products of TMAH thermochemolysis

NO ONO O

NO O

TIC

127

141

155

R 'R

HN

R'

HNOCCO

R'

COHN NH

CO

R' R'


with TMAH

without TMAH

Synthesis of referencesubstances

NO O

O

OHOH

O

NN

NN

NO O

+

+

H3PO4 / >200°C

K2CO3 + MeI / PTK

1,3-Dimethylglutarimide


time temperature

On-line(TMAH) T

400 °C30 min

650 °C2.5 s

Optimization of pyrolysis

Tt

t

Off-line(TMAH)

35 40 45 min

On-line pyrolysis (650°C, 2.5 s)25 µg of a cationic PAbF

reproducibility

Linearity / Sensitivity

R2 = 0.99

R2 = 0.99

2 4 6 8 10 12 µg

NO ONO O

Peak

area

Optimization of pyrolysis

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 MeOH)

Detection of PAbF in a complex matrix

Soil sample spiked with PAbF

TIC

TIC

m/z 139m/z 127

m/z 127

m/z 153

m/z 153

m/z 141

m/z 141

m/z 113

m/z 113


Soil sample affected by sewage slugde

TIC

113 127 139 141 153

TIC

113 127 139 141 153

approx. 70 µg/g


Mass spectrometic identification

42

5570

83 101

127

55 7098

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

NO O9870


Polymers in drilling fluids

Drilling fluids are important additives for exploration and production drilling interrestrial and marine environments. Up to 95% of all exploration and productionwells used water-based muds. These are mixed with clays and polymers, in orderto meet subsurface requirements like stabilization of the borehole and regulationof 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 continuousemission of drilling fluids towards ecosystems are evident.(Apaleke et al. 2012)

Detection and quantitation of drilling emissions are highly relevant

Example 3


• Preparation andexecution of drilling

• Handling of drillingmud

Storage and disposalof drilling mud

Transport ofdrilling mud

Execution of drilling

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

Water-based drilling cuttings areallowed to be discharged offshoreCurrent amount of in-situ cuttingpiles: Central North Sea 700,000 m3

Carboxymethyl-cellulose (CMC)

Hydroxyethyl-cellulose (HEC)

Further components: Xanthan, Bentonite, Barite, etc.

Polyacrylamide (PAA)

Chemical structures of common drilling additive polymersDrill cutting – 4300 times enlarged

Detection of drilling activities in marine environment

Identification of characteristic pyrolysis products ofpolymers used as main compounds in drilling fluids

Proof of ability if these specific substances can actas drill cutting indicators


Carboxymethylcellulose (CMC)


Hydroxyethylcellulose (HEC)


Reproducibility

Influence of pyrolysis temperature


< 1 mg DF/g

Quantity/LOQ


Cellulose based drilling fluids

< 1 mg DF/g


Conclusions

Py-GC/MS is a key method for polymer analyses–

but not a simple one

mass spectrometry in support of the environment, food, and ... · pyrolysis-gc/ms jan schwarzbauer...

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