Advantages in testing: Possibilities with quadrupole mass ......Institute for Testing and Certification – Zlín (CZ) Advantages in testing: Possibilities with quadrupole mass spectrometry

Institute for Testing and Certification – Zlín (CZ)

Advantages in testing:

Possibilities with

quadrupole mass spectrometry

at

Institute for Testing and

Certification-Zlín

Franky Puype, Jiří Samsonek

[email protected] , [email protected]

Analytical laboratory

mailto:[email protected]


Define problem/directive

Selecting method

Analytical support

Evaluate data

Working out cases scientifically

Working out cases technically

Prevention / Cost saving/ Market screening



Analytical chemistry for clients:


Quadrupole - mass filter


http://en.wikipedia.org/wiki/File:Mass_spectrometer_quadrupole.JPG

http://upload.wikimedia.org/wikipedia/commons/9/99/Paul_Patent_2939952_Fig5.gif

http://en.wikipedia.org/wiki/File:QuadrupoleContour.jpg

http://en.wikipedia.org/wiki/File:VFPt_quadrupole_coils_1.svg

http://en.wikipedia.org/wiki/File:Magnetic_quadrupole_moment.svg

http://upload.wikimedia.org/wikipedia/commons/8/8d/Aust.-Synchrotron%2C-Quadrupole-Focusing-Magnet%2C-14.06.2007.jpg



Solid Phase Micro Extraction (SPME)-GC

Headspace-GC

Direct liquid injection-GC

Direct Thermal Desorption-GC

Refocussation Thermal Desorption-GC

Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI



Volatiles in general (VVOCs, VOCs)

Free monomers

Smell analysis, defect analysis

Emission tests

Automotive specific tests

Food contact material

SPME-GC-MS and HS-GC-MS

13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0

0.25

0.50

0.75

1.00

1.25

1.50

1.75

(x100,000)


GMW8081:

car interior emissions

by static

headspace GC-MS

Identification report

Smelling compound

Not smelling sample

Sample blank

8.7 8.8 8.9 9.0 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 10.0

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

2.75

3.00

3.25

(x100,000)

Monomers in SML by

SPME-GC-MS

Defect analysis for automotive industry – from the analytical point of view

Puype F., Samsonek J. (2011) (4/2011) Chemické listy105/370-373 -- ISSN 0009-2770




Headspace-GC




Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI


22.00 22.25 22.50 22.75

250

500

750

1000

1250

1500

1750

113.10


Quantification of allergens: Fungicide dimethylfumarate

Banning allergies, DMF screening of leather and textile products

Puype F., Samsonek J. (2010) Shimadzu News 1:12-13

Directive 2009/251/EC:DMF < 0,1 mg kg-1 in consumer goods

0,1 mg kg-1

O

O

O

O


http://www.linkedin.com/redirect?url=http%3A%2F%2Fwww%2Eshimadzu%2Eco%2Euk%2FUpload%2Ffile%2FWeb_NEWS_0110_GB_a%2Epdf&urlhash=fLbu



MF DNES: 15.07.2009

Quantification of allergens: dimethylfumarate







Headspace-GC



Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI



Direct thermal desorption-GC-MS

Rapid determinatin of certain BFRs in plastics by thermal desorption

GC-MS (TD-GCMS) for the RoHS directive

Puype F., Samsonek J., Vít D. (2007) Organohalogen Compounds, 69:2789-2792

Sample Tube/Cup



Evaluation of the quantitative analysis of PBDEs in plastics by

thermal desorption GC-MS for soluble polymers

Puype F., Samsonek J. (2008) Organohalogen Compounds, 70;1522-1525



decaB

DE

-209

octa

BD

Es

nonaB

DE

s

hepta

BD

E-1

83

hexaB

DE

-154

hexaB

DE

-153

penta

BD

E-9

9

penta

BD

E-1

00

tetr

aB

DE

-47


Identification of TBBPA-DBPE in plastics by direct thermal desorption-GC-MS

Puype F., Samsonek J. (2008) Organohalogen Compounds, 70:000914-000917

100 200 300 400 500 600 700 800 900 10000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

(x10,000)

119.1

528.8

382.9

292.9

200.9 462.9

502.9

275.0165.2

63.1 623.9343.1

626.0 702.9

783.9743.9

943.8864.8 975.9

Br

Br

Br

Br

Br

Br

Br

Br

O

O



Defect analysis - fogging

Thermal desorption

GC-MS

50.0 75.0 100.00

10

20

30

40

50

60

70

80

90

100

%

55.1

112.2

57.1

89.1

70.1

84.1

97.1

111.2103.172.181.051.0 94.066.1 119.2

Amine




Puype F., Samsonek J. (4/2011) Chemické listy, ISSN 0009-2770



Direct thermal desorption-GC-MS degradation study

Behaviour of bromine content and low molecular weight

emissions from decaBDE, HBCD and brominated polystyrene in

polystyrene after artificial ageing in UV light

Puype F., Samsonek J. (2010) Poster BFR2010, Kyoto





Headspace-GC



Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI



Thermal desorption with refocussation

Cryo-trap


-20ºC


Candidate List of Substances of Very High Concern (SVHC)

Possibilities with refocussing thermal desorption (TD-GC-MS) for the characterisation of synthetic polymers

Puype F., Samsonek J. (2008) Polymery 2008, P-02 (ISBN 978-80-968433-5-0)



Emission measurements: indoor material / automotive-VDA 278

Lifetime emissions

of the product are simulated

Quality requirements in

automotive are getting

higher !!

Emission testing of non-metal vehicle material according to VDA 278

Puype F., Samsonek J. (4/2011) Chemické listy105/370-373 -- ISSN 0009-2770


http://www.internationalrubberconference.org/





Headspace-GC



Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI


Sample Tube/Cup


Pyrolysis-GC-MS: Polyisobutylene

14

Decamer

Pentamer


Pyrolysis coupled with gas chromatography and mass spectrometry (PY-GC-MS)

for the rapid characterisation of synthetic polymers

Puype F., Samsonek (2008) Polymery 2008,L-16 (ISBN 978-80-968433-5-0)


Brominated polymeric additives

No migration/ non-blooming

Some are restricted/limited – speciation required (PBDEs, PBBs, HBCD)

Brominated polystyrene

Monomer region

Dimers and cyclic

combination products

Pyrogram: brominated polystyrene




Brominated polystyrene in PA6

Br2-styrenes Br3-styrenes

Radical unzipping – depolymerization PS

Ai

AiBi

Bn

).(Pyrogram: brominated polystyrene

Br-styrenes/

Br-benzenes

Br4-styrene


Bromination degree: 2,7 (2% RSD, n=3)



Unknown BFR in toluene extracts from PBT

OH

OHBr

Br

Br

Br

Tribromo-toluene TBBPA

Pyrogram

Br

Br

Br

OH


Mass spectrometric analysis of polymeric additives in polymer extracts by pyrolysis-GC-MS



100 200 300 400 500 600 7000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

(x10,000)62.10 356.90312.90

57.15

143.10

233.95

585.00

132.20

519.10 608.85197.00250.00

530.95483.90 687.85

405.10 449.10733.80

648.90


Unknown BFR in toluene extracts from PBT

OH

OHBr

Br

Br

Br

TBT

TBBPA TBT

TBBPA

Br

Br

Br

OHPyrogram

MS spectrum OH

BrBr

Br

OBr

Br

O

R

Br

Br

M/e 312,9




BFRs in toluene extracts from PBT – reactive pyrolysis

OH

BrBr

Br

OBr

Br

O

R

Br

Br

Can we find glyceroltrimethylether with reactive pyrolysis?

RR

O

TMAH/MeOH

400 C

R

O

R

O+





OH

BrBr

Br

OBr

Br

O

R

Br

Br

Can we find glyceroltrimethylether with reactive pyrolysis?

50 60 70 80 90 1000.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75(x1,000,000)

59.10

89.15

102.1572.15 88.15

75.1050.05

94.0056.1061.10 79.0067.10 105.20

O

O

O

Pyrogram/TMAH

RR

O

TMAH/MeOH

400 C

R

O

R

O+

MS


nOH

OH

BrBr

Br

OBr

Br

O

O

Br

Br Br

Br

Br

O




End Capped Brominated Epoxy

F-3000

CAS: 135229-48-0

MW: approx. 2000

Mass spectrometric analysis of polymeric additives in polymer extracts by pyrolysis-GC-MS




Polymeric hindered amine light stabilizers

(p-HALS) – stabilizer 944

Mn = 2000-3100

Polyolefins/PVC/PA

Cyclic depolymerization

Monomer

M/e 598,4

50 100 150 200 250 300 350 400 450 500 550 600 6500.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

(x100,000)

460.3

58.1

124.2

321.1

498.3209.1 348.1 598.498.2

527.3

583.355.1

235.1 388.2 444.3167.1

275.1 361.2

666.3

Pyrogram

MS spectrum


50 100 150 200 250 300 350 400 450 5000.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

(x1,000,000)

152.2

84.1

70.1

433.1351.1

123.1

147.6

209.1

268.1228.0 294.1184.0 417.1377.1333.1 450.2


Polymeric hindered amine light stabilizers

(p-HALS) – MIXTURE 783

50 100 150 200 250 300 350 400 450 500 550 600 6500.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

(x100,000)

460.3

58.1

124.2

321.1

498.3209.1 348.1 598.498.2

527.3

583.355.1

235.1 388.2 444.3167.1

275.1 361.2

666.3

M/z 433 M/z 460

Pyrogram: single ion monitoring






Headspace-GC



Pyrolysis-GC

Direct Inlet

MS

EI (70eV)

NCI

PCI



Hydrotalcites in polymers, sources for yellowing?

metal content

0

25

50

75

100

125

Yellow White Yellow White White

Mg

/Al

co

nte

nt

mg

/kg

Al content

Mg content

Hydrotalcites -Mg6Al2CO3(OH)16 · 4(H2O) –

can catalyze the releasing of

BHT and BHT derivates from

phenolic antioxidants


Irganox 3114 is a big molecule

cannot be separated by classical GC

(MW 784 Da)


Direct inlet analysis: extracts from yellow samples

100 200 300 400 500 600 7000.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25(x10,000)

57.20

203.20

161.15

91.15

147.15

260.30 332.20436.45 647.55565.40346.30

303.15

783.80

384.75 592.40493.40 631.40 708.60

M-H+

M-BHTQM+H

M-BHTQM2+2H

163.2 BHT-tert.butyl

161.1 BHTQM-tert.butyl

At M+-1 (irganox

3114QM) no peaks

seen

782.6

203,2 BHTQM-tert.butyl








Headspace-GC



Pyrolysis-GC

Direct Inlet

qMS

EI (70eV)

NCI

PCI

qMS

ICP (hot

and cool)



Sample

preparation

Migration test

Dillution

Internal standard

External

calibration

Sample

introduction

Pumping

Nebulization

Atomization

Ionization

Detection

Background corr.

Resolution

Spectral

interference

Mass spectrometry

Polyatoms

Inductively coupled plasma-MS

Ion mirror

Q-MS ICP

Mass spectrum

ISOTOPES Sampling

cone

Argon hot plasma,

1500 W, 10.000 ºC

Results

RSD (< 5 %)

Recovery

Duplicates

LOD (ppt)

Test report



54Fe: 40Ar14N, 53Cr1H, 108Cd++, 108Pd++,

56Fe: 40Ca16O, 40Ar16O, 55Mn1H, 112Cd++, 112Sn++

57Fe : Ar16O1H, 40Ca16O1H, 56Fe1H, 114Cd++, 114Sn++

58Fe: Ar18O, 40Ca18O, 42Ca16O,57Fe1H, 116Cd++, 116Sn++, 58Ni

40Ar (plasma) + 16O (water) = 56Fe (target)

Spectral interferences (isobaric overlap) for 56Fe…Polyatoms!




Trace analysis in food contact materials

Elemental speciation analysis

Impurities

Defect analysis

Difficult matrixes (e.g. low power explosives, tetrahedral white phosphorus, LiBr from heat pumps, etc…)

Supporting research and development

Toy testing

Varian ICP-qMS


- Analytical laboratory:

analytical plasma spectrometry

and

atomic emission spectrometry

- Analytical laboratory:

analytical mass spectrometry

and

separation science


And, and, and,…





Many thanks

for your

attention !





Documents

Advantages in testing: Possibilities with quadrupole mass ......Institute for Testing and Certification – Zlín (CZ) Advantages in testing: Possibilities with quadrupole mass spectrometry