Thermo Scientific DFSHigh Resolution Sector Field MS

Dual Data Acquisition on a DFS

Heinz Mehlmann, Thermo Fisher, Bremen, Germany

2

Dual Data Acquisition

- Hardware

- Theoretical Background

- Performance

- Realisation

Dual GC single MS wide AS configuration

3

first peak last peak

Typical dioxin GC run on a 60m column

The first and last peak of a chromatogram defines the section of analytical intrest.

Theoretical Background

section of analytical interestwasted time wasted time

4

GC 1

GC 2

sequence timescale in normal mode

sample 1 sample 3

Theoretical Background

sample 2

Dual GC-MS systemSingle GC-MS system

No timesaving.

Why?

5

Theoretical Background

Both columns are directed into the source.

column GC 1 column GC 2

6

GC 1

GC 2

GC 1

GC 2

sequence timescale in normal mode

sequence timescale with DUAL DATA Aquisition.

sample 1

sample 2

sample 3

sample 1

sample 2

sample 3

sample 4

sample 5

sample 6

Theoretical Background

7

Theoretical Background

Continuous Dataflow

8

The following sample in the sequence will be injected during aquisition of the previous GC run.

Realisation

GC 1

GC 2

Sequence timescale with DUAL DATA Aquisition.

A hardware based modification is necessary.

9

Dynamic Flow Switching System

Realisation

A staggert injection can be realised with a hardware based modification in each GC.

Injector

analytical columnT-connector

swiching

valves

to MS

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Dynamic Flow Switching System

The column-flow is directed into the MS.

The column-flow is directed into the service vacuum

and He compensates the flow into the ionsource.

Realisation

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Cutout of a high conc. sample

Realisation

12

Cutout of solventpeaks

Realisation

13

Dynamic Flow Switching System

Hardware

Transfereline

Injector

Analytical Column

He

Vacuum

T-Connector

soldered stainless steel capillary

14

Dynamic Flow Switching System

Hardware

15

Dynamic Flow Switching System

DFS

Column

Hardware

16

GC 1

GC 2

DFS

Time

GC 1 GC 2GC 2GC 1

Principle

Timing

17

Sample: 1µl CS3 / CPM 8290/1613; Column: Thermo TR-Dioxin 60m x 0.25mm ID x 0.1µm film; Oven: 150 (2)-25-230(25)-6-320(6)

Performance PCDF/PCDD

native TCDF (303.9010 m/z)

native TCDF (305.8913 m/z)

13C12 Standard TCDF (315.9413 m/z)

13C12 Standard TCDF (315.9413 m/z)

RT: 20.16 - 31.84 :

21 22 23 24 25 26 27 28 29 30 31

Time (min)

50

100

50

100

50

100

50

100

50

100

Rela

tive A

bundance

50

100

50

100

50

10020.88

27.1731.08

25.75

20.88

27.1631.08

25.77

27.12

27.12

23.0730.6928.7128.42

28.1227.52

23.0730.6928.7128.42

28.1127.52

28.6627.49

28.6627.49

NL: 5.31E4

m/z= 303.8716-303.9324 MS DioxFur_5w_01_090316165536

NL: 6.78E4

m/z= 305.8684-305.9296 MS DioxFur_5w_01_090316165536

NL: 3.96E5

m/z= 315.9104-315.9736 MS DioxFur_5w_01_090316165536

NL: 5.01E5

m/z= 317.9072-317.9708 MS DioxFur_5w_01_090316165536

NL: 3.18E4

m/z= 319.8650-319.9290 MS DioxFur_5w_01_090316165536

NL: 4.24E4

m/z= 321.8618-321.9262 MS DioxFur_5w_01_090316165536

NL: 2.50E5

m/z= 331.9038-331.9702 MS DioxFur_5w_01_090316165536

NL: 3.19E5

m/z= 333.9006-333.9674 MS DioxFur_5w_01_090316165536

native TCDD (319.8960 m/z)

native TCDD (321.8930 m/z)

13C12 Standard TCDD (331.9363 m/z)

13C12 Standard TCDD (333.9333 m/z)

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Sample: 1µl CS3 / CPM 8290/1613; Column: Thermo TR-Dioxin 60m x 0.25mm ID x 0.1µm film; Oven: 150 (2)-25-230(25)-6-320(6)

Performance PCDF/PCDD

native HxCDF (373.8202 m/z)

native HxCDF (375.8172 m/z)

13C12 Standard HxCDF (383.8633 m/z)

13C12 Standard HxCDF (385.8604 m/z)

native HxCDD (389.8151 m/z)

native HxCDD (391.8121 m/z)

13C12 Standard HxCDD (401.8554 m/z)

13C12 Standard HxCDD (403.8524 m/z)

RT: 38.44 - 43.53

38.5 39.0 39.5 40.0 40.5 41.0 41.5 42.0 42.5 43.0 43.5

Time (min)

0

50

100

0

50

100

0

50

100

0

50

100

0

50

100

Rela

tive A

bundance

0

50

100

0

50

100

0

50

10039.39 41.8841.1641.01

42.91

41.8841.1639.39 41.01 42.89

41.8641.1440.99 42.89

41.8641.1440.99 42.88

40.16 42.5142.19

40.16 42.19 42.5142.08

42.18 42.4942.06

42.18 42.4942.06

NL: 5.27E5

m/z= 373.7836-373.8584 MS DioxFur_5w_01_090316165536

NL: 4.28E5

m/z= 375.7804-375.8556 MS DioxFur_5w_01_090316165536

NL: 5.76E5

m/z= 383.8042-383.8810 MS DioxFur_5w_01_090316165536

NL: 1.07E6

m/z= 385.8216-385.8988 MS DioxFur_5w_01_090316165536

NL: 3.87E5

m/z= 389.7770-389.8550 MS DioxFur_5w_01_090316165536

NL: 3.06E5

m/z= 391.7738-391.8522 MS DioxFur_5w_01_090316165536

NL: 7.43E5

m/z= 401.8158-401.8962 MS DioxFur_5w_01_090316165536

NL: 5.95E5

m/z= 403.8126-403.8934 MS DioxFur_5w_01_090316165536

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Peakshape (separation)

Performance Peakshape

The separation of 2,3,7,8-TCDD

from most closely eluted isomers

is below 25% Valley, according to

EPA 1613.

2,3,7,8-TCDD

< 25%

Sample: 1µl CS3 / CPM 8290/1613; Column: Thermo TR-Dioxin 60m x 0.25mm ID x 0.1µm film; Oven: 150 (2)-25-230(25)-6-320(6)

RT: 22.57 - 31.20

23 24 25 26 27 28 29 30 31

Time (min)

20

40

60

80

100

20

40

60

80

100

20

40

60

80

100

Rela

tive A

bundance

20

40

60

80

10023.07

30.6928.7128.42

28.1227.52

23.07

30.6928.7128.42

28.1127.52

28.6627.49

28.6627.49

NL:3.20E4

m/z= 319.8650-319.9290 MS DioxFur_5w_01_090316165536

NL:4.28E4

m/z= 321.8618-321.9262 MS DioxFur_5w_01_090316165536

NL:2.51E5

m/z= 331.9038-331.9702 MS DioxFur_5w_01_090316165536

NL:3.21E5

m/z= 333.9006-333.9674 MS DioxFur_5w_01_090316165536

native TCDD (319.8960 m/z)

native TCDD (321.8930 m/z)

13C12 Standard TCDD (331.9363 m/z)

13C12 Standard TCDD (333.9333 m/z)

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Sample: 1µl CS4-7474-62 CVS; Column: Restek Rtx@-1614 15m x 0.25mm ID x 0.1µm film; Oven: 120 (3)-10-300(6)

Performance PBDE

native TriBDE (405.8021 m/z)

native TBDE (485.7106 m/z)

native PeBDE (563.6311 m/z)

native HxBDE (643.5296 m/z)

native HpBDE (721.4401 m/z)

native DecBDE -2Br (799.3329 m/z)

native DiBDE (327.8916 m/z)

RT: 5.67 - 26.50

6 8 10 12 14 16 18 20 22 24 26

Time (min)

0

50

100

0

50

100

0

50

100

0

50

100R

ela

tive A

bundance 0

50

100

0

50

100

0

50

1008.16 8.36

7.887.25

10.8311.25

10.31

9.66

13.6112.40

14.3715.64

15.77

17.24

15.6315.93

16.49 17.22

20.1117.96

19.73 20.23 21.79

18.08

21.7818.8921.99

19.0022.44

17.81 20.11

25.50

NL:7.60E5

m/z= 327.8815-327.9015 MS D90311A20

NL:4.34E5

m/z= 405.7981-405.8181 MS D90311A20

NL:3.09E5

m/z= 485.7010-485.7210 MS D90311A20

NL:3.47E5

m/z= 563.6120-563.6320 MS D90311A20

NL:3.93E5

m/z= 643.5200-643.5400 MS D90311A20

NL:1.97E5

m/z= 721.4310-721.4510 MS D90311A20

NL:1.97E4

m/z= 799.3230-799.3430 MS D90311A20

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Performance Deca BDE

RT: 24.56 - 26.33

24.6 24.8 25.0 25.2 25.4 25.6 25.8 26.0 26.2

Time (min)

0

20

40

60

80

100

0

20

40

60

80

100

0

20

40

60

80

100

Rela

tive A

bundance

0

20

40

60

80

10025.49

25.49

25.49

25.49

NL:1.81E4

m/z= 799.2481-799.4079 MS D90311A20

NL:1.39E4

m/z= 801.2438-801.4041 MS D90311A20

NL:2.36E4

m/z= 811.2844-811.4467 MS D90311A20

NL:1.85E4

m/z= 813.2802-813.4428 MS D90311A20

13C12 Standard DecBDE -2Br (811.3732 m/z)

native DecBDE -2Br (799.3329 m/z)

native DecBDE -2Br (801.3309 m/z)

13C12 Standard DecBDE -2Br (813.3711 m/z)

Sample: 1µl CS4-7474-62 CVS; Column: Restek Rtx@-1614 15m x 0.25mm ID x 0.1µm film; Oven: 120 (3)-10-300(6)

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Sensitivity

1µl blood sample in the range of 20fg TCDD

Sample: 1µl Blood Sample; Column: Thermo TR-Dioxin 60m x 0.25µm x 0.1µm film; Oven: 120 (2)-10-220(10)-3-235(7)-4.6-310(1)

Performance Sensitivity

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Productivity

Performance Samplethrougput

Dual Data Acquisition

Increase of samplethrougput with no loss in performance.

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Dual Data AcquisitionTechnical Note

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Acknowledgment

Chuck Sueper Minneapolis /MN USA

Stefan Ahlbrand Altenberge Germany