Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic...

51
The world leader in serving science Modernizing Persistent Organic Pollutants (POPs) Analysis

Transcript of Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic...

Page 1: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

The world leader in serving science

Modernizing Persistent Organic Pollutants (POPs) Analysis

Page 2: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

2

• Introduction to POPs

• Dioxin analysis with the DFS

• Recent regulatory changes:• Dioxin analysis in food with the Thermo Scientific™ TSQ™

9000 triple quadrupole GC-MS/MS system

• Analysis of PBDEs with the Thermo Scientific™ TSQ™ 9000 triple quadrupole GC-MS/MS system

• Analysis of PBDEs with the Thermo Scientific™ Q Exactive™ GC Orbitrap™ GC-MS/MS

• Analysis of SCCPs wit the Thermo Scientific™ Q Exactive™ GC Orbitrap™ GC-MS/MS

• Conclusions

Agenda

Page 3: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

3

• POPs are toxic chemicals that adversely affect humans• Bioaccumulate and transferred via the environment and the

food chain• Long half lives and difficult to break down• POPs are regulated by the Stockholm convention

• 2,3,7,8-TCCD is know the most toxic compound in the world

What are Persistent Organic Pollutants (POPs)

Aldrin A

Chlordane A

DDT B

Dieldrin A

Endrin A

Heptachlor A

Hexachlorobenzene A and

CMirex A

Toxaphane A

Polychlorinated biphenyls (PCB)

A and

C Polychlorinated dibenzo-p-dioxins (PCDD)

C

Polychlorinated dibenzofurans (PCDF)

C

Alpha hexachlorocyclohexane A

Beta hexachlorocyclohexane A

Chlordecone A

Hexabromobiphenyl A

Hexabromocyclododecane A

Hexabromodiphenyl ether and heptabromodiphenyl ether (commercial “Octa”)

A

Hexachlorobutadiene A

Lindane A

Pentachlorobenzene A and C

Pentachlorophenol and its salts and esters

A

Perfluorooctane sulfonic acid, its salts and perfluorooctane sulfonyl fluoride

A

Polychlorinated naphthalenes A and C

Technical Endosulfan and related isomers

A

Tetrabromodiphenyl ether and pentabromodiphenyl ether (commercial “Penta”)

AViktor Yushchenko exposure to dioxins causing chloracne

Page 4: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

4

• Emerging POPs of interest:• Mixed halogenated dioxins and furans• Short-chain chlorinated paraffins (SCCPs)

• Challenges with the analysis of POPs:• Low regulatory limits• Varied matrices • Covering expanding lists of target analytes• Producing consistent results

• Need instrumentation suitable for the analysis and the regulation

Emerging POPs and Analysis Challenges

4000+ congenersof mixed halogenateddioxins and furans

Short chainedchlorinated paraffins

(SCCPs)

Page 5: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

5

Thermo Scientific DFS Magnetic Sector GC-HRMS – worldwide compliance

• Global compliance with any official Dioxin, PCB, or PBDE method (e.g. EPA 1613, 1668..)

• Proven leadership with robust sensitivity for routine applications thanks to large-volume ion source

• Exceptional productivity and flexibility with New DualData XL option, for up to doubled sample throughput

• Future committed for Dioxins and POPs regulations compliance today and tomorrow

thermoscientific.com/GoldStandard

Page 6: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

6

Worldwide Compliance - Official Methods Recognizing Magnetic Sector Technology

Do you have international customers? Are you working globally? Already now or in the future…

Page 7: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

7

15.2 MS Resolution - A static resolving power of at least 10,000 (10% valleydefinition) must be demonstrated at the appropriate m/z before any analysis isperformed. Static resolving power checks must be performed at the beginning andat the end of each 12 hour shift according to procedures in Section 10.1.2. Correctiveactions must be implemented whenever the resolving power does not meet therequirement.

DFS

Here: EPA 1613 compliance

10.2.1.2 The mass spectrometer shall be operated in a mass-drift correction mode,using perfluorokerosene (PFK) to provide lock m/z's. The lock-mass for each groupof m/z's is shown in Table 8. Each lock mass shall be monitored and shall not varyby more than ±20% throughout its respective retention time window. Variations of thelock mass by more than 20% indicate the presence of coeluting interferences that maysignificantly reduce the sensitivity of the mass spectrometer.

DFS DFS DFS

DFS & EPA 1613:

• 10.000 resolution • Resolution checks• Use PFK• mass-drift correction• lock mass monitoring

Official Method Compliance – EPA 1613

Page 8: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

8

Ultimate Sensitivity Combined with Robustness

RT: 23.82 - 27.83

24.0 24.2 24.4 24.6 24.8 25.0 25.2 25.4 25.6 25.8 26.0 26.2 26.4 26.6 26.8 27.0 27.2 27.4 27.6 27.8Time (min)

0

50

100

0

50

100

0

50

100

0

50

100

0

50

100

Rel

ativ

e A

bund

ance

0

50

100

0

50

100

0

50

100

RT: 25.22MA: 375

24.0823.90 25.52 27.40 27.7527.2324.19 24.36 27.0726.2925.3724.54 25.63 26.6625.83 26.9226.4626.0324.74

RT: 25.22MA: 432

24.13 24.52 27.6424.95 27.2926.7726.22 27.0526.0325.54 25.85 26.55 27.5126.9026.3524.67

RT: 25.20AA: 172156

RT: 25.20AA: 218158

RT: 25.81MA: 165

27.54

27.6724.17 27.1625.26 27.4024.60 26.1825.57 26.9926.6624.87 25.9624.39 26.46

RT: 25.85MA: 202

26.73 27.2527.7725.57 27.5424.61 27.1224.32 26.6026.2224.02 25.26 25.4624.96 27.0125.70 26.4626.05

RT: 25.22AA: 153519

RT: 25.79AA: 116608

RT: 25.22AA: 198314 RT: 25.79

AA: 159458

NL: 1.13E2m/z= 303.8868-303.9172 MS PCDDF_sample_219448-703_2ul_01

NL: 1.22E2m/z= 305.8837-305.9143 MS PCDDF_sample_219448-703_2ul_01

NL: 4.01E4m/z= 315.9262-315.9578 MS ICIS PCDDF_sample_219448-703_2ul_01

NL: 5.11E4m/z= 317.9231-317.9549 MS ICIS PCDDF_sample_219448-703_2ul_01

NL: 7.50E1m/z= 319.8810-319.9130 MS PCDDF_sample_219448-703_2ul_01

NL: 7.00E1m/z= 321.8779-321.9101 MS PCDDF_sample_219448-703_2ul_01

NL: 3.52E4m/z= 331.9204-331.9536 MS ICIS PCDDF_sample_219448-703_2ul_01

NL: 4.62E4m/z= 333.9173-333.9507 MS ICIS PCDDF_sample_219448-703_2ul_01

Real sample: serum extract (col.: 60m x 0.25 (0.25))

3 fg TCDF

2 fg TCDD

7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

10.83

10.91 11.0910.299.09 11.609.268.81 11.268.78 10.04 10.539.749.338.478.137.68 7.92 9.638.407.59

20 fg 2378-TCDD SN ≥ 200:1 (PtP, 4σ)

Best Dioxin specification on the market

Proof spec demonstrated to customers during DFS GC-HRMS installation

Page 9: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

9

Ultimate Sensitivity for Confidence

RT: 10.57 - 11.67

10.6 10.8 11.0 11.2 11.4 11.6Time (min)

0

20

40

60

80

1000

20

40

60

80

100

Rel

ativ

e Ab

unda

nce

Quantification mass trace

Qualifier (ratio) mass trace

100 fg

25 fg

50 fg

10 fg5 fg2 fg

1368-TCDD1379-TCDD

1378-TCDD

1478-TCDD

1234-TCDD

2378-TCDD

6 different native tcdd isomers at different concentrations (2 – 100 fg/ul)

Page 10: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

10

RT: 21.36 - 26.69

21.4 21.6 21.8 22.0 22.2 22.4 22.6 22.8 23.0 23.2 23.4 23.6 23.8 24.0 24.2 24.4 24.6 24.8 25.0 25.2 25.4 25.6 25.8 26.0 26.2 26.4 26.6Time (min)

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100R

elat

ive

Abu

ndan

ce

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

RT: 25.80AA: 8787

RT: 25.22AA: 4505

RT: 24.69AA: 2042

RT: 24.30AA: 651

RT: 22.98MA: 356RT: 22.68

AA: 181

RT: 25.81AA: 8332

RT: 25.25AA: 4356

RT: 24.72AA: 2250RT: 24.32

AA: 843

RT: 23.01AA: 472RT: 22.68

AA: 165

RT: 25.81AA: 8621

RT: 25.22AA: 4231

RT: 24.69AA: 2097RT: 24.30

AA: 918

RT: 23.00AA: 440RT: 22.66

MA: 130

RT: 25.79AA: 8982

RT: 25.23AA: 4343

RT: 24.70AA: 2172RT: 24.29

AA: 923

RT: 22.99AA: 419RT: 22.68

MA: 157

RT: 25.80AA: 8955

RT: 25.24AA: 4324

RT: 24.71AA: 1797RT: 24.30

AA: 928

RT: 22.98AA: 392RT: 22.71

AA: 165

RT: 25.79AA: 8448

RT: 25.23AA: 4063

RT: 24.70AA: 2075RT: 24.29

AA: 968

RT: 22.97AA: 515

RT: 22.66AA: 152

NL: 2.13E3m/z= 321.8876-321.9004 MS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_01

NL: 1.93E3m/z= 321.8876-321.9004 MS ICIS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_02

NL: 2.04E3m/z= 321.8876-321.9004 MS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_03

NL: 2.29E3m/z= 321.8876-321.9004 MS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_04

NL: 2.24E3m/z= 321.8876-321.9004 MS ICIS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_05

NL: 2.12E3m/z= 321.8876-321.9004 MS ICIS Dioxin_2-5-10-25-50-100fg_TCDD_1ul_06

x5

Inj. 1

Inj. 2

Inj. 3

Inj. 4

Inj. 5

Inj. 6

- zoomed - all data unsmoothed!

2 – 100 fg TCDD on 60 m Column

Page 11: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

11

Customer Lab in Japan (2010)

D:\Xcalibur\...\tcdd_001 3/9/2010 1:48:35 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.10 - 11.78

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100R

elat

ive

Abun

danc

e

10.78

10.7210.836.49 11.508.98 10.34 11.209.949.347.04 8.334.42 9.925.975.82 6.524.47 8.868.297.877.616.445.715.26

NL:7.34E2m/z= 321.48-322.48 MS tcdd_001

Base Peak Retention Time : 10.78 Scan : 1028 Intensity : 734

Calculated values Noise Range : 7.11 - 8.94 minutes (279 scans) Baseline : 19.3 Signal To Noise : 212.6 (4 sigma) Noise : 0.840 Algorithm: Statistical

212 : 1D:\Xcalibur\...\tcdd_007 3/9/2010 3:56:56 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.04 - 11.58

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.84

9.3310.889.405.34 7.73 11.506.195.664.96 6.26 10.12 10.697.95 8.727.64 8.394.08 7.304.30 9.227.15

NL:1.21E3m/z= 321.48-322.48 MS tcdd_007

Base Peak Retention Time : 10.84 Scan : 1036 Intensity : 1214

Calculated values Noise Range : 6.27 - 7.62 minutes (205 scans) Baseline : 19.6 Signal To Noise : 217.3 (4 sigma) Noise : 1.374 Algorithm: Statistical

217 : 1D:\Xcalibur\...\tcdd_008 3/9/2010 4:16:44 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 0.00 - 16.00

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.84

14.0213.849.81 15.3910.92 11.466.13 8.34 14.886.47 7.39 9.775.955.064.44

NL:1.24E3m/z= 321.48-322.48 MS tcdd_008

Base Peak Retention Time : 10.84 Scan : 1036 Intensity : 1244

Calculated values Noise Range : 8.48 - 9.80 minutes (200 scans) Baseline : 19.5 Signal To Noise : 204.6 (4 sigma) Noise : 1.497 Algorithm: Statistical

205 : 1

# tcdd S/N (4σ)1 20 fg 212 : 12 20 fg 217 : 13 20 fg 205 : 1

D:\Xcalibur\...\tcdd_009 3/9/2010 5:19:31 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.06 - 12.02

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.85

10.89 11.1210.49 11.5210.249.327.07 9.614.27 8.797.104.61 4.92 8.675.48 7.905.98 6.00 8.537.00

NL:1.04E3m/z= 321.48-322.48 MS tcdd_009

Base Peak Retention Time : 10.85 Scan : 1039 Intensity : 1040

Calculated values Noise Range : 7.56 - 8.56 minutes (152 scans) Baseline : 19.3 Signal To Noise : 237.3 (4 sigma) Noise : 1.075 Algorithm: Statistical

237 : 1

4 20 fg 237 : 1

D:\Xcalibur\...\tcdd_005 3/9/2010 3:15:13 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.04 - 11.96

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.83

10.915.50 11.097.355.804.84 10.299.09 11.606.39 9.268.818.78 10.044.48 5.25 8.477.397.215.83 6.554.11

NL:1.44E3m/z= 321.48-322.48 MS tcdd_005

Base Peak Retention Time : 10.83 Scan : 1033 Intensity : 1444

Calculated values Noise Range : 9.37 - 10.04 minutes (101 scans) Baseline : 19.5 Signal To Noise : 241.6 (4 sigma) Noise : 1.474 Algorithm: Statistical

242 : 1

5 20 fg 242 : 1

D:\Xcalibur\...\tcdd_010 3/9/2010 5:39:08 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.10 - 11.84

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.84

10.54 11.178.354.48 11.3910.376.52 9.989.539.176.845.19 6.25 8.145.434.83 8.387.11 9.138.077.626.17

NL:1.06E3m/z= 321.48-322.48 MS tcdd_010

Base Peak Retention Time : 10.84 Scan : 1035 Intensity : 1062

Calculated values Noise Range : 6.59 - 7.97 minutes (209 scans) Baseline : 19.3 Signal To Noise : 235.8 (4 sigma) Noise : 1.106 Algorithm: Statistical

236 : 1

6 20 fg 236 : 1

D:\Xcalibur\...\tcdd_004 3/9/2010 2:54:44 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.07 - 11.80

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.82

10.86

10.479.33 10.948.34 11.245.26 9.45 10.067.72 8.405.50 8.958.237.045.71 7.255.16 6.104.39 6.734.43 6.70

NL:1.20E3m/z= 321.48-322.48 MS tcdd_004

Base Peak Retention Time : 10.82 Scan : 1033 Intensity : 1200

Calculated values Noise Range : 10.06 - 10.46 minutes (61 scans) Baseline : 19.6 Signal To Noise : 212.2 (4 sigma) Noise : 1.391 Algorithm: Statistical

212 : 1

7 20 fg 212 : 1

D:\Xcalibur\...\tcdd_006 3/9/2010 3:36:00 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.04 - 11.77

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.84

10.87

7.54 9.53 10.898.284.20 10.78 11.726.575.98 10.289.204.904.28 6.22 10.059.056.84 7.925.16 7.13 8.315.96

NL:1.14E3m/z= 321.48-322.48 MS tcdd_006

Base Peak Retention Time : 10.84 Scan : 1036 Intensity : 1136

Calculated values Noise Range : 8.30 - 9.17 minutes (132 scans) Baseline : 19.5 Signal To Noise : 234.9 (4 sigma) Noise : 1.188 Algorithm: Statistical

235 : 1D:\Xcalibur\...\tcdd_003 3/9/2010 2:35:42 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.04 - 11.69

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.78

10.82 11.029.715.514.05 10.314.34 9.926.31 7.66 7.85 9.504.51 9.428.425.20 8.727.406.876.355.74

NL:1.27E3m/z= 321.48-322.48 MS tcdd_003

Base Peak Retention Time : 10.78 Scan : 1028 Intensity : 1274

Calculated values Noise Range : 8.87 - 9.45 minutes (87 scans) Baseline : 19.6 Signal To Noise : 222.3 (4 sigma) Noise : 1.411 Algorithm: Statistical

222 : 18 20 fg 235 : 19 20 fg 222 : 1

D:\Xcalibur\...\tcdd_002 3/9/2010 2:13:49 AM 20fg tcddinj. volume: 1ul column: Thermo TR-Dioxin 30m ID: 0.25mm film: 0.1um oven: 120(2)-15-240(0)-6-280(1)

RT: 4.04 - 11.81

4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e Ab

unda

nce

10.79

10.82 11.168.16 10.649.266.64 7.14 7.895.735.63 9.926.21 11.749.754.84 7.46 8.204.59 8.644.48

NL:1.06E3m/z= 321.48-322.48 MS tcdd_002

Base Peak Retention Time : 10.79 Scan : 1026 Intensity : 1055

Calculated values Noise Range : 8.17 - 9.02 minutes (129 scans) Baseline : 19.5 Signal To Noise : 227.2 (4 sigma) Noise : 1.139 Algorithm: Statistical

227 : 110 20 fg 227 : 1

10 times repeated TCDD spec

Page 12: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

12

Dioxins & POPs Productivity – Thermo Scientific DFS DualData XL Option

32 samples in 12 hour shift16 samples in 12 hour shift

Technology based on Magnetic Sector MS provides a solution for maximum productivity in terms of number of samples analyzed per time.

With DualData XL Option you can double your throughput, even with mixed Applications such as Dioxins, PCBs, PBDEs, OCPs and other.

• same hardware • same software • same lab space

= same cost of ownership as standard magnetic sector MS

...but with up to double productivity

DualDataXL

Page 13: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

13

Thermo Scientific TSQ 9000 Triple Quadrupole GC-MS/MS System

Feature BenefitHighly efficient

ionization A greater ion flux reaching

the detectorA more tightly focused

ion beam Less ion burn and a higher

degree of robustness

Thermo Scientific™ TSQ™ 9000 triple quadrupole GC-MS/MS system

Thermo Scientific™ Advanced Electron Ionization (AEI) source

IDLRSD = 120 ag

n = 8 injectionsOFN1 fg on-column

2.400 2.500 2.600 2.700 2.800 2.900 3.000500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

4,500

min

counts

Page 14: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

14

Ion Source Quadrupole 1 (Q1)

Ion Source

Ion Transfer Optics

Quadrupole

Single Quadrupole GC-MS

Triple Quadrupole GC-MS/MS

MS

MS MS

Quadrupole 2 (Q2)

Collision CellQuadrupole 3 (Q3) EM Detector

EM Detector

Why Triple Quadrupole GC-MS/MS?

Ion Transfer Optics

Page 15: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

15

• Low detection limits• Optimized sample

preparation• Consolidated analytical

methods• Faster, automated data

processing

...it’s a high selectivitytechnique...

GC-MS/MS – What’s So Special?

Page 16: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

16

EU Compliance – Thermo Scientific TSQ 9000 triple quadrupole GC-MS/MS system

EU regulations amended in 2014 (589/2014 & 709/2014)Allowing the use of GC-MS/MS for confirmatory methods providing the following criteria are met:

Regulatory compliant sensitivity•10fg on-column TCDD with ion ratios (2 specific SRM transitions) within ±15% tolerance.

•Routine method (all 17 toxic PCDDFs + 4 non-ortho dl-PCBs).

Chromatographic and mass spectral resolution•Peak to peak separation of HxCDF isomers <25% (5.9%)•Q1 and Q3 both set to 0.7Da @FWHM – giving EU compliant separation between masses

LOQ compliance•For GC-MS/MS European guidance is to demonstrate LOQ throughout sequence (as opposed to using S:N ratios.•±15% ion ratios.•≤30% deviation from average RF.

•Demonstrated over multi-site validation study on three separate systems and ~2 weeks continuous runtime.

21 CFR, part 11 compliance•Chromeleon software has the tools to be fully compliant with FDA requirements, including audit trails.

•Real time results updates including SUM WHO-PCDD/F-TEQ values during data review.

•All data can be digitally reviewed and signed.

Resolution ≤1(separation of two peaks one mass

unit apart) for each quadrupole

Ion ratio ± 15% max deviation from theoretical

value for product ions of the two

transitions

2 specific SRM transitions

for all labelled and native congeners.

Chromatographic separation of Heptafurans

better than 25% peak to peak.

Page 17: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

17

• … An online search engine for Thermo Fisher Scientific applications• … Provides comprehensive application information and ready-to-run analytical methods• … A central repository for Thermo Scientific chromatography and MS application information

Method Development Resource: The AppsLab Library of Analytical Applications

Visit: www.thermofisher.com/appslab

Page 18: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

18

LOQ Consistency for Dioxin Analysis in Matrix

22

23

53

66

79

92

101

88.33 71.76 94.59 93.48 67.18 96.42 101.79 62.34 92.28 104.45 69.42 97.60 107.36 60.28 91.57 97.07 73.03 100.00 90.36 67.25 89.31

LOQ

/4LO

Q/4

LOQ

/4LO

Q/4

LOQ

/4LO

Q/4

LOQ

/4

2378-TCDD 123478-HxCDD OCDDInjection #

10 fg on-column 40 fg on-column 160 fg on-column

• Consistent results at the LOQ• Reproducibility within the regulatory

requirements

19.275 19.400 19.500 19.600 19.700 19.800 19.900 20.0006575100125150175200225250275300325350375400425450475500

2378-TCDD

n = 8 injections 2,3,7,8-TCDD5fg on-column

IDL0.58 fg

Page 19: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

19

Reporting to Regulations Made Easy with Chromeleon

RT:20.86

ISTD

Con

f 1

RT:20.86

ISTD

Qua

n

RT:20.88

Con

f 1

RT:20.88

Qua

n

RT:25.96

ISTD

Con

f 1

RT:25.96

ISTD

Qua

n

RT:25.98

Con

f 1

RT:25.97

Qua

n

RT:38.39

ISTD

Con

f 1

RT:38.39

ISTD

Qua

n

RT:38.40

Con

f 1

RT:38.40

Qua

n

2,3,7,8-TCDD 12378-PeCDD OCDD

Automatic flagging of results outside tolerance

Page 20: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

20

Agreement of Total TEQ with Reference Animal Fat Sample

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

WHO

-PCD

D/F-

TEQ

cont

ribut

ion

(pg/

g)

QK 1 - Reference value QK1 Avg (n=14)

Page 21: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

21

Long Term Robustness for Dioxin Analysis

100

1000

10000

0 20 40 60 80 100 120 140 160

Peak

are

a(c

pm)

Injection number

Peak area repeatability

2378-TCDD - 6.4% RSD 0.17 pg 12378-PeCDF - 6.3% RSD 0.36 pg 23478-PeCDF - 4.2% RSD 0.92 pg

12378-PeCDD - 6.0% RSD 0.21 pg 234678-HxCDF - 4.4% RSD 0.31 pg 123789-HxCDD - 5.3% RSD 0.2 pg

1234678-HpCDD - 3.5% RSD 0.71 pg OCDD - 2.8% RSD 6.12 pg

A

Page 22: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

22

LOQ Calculation Reproducibility

0

0.002

0.004

0 20 40 60 80 100 120 140 160Calc

ulat

ed a

mou

nt

(pg/

µL)

Injection number

2378-TCDD RF repeatability (n=39) 2378-TCDD

40

90

140

0 20 40 60 80 100 120 140 160

Qua

lifie

r Ion

Rat

io

(%)

Injection number

2378-TCDD IR stability (n=39) 2378-TCDD

B

Page 23: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

23

4.10 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00 9.50 10.00 10.50 11.00 11.47-5.0e70.0e05.0e71.0e81.5e82.0e82.5e83.0e83 5e8

BD

E-3

BB

DE

-15

BD

E-1

7B

DE

-28

BD

E-4

9B

DE

-71

BD

E-4

7B

DE

-66

BD

E-7

7B

DE

-100

BD

E-1

19B

DE

-99

BD

E-8

5B

DE

-126

BD

E-1

54B

DE

-153

BD

E-1

38B

DE

-156 B

DE

-184

BD

E-1

83B

DE

-191

BD

E-1

97B

DE

-196

BD

E-2

07B

DE

-206

BD

E-2

09

PBDE Analysis - Highest Calibration Standard

TetraTriDiMono Penta Hexa Hepta Octa Nona Deca

800 pg oc* 1600 pg OC 4000 pg OCRT (minutes)

Cou

nts

BD

E-7

1

BD

E-4

9

BD

E-2

09BDE-49/71 % Resolution = 0.4%<40% = PASS

BDE-209 USP Tf @10% height = 1.4<3 = PASS

BDE-99 USP Tf @10% height = 1.1<3 = PASS

BD

E-9

9

Page 24: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

24

4.10 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00 9.50 10.00 10.50 11.00 11.47-1.0e50.0e01.0e52.0e53.0e54.0e55.0e56.0e57.0e5

BD

E-3

BDE-

15

BDE-

17BD

E-28

BDE-

49BD

E-71 BD

E-47

BDE-

66BD

E-77 BD

E-10

0BD

E-11

9BD

E-99

BDE-

85BD

E-12

6 BDE-

154

BDE-

153

BDE-

138

BDE-

156

BDE-

184

BDE-

183

BDE-

191

BDE-

197

BDE-

196

BDE-

207

BDE-

206

BDE-

209

PBDE Analysis - Lowest Calibration Standard

• *oc = on column, solvent standard, overlay of quantification SRM transitions. (No signal normalization)

TetraTriDiMono Penta Hexa Hepta Octa Nona Deca

2 pg oc* 4 pg OC 10 pg OC

BD

E-2

09

RT (minutes)

Cou

nts

876

P

BD

E-4

9

BD

E-7

1

BDE-49/71 % Valley = 0.6 % <40% = PASS(EPA-1614 criteria)

BDE-209 USP Tf @10% height = 1.3<3 = PASS

BDE-99 USPTf @10% height = 0.8<3 = PASS

Page 25: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

25

Sensitivity

• Solvent standard 0.25 pg/uL

• t-score = 2.624

• n=15 injections

• n=14 degrees of freedom

• 99% confidence level

• Peak area % RSD < 15%

Excellent sensitivity for PBDEs using the AEI source

9.6459.750-2.5e2

1.0e32.0e33.0e34.0e35.0e36.0e37.0e38.0e39.0e39.8e3counts

BDE-209, 500 fg OC, n=15 injections% RSD peak area = 7.7 %

Calculated IDL = 100 fg OC (0.1 ng/Kg in sample)

RT (minutes)

Cou

nts

Page 26: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

26

Peak Area Repeatability (IDL concentration)

6%4%

7%9%

11% 11%9%

7%

11%10% 11%

6%

9%

6%

11% 10%9%

13% 13%

6% 6% 7%9% 10%

5% 6%8%

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

Peak area % RSD

Peak

are

a %

RSD

Compound

Peak area % RSD, n=15 injectionsPB

DE-3

PBDE

-7

PBDE

-15

PBDE

-17

PBDE

-28

PBDE

-49

PBDE

-71

PBDE

-47

PBDE

-66

PBDE

-77

PBDE

-100

PBDE

-119

PBDE

-99

PBDE

-85

PBDE

-126

PBDE

-154

PBDE

-153

PBDE

-138

PBDE

-156

PBDE

-184

PBDE

-183

PBDE

-191

PBDE

-197

PBDE

-196

PBDE

-207

PBDE

-206

PBDE

-209

• Solvent standards 0.02-0.25 pg/uL, t-score = 2.624, n=15 injections, n=14 degrees of freedom, 99% confidence level and peak area % RSD < 15%.

Page 27: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

27

Instrument Detection Limit (IDL)

8.5 % 5.2 %

6 2 4 5 6 6 5 3 6 8 6 3 5

15

2821 19

2720

9 10 1115 15

71

82

100

0

20

40

60

80

100

120

IDL (fg OC)

IDL

(fgO

C)

Compound

Instrument detection limit (fg OC)

BDE-

3

BDE-

7

BDE-

15

BDE-

17

BDE-

28

BDE-

49

BDE-

71

BDE-

47

BDE-

66

BDE-

77

BDE-

100

BDE-

119

BDE-

99

BDE-

85

BDE-

126

BDE-

154

BDE-

153

BDE-

138

BDE-

156

BDE-

184

BDE-

183

BDE-

191

BDE-

197

BDE-

196

BDE-

207

BDE-

206

BDE-

209

Mon

o

Di

Tri Te

tra

Pent

a

Hex

a

Hep

ta

Oct

a

Non

a Dec

a

Page 28: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

28

Example Linearity of Response

Excellent linearity, R² > 0.98 and RRF % RSD < 10%

• Solvent standards

• 1.0-2000 pg/uL

• Internal standard adjusted with 13C BDE stds

• No weighting applied as RRF was used

• Triplicate injection per level

Page 29: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

29

Linearity of Response

Excellent low end precision and accuracy for triplicate standard injections

Page 30: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

30

Robustness

1.E+03

1.E+04

1.E+05

1.E+06

1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73 76 79 82 85 88 91 94 97 100 103

Peak

are

a co

unts

.s-1

Injection number

BDE-7

BDE-49

BDE-119

BDE-153

BDE-183BDE-209

453 fg OC, % RSD= 7

255 fg OC, % RSD= 6

1.4 pg OC, % RSD= 5

2.0 pg OC, % RSD= 5

9.1 pg OC, % RSD= 3

11 fg OC, % RSD= 9

Peak area repeatability: n=105 unspiked extracted fish matrix injections

Peak area stable (no inlet, column, MS maintenance or tuning)

Page 31: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

31

ASMS 2015:Thermo Scientific™ Q Exactive™ GC Orbitrap™ GC-MS/MS system

Unprecedented Depth in Analysis

RP 120,000 (FWHM @ m/z 200)

EI (VeV) / CI; Full-scan, Timed-SIM

MS/MS capability

Redefining Routine GC-MS

RP 60,000 (FWHM @ m/z 200)

EI (VeV) / CI; Full-scan; Timed-SIM

NACRW 2016:Thermo Scientific™ Exactive™ GC Orbitrap™ GC-MS system

Orbitrap GC-MS Family

Instrument.com 2015 China Outstanding New Instrument

Page 32: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

32

Well Established and Proven Technologies

NeverVent™ technology

ExtractaBrite™ ion source

V-Lock source plug

Orbitrap mass analyzer

Incredible HR/AM performance

Highly regarded Q Exactive platform

TRACE 1310 GC

Unique modular injector and detector design

Rapid heat cycling

Page 33: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

33

Thermo Scientific Q Exactive GC Orbitrap GC-MS/MS System : The Technology Inside

ExtractaBrite Ion Source

BentFlatapole

Curved Linear Trap(C-TRAP)

Orbitrap Mass Analyzer

HCD CellMS/MS fragmentation

AQT Quadrupole(Precursor ion isolation)

Page 34: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

34

EI 70eVVeV

Orbitrap GC System Highlights

SensitivityMass AccuracyResolving Power Dynamic Range

Up to 120,000 at m/z 200

< 1ppm ppt >6 orders

Harder Softer

CI

Ionization Range

• Standard library searchable spectra • Molecular ion

confirmation (incl. adducts)

Page 35: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

35

Achieve Maximum Resolution and Maintain Sensitivity

15K 30K 60K

High selectivity analysis all of the time

• TIC signal intensity vs. scan number

• Increase the resolving power during acquisition

• Negligible drop in sensitivity

Page 36: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

36

Advantages for POPs analysis

Key BenefitsFast instrument and method set-up

Method consolidation

High efficiency data processing

Quantitative and qualitative

information in a single injection

Adjustable scope of analysis

Retrospective data analysis

Page 37: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

37

Polybrominated Diphenyl Ethers

Persistent Organic

Pollutants

“GC-Orbitrap is a useful tool for control labs,

outstanding sensitivity…high selectivity when

analyzing complex matrices…high robustness

…helps to fulfill new regulations with

extremely low limits (e.g. PCBs, PBDEs)”

Practical Experiences of Implementing POPs Methods using Orbitrap™ GC-MS. Nuria Cortés-Francisco, BFR 2017

Page 38: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

38

PBDE Analysis of Environmental Samples

4.06 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00 9.50 10.00 10.50 11.00 11.25-4.5e10

-3.8e10

-2.5e10

-1.3e10

0.0e0

1.3e10

2.5e10

3.8e10

5.0e10

6.3e10

7.5e10

BDE -

7

BDE -

15

BDE -

17BD

E -28

BDE -

49BD

E -71

BDE -

47BD

E -66

BDE -

77

BDE -

100 BD

E -11

9

BDE -

99

BDE -

85 BDE -

154

BDE -

153

BDE -

138

BDE -

184

BDE -

183

BDE -

191

BDE -

197

BDE -

196

BDE -

207

BDE -

206

BDE -

209

BDE -

3

BDE -

156

-1.4e50.0e0

5.0e5

1.0e6

1.5e6

2.0e6

2.5e6

3.0e6

3.5e6

3.9e6

di-BDEs

tetra-BDEs

tri-BDEs

penta-BDEs

hexa-BDEs

hepta-BDEs

octa-BDEs

nona-BDEs

deca-BDE

mono-BDE

BDE-

261

Page 39: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

39

Chromatography – Extracted Ion Chromatogram

Page 40: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

40

Sensitivity

Page 41: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

41

Tuna Sample Spiked 0.01 ng/g PBDEs

x=1-5, y=0-5

Page 42: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

42

Mass Accuracy and Isotope Pattern T:FTMS + p EI Full ms [75.0000-1050.0000]

949 950 951 952 953 954 955 956 957 958 959 960 961 962 963 964 965 966m/z

05

101520253035404550556065707580859095

100

Rela

tive

Abun

danc

e

959.16665C12OBr5

81Br5= 959.16751-0.89 ppm

957.16858C12OBr681Br4= 957.16956

-1.01 ppm 961.16437

C12OBr4 81Br6= 961.16546-1.13 ppm

955.17037C12OBr7 81Br3= 955.17160

-1.28 ppm 963.16210C12OBr3 81Br7= 963.16342

-1.36 ppm

953.17196C12OBr881Br2= 953.17365

-1.70 ppm965.16011

C12OBr281Br8= 965.16137-1.30 ppm

951.17438C12OBr981Br= 951.17570

-1.30 ppm

957.16960

949 950 951 952 953 954 955 956 957 958 959 960 961 962 963 964 965 966m/z

05

101520253035404550556065707580859095

100

Rela

tive

Abun

danc

e

959.16758C12OBr5

81Br5

12OBr681Br4 961.16556

C12OBr4 81Br6

955.17163C12OBr781Br3 963.16356

C12OBr381Br7

953.17367C12OBr881Br2 965.16159

C12OBr281Br8

951.17570C12OBr981Br

BDE-209acquired isotopic pattern

BDE-209theoretical

isotopic pattern

C

BDE-209

Page 43: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

43

POPs in Salmon: A New Approach using High Resolution Full Scan

SCCPsMCCPsPCBs,Pesticides Toxaphenes

5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0 7.2Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

SCCP TIC

C10H16Cl6m/z 312.9671

C11H17Cl7m/z 360.9437

C12H19Cl7m/z 374.9589

C13H20Cl8m/z 422.9361

C12H18Cl8m/z 408.9204

C13H19Cl9m/z 458.8936

C11H18Cl6m/z 326.9822

MCCP TIC

C14H24Cl6m/z 368.0218

C15H26Cl6m/z 382.0375

C15H25Cl7m/z 417.0058

C16H27Cl7m/z 431.0220

Page 44: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

44

HRAM Selectivity 63% C10-C13 Technical Mix, NCI, 60k Resolution

C10H15Cl6

C11H17Cl6

10.15

C11H16Cl7

10.73

C12H18Cl7

10.69

11.21

10.22

11.70

9.72

RT:6.48 - 14.43

6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

NL:2.00E8TIC MS

NL:2.00E7m/z= 346.92652

NL:3.00E7m/z= 360.94208

NL:3.00E7m/z= 394.90330

NL:2.00E7m/z= 408.91872

NL:2.00E7m/z= 444.87597

NL:2.00E7m/z= 458.89157

NL:2.00E7m/z= 492.85283

TIC

11.20

C12H17Cl8

11.73C13H19Cl8

C13H18Cl9

Page 45: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

45

Table 2. SCCP Linearity

• Linearity was assessed using the following dilution series for each SCCP chlorinationdegree (63% and 55.5%):

• 25• 50• 100• 250• 500• 1,000• 5,000• 10,000

• Concentrations as pg/µL.• In each standard, ~400 pg/µL p-Terphenyl-d14 was added and used as an IS

10,000 ppb

5000 ppb

Page 46: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

46

Negative Chemical Ionization: Linearity for SCCP 63% C10

R² = 0.9998

R² = 0.9998

R² = 0.9997

R² = 0.9996

0.00E+00

1.00E+07

2.00E+07

3.00E+07

4.00E+07

5.00E+07

6.00E+07

0 1000 2000 3000 4000 5000 6000

peak

are

a co

unts

Concentration [pg/µL]

m/z 312.9665

m/z 346.9275

m/z 380.8886

m/z 416.8466

Excellent compound linearity (25-5,000 ppb) was obtained for these C10 chlorinated homologues present in the SCCP 63% technical mixture.

Page 47: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

47

Peak Area Repeatability

• Peak area repeatability using full-scan NCI across n=10 repeatinjections of 25 ppb solvent standard (63% C10-C13).

inj. no m/z 492.8546(C13H18Cl9)

m/z 458.8936(C13H19Cl8)

1 765881 1308232

2 822551 1428540

3 795041 1361253

4 781911 1363928

5 776597 1321808

6 731874 1250508

7 761201 1305483

8 749797 1284342

9 737987 1257718

10 757772 1286412

mean 768061 1316822

StDev 27217.2 54540.3

%RSD 3.5 4.1

Page 48: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

48

Chlorinated Paraffins, PCBs, toxaphenes, pesticides

Persistent Organic

Pollutants

“using high resolution, accurate mass Orbitrap-MS enables much deeper insights into the pattern and content of CPs without having to fear mass interferences from other CPs or halogenated compounds such as PCBs. Preliminary results suggest that determination of both CPs and PCBs in the same sample in one run is possible, representing a potential for shorter sample preparation and quicker analyses of these types of POPs in food”

HIGH RESOLUTION ACCURATE MASS SCREENING FOR CHLORINATED PARAFFINS IN FOOD SAMPLES USING GC-ORBITRAP MASS SPECTROMETRY (Kerstin Krätschmer et al. Dioxin 2017)

Page 49: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

49

Summary - POPs Portfolio

Thermo Scientific™ TSQ™ 9000 GC-MS/MS

Orbitrap GC-MS

Magnetic Sector GC-HRMS

Thermo Scientific™ DFS™ Magnetic Sector GC-HRMS

GC-MS Triple Quadrupole

• Target compound analysis in routine • World-Wide compliance (e.g. EPA 1613) • Sensitivity combined with robustness for routine analysis• Robust-by-size with large volume ion source

• Target compound analysis in routine• Ease-of-use • Compliant with EU regulations for Dioxin food & feed analysis • Great price/performance ratio

Thermo Scientific™ Q Exactive™ GC Orbitrap™ GC-MS/MS

• Untargeted compound analysis • Method consolidation• Highest resolution and mass accuracy • Unique unknown identification capabilities

• Analysis of POPs is a challenging and varied application

• Legislation changes are allowing methods to be run on different instrumentation

• Thermo offers instrumentation to meet all the requirements for current and future analysis

Page 50: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

50

Thank You!

Q & A

Page 51: Modernizing Persistent Organic Pollutants (POPs) Analysis · Modernizing Persistent Organic Pollutants (POPs) Analysis . 2 • Introduction to POPs • Dioxin analysis with the DFS

51

Thank You

Please return our survey to receive a drink ticket for our daily networking event where you can continue discussions with our experts!