dioxin/furan screening method

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Dioxin/Furan Screening Method. John D. Ragsdale, GC/MS Product Specialist. GC/MS/MS Dioxin Screening. In The Beginning… Current Methodology The Plan Sample Preparation The GC/MS/MS Configuration The data. In The Beginning…. - PowerPoint PPT Presentation

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Page 1: Dioxin/Furan Screening Method
Page 2: Dioxin/Furan Screening Method

Dioxin/Furan Screening Method

John D. Ragsdale, GC/MS Product Specialist

Page 3: Dioxin/Furan Screening Method

GC/MS/MS Dioxin Screening

In The Beginning… Current Methodology The Plan Sample Preparation The GC/MS/MS Configuration The data

Page 4: Dioxin/Furan Screening Method

In The Beginning…

Interest in the analysis of dioxins and furans have increased due to the contamination of feed for livestock and poultry in Europe. The local sales force has responded by requesting application notes and other literature for this analysis on PolarisQ.

Similar requests have come from our Pan-Pacific and Asian sales force. This group also includes a current Finnigan customer directly involved in the analysis of dioxin and furan contaminated samples.

Page 5: Dioxin/Furan Screening Method

Dioxin/Furan Analysis EPA Methods

Low Resolution MS– 8270 ( full scan )– 8280 ( SIM )– Part per million and

part per billion detection limits

High Resolution MS– 8290 ( SIM )– 1613 ( SIM )– Part per trillion

detection limits

Page 6: Dioxin/Furan Screening Method

The Plan

Sample Preparation– Minimal cleanup required

Chromatographic Resolution– BPX-5; 25M; 0.15mm ID

column

Robust Chromatography– Split injections (2 ul injection)

Specificity– MS/MS

Deliverables– Write SOPs

Page 7: Dioxin/Furan Screening Method

Sample Preparation

25 grams of material mixed with 50 grams of sodium sulfate.

Soxhlet extraction for 24 hours with 50:50 hexane : methylene chloride.

Partition against 4 X 40ml concentrated sulfuric acid.

Concentrate to 100 ul of 5X dilution of CS3 (2pg/ul of tetra-isomers)

Page 8: Dioxin/Furan Screening Method

Additional Sample Preparation

Gel Permeation Chromatography– Removes high molecular weight interferences

Acid, neutral, and basic silica gel and carbon– Removes nonpolar and polar interferences

Alumina, Florosil– Removes chlorodiphenyl ethers

Any additional cleanup will lower ultimate detection limits but is not required for this MS/MS screening technique

Page 9: Dioxin/Furan Screening Method

Dioxin Screening GC/MS/MS System

Trace GC with split/splitless inlet PPKD DPFC 700kPa with Manual Split Flow 250 Liter Turbo pump PolarisQ EI only / Vacuum Interlock AS2000 Liquid Autosampler SGE BPX-5, 25 meter, 0.15 mm ID, 0.25

micron film column Restek Silco-Steel split liners w/glass wool

plug

Page 10: Dioxin/Furan Screening Method

Configuration Rationale

Split Injections allow for “dirtier” sample introduction.

Extracts can be screened without the time and cost of extensive cleanup.

MS/MS affords the selectivity to remove matrix interference from “dirty” extracts.

Page 11: Dioxin/Furan Screening Method

Chromatographic Conditions

Injector: – 250C

Column Flow: – 0.9 ml/min

Split flow: – 10 ml/min

Ramp:

– 150C (1min) to 200C @ 20C/min (1.5min)– to 300C @ 3C/min (1.7min) : 40min total

Page 12: Dioxin/Furan Screening Method

Chromatographic Resolution

Tetra-Dioxins Tetra-FuransRT: 16.93 - 20.35 SM: 3G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

0

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100

Relati

ve Ab

unda

nce

NL:2.25E5

m/z= 321.50-322.50 MS pcb1248-20psi-05

NL:4.70E4

m/z= 333.50-334.50 MS pcb1248-20psi-05

RT: 16.93 - 20.35 SM: 5G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

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Relati

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nce

NL:2.66E5

m/z= 305.50-306.50 MS pcb1248-20psi-05

NL:5.20E4

m/z= 317.50-318.50 MS pcb1248-20psi-05

2,3,7,8TCDD-IS

2,3,7,8TCDF-IS

2,3,7,8TCDD 2,3,7,8

TCDF

Page 13: Dioxin/Furan Screening Method

Full Scan, SIM, or MS/MS

Page 14: Dioxin/Furan Screening Method

Full Scan – 10pg/ul in 25g Cow’s milkRT: 0.00 - 40.04

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Re

lativ

e A

bu

nd

an

ce

7.927.75

7.26

8.26

27.28

6.99

26.788.42

27.4625.34

29.00

25.0829.31

6.46 24.8437.3621.60 29.72

23.3829.96

8.73 20.8420.09 30.4019.85

35.1318.1331.288.99 17.49 34.5112.23 12.78 38.0036.126.08 9.76

5.69

NL:2.93E7

TIC MS CS3-MILK-PCDD-PCDF-FS-402

Page 15: Dioxin/Furan Screening Method

Dioxins: EPA Method 1613

Linearity to 500 fg/uL to 200 pg/uL for 2,3,7,8-TCDD

Page 16: Dioxin/Furan Screening Method

Dioxins: Typical 500 fg/ul injection

RT: 17.09 - 20.19 SM: 7G

17.5 18.0 18.5 19.0 19.5 20.0

Time (min)

0

10

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30

40

50

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1000

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Re

lativ

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bu

nd

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ce

500fg 2,3,7,8-TCDD

100pg C13-2,3,7,8-TCDD

NL: 3.60E1

m/z= 256.5-257.5+258.5-259.5 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS ICIS CS1-MSMS-012001-102

NL: 7.11E3

m/z= 267.5-268.5+269.5-270.5 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS ICIS CS1-MSMS-012001-102

Page 17: Dioxin/Furan Screening Method

Dioxins:Typical Precision for 1613

COMPOUND % RSD

2,3,7,8-TCDD 10.8

1,2,3,7,8-PeCDD 6.4

1,2,3,4,7,8-HxCDD 6.9

1,2,3,6,7,8-HxCDD 9.1

1,2,3,7,8,9-HxCDD 8.7

1,2,3,4,6,7,8-HpCDD 4.9

OCDD 5.2

Page 18: Dioxin/Furan Screening Method

Dioxins:Typical Precision for 1613 ISTD

COMPOUND % RSD

C13-2,3,7,8-TCDD 4.2

C13-1,2,3,7,8-PeCDD 5.6

C13-1,2,3,4,7,8-HxCDD 8.6

C13-1,2,3,6,7,8-HxCDD 6.9

C131,2,3,7,8,9-HxCDD 7.0

C13-1,2,3,4,6,7,8-HpCDD

8.9

C13-OCDD 9.2

Page 19: Dioxin/Furan Screening Method

Dioxins: Isotope Ratio StabilityCOMPOUND

IONS RATIO % RSD

2,3,7,8-TCDD

259/257 0.97 22.7

1,2,3,7,8-PeCDD

275/277 0.83 10.0

1,2,3,4,7,8-HxCDD

325/327 0.69 20.1

1,2,3,6,7,8-HxCDD

325/327 0.66 13.15

1,2,3,7,8,9-HxCDD

325/327 0.69 14.4

1,2,3,4,6,7,8-HpCDD

361/363 1.35 9.5

OCDD 395/397 1.14 5.7

Page 20: Dioxin/Furan Screening Method

Dioxins: Full Scan – 10pg/ul std vs. cow’s milk

RT: 16.93 - 20.35 SM: 7G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

0

10

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Relati

ve Abu

ndance

NL:2.82E3

m/z= 321.5-322.5 MS CS3--PCDD-PCDF-FS-404

NL:2.07E4

m/z= 333.5-334.5 MS CS3--PCDD-PCDF-FS-404

RT: 16.93 - 20.35 SM: 7G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

0

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Relativ

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dance

NL:1.91E4

m/z= 321.5-322.5 MS CS3-MILK-PCDD-PCDF-FS-402

NL:3.41E4

m/z= 333.5-334.5 MS CS3-MILK-PCDD-PCDF-FS-402

Nonane Cow’s milk

2,3,7,8TCDD

2,3,7,8TCDD-IS

2,3,7,8-TCDD ??

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

1,2,3,4TCDD-RS

Page 21: Dioxin/Furan Screening Method

Dioxins: MS/MS – 10pg in nonaneCS3--PCDD-PCDF-MSMS-403 01/17/2001 06:14:33 PM1613 CS3 MSMS :: 120 :: WFON

RT: 16.93 - 20.35 SM: 7G

17.0 17.5 18.0 18.5 19.0 19.5 20.0Time (min)

0

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1000

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18.97

18.44

19.24 19.4617.46 18.75 19.83 20.0717.9517.2518.95

18.45

19.44 19.7617.80 20.2317.9417.5517.06

NL: 1.00E3m/z= 256.50-257.50+258.50-259.50 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS CS3--P CDD-P CDF-MSMS-403

NL: 9.38E3m/z= 267.50-268.50+269.50-270.50 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS CS3--P CDD-P CDF-MSMS-403

CS3--P CDD-P CDF-MSMS-403 #966-1043 RT: 18.83-19.12 AV: 16 NL: 1.53E2F: + c SRM ms2 [email protected] [ 253.00-263.00]

253 254 255 256 257 258 259 260 261 262 263m/z

0

5

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Rel

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bun

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257

259

261

263258253

260

256254 262255

264261

2,3,7,8TCDD

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

Page 22: Dioxin/Furan Screening Method

Dioxins: MS/MS – 10pg/ul in cow’s milkCS3-MILK-PCDD-PCDF-MSMS-403 01/17/2001 06:58:07 PM

1613 CS3 MILK MSMS :: 120 :: WFON

RT: 16.93 - 20.35 SM: 7G

17.0 17.5 18.0 18.5 19.0 19.5 20.0Time (min)

0

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100R

elat

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Abu

nda

nce

19.01

18.4720.0019.5617.63 17.7417.25 18.16 18.64

19.00

18.49

19.33 19.56 20.0217.87 18.3017.14 17.53

NL: 1.32E3m/z= 256.50-257.50+258.50-259.50 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS CS3-MILK-P CDD-P CDF-MSMS-403

NL: 1.36E4m/z= 267.50-268.50+269.50-270.50 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS CS3-MILK-P CDD-P CDF-MSMS-403

CS3-MILK-P CDD-P CDF-MSMS-403 #1263-1342 RT: 18.93-19.15 AV: 16 NL: 2.53E2F: + c SRM ms2 [email protected] [ 253.00-263.00]

253 254 255 256 257 258 259 260 261 262 263m/z

0

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Rel

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257

259

263

253

261

258

260 262

254255

256264

2,3,7,8TCDD

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

Page 23: Dioxin/Furan Screening Method

Furans: EPA Method 1613

Linearity from 500 fg/uL to 200 pg/uL for 2,3,7,8-TCDF

Page 24: Dioxin/Furan Screening Method

Furans: Typical 500 fg/ul InjectionRT: 17.09 - 20.19 SM: 7G

17.5 18.0 18.5 19.0 19.5 20.0

Time (min)

0

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Re

lativ

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nd

an

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500fg 2,3,7,8-TCDF

100pg C13-2,3,7,8-TCDF

NL: 7.27E1

m/z= 240.5-241.5+242.5-243.5 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS ICIS CS1-MSMS-012001-102

NL: 8.90E3

m/z= 251.5-252.5+253.5-254.5 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS ICIS CS1-MSMS-012001-102

Page 25: Dioxin/Furan Screening Method

Furans:Typical Precision for 1613

COMPOUND %RSD

2,3,7,8-TCDF 17.41,2,3,7,8-PeCDF 5.52,3,4,7,8-PeCDF 6.21,2,3,4,7,8-HxCDF 3.51,2,3,6,7,8-HxCDF 4.02,3,4,6,7,8-HxCDF 5.61,2,3,7,8,9-HxCDF 6.41,2,3,4,6,7,8-HpCDF 4.51,2,3,4,7,8,9-HpCDF 5.8OCDF 5.4

Page 26: Dioxin/Furan Screening Method

Furans:Typical Precision for 1613 ISTD

COMPOUND %RSD

C13-2,3,7,8-TCDF 4.0C13-1,2,3,7,8-PeCDF 4.5C13-2,3,4,7,8-PeCDF 4.7C13-1,2,3,4,7,8-HxCDF 7.2C13-1,2,3,6,7,8-HxCDF 5.5C13-2,3,4,6,7,8-HxCDF 6.2C13-1,2,3,7,8,9-HxCDF 7.7C13-1,2,3,4,6,7,8-HpCDF 8.1C13-1,2,3,4,7,8,9-HpCDF 9.4C13-OCDD 9.2

Page 27: Dioxin/Furan Screening Method

Furans: Isotope Ratio StabilityCOMPOUND IONS RATIO % RSD2,3,7,8-TCDF 243/241 0.81 22.71,2,3,7,8-PeCDF 275/277 0.81 7.12,3,4,7,8-PeCDF 275/277 0.82 7.01,2,3,4,7,8-HxCDF

309/311 0.67 10.4

1,2,3,4,7,8-HxCDF

309/311 0.67 8.1

1,2,3,6,7,8-HxCDF

309/311 0.65 5.5

2,3,4,6,7,8-HxCDF

309/311 0.65 7.9

1,2,3,4,6,7,8-HpCDF

345/347 1.26 7.3

1,2,3,4,7,8,9-HpCDF

345/347 1.29 7.0

OCDF 379/381 1.14 5.6

Page 28: Dioxin/Furan Screening Method

Furans: Full Scan – 10pg/ul std vs. cow’s milk

RT: 16.93 - 20.35 SM: 7G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

0

10

20

30

40

50

60

70

80

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1000

10

20

30

40

50

60

70

80

90

100Re

lative

Abunda

nceNL:2.96E3

m/z= 305.5-306.5 MS CS3--PCDD-PCDF-FS-404

NL:2.53E4

m/z= 317.5-318.5 MS CS3--PCDD-PCDF-FS-404

RT: 16.93 - 20.35 SM: 7G

17.0 17.2 17.4 17.6 17.8 18.0 18.2 18.4 18.6 18.8 19.0 19.2 19.4 19.6 19.8 20.0 20.2

Time (min)

0

10

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Relati

ve Ab

undanc

e

NL:1.36E4

m/z= 305.5-306.5 MS CS3-MILK-PCDD-PCDF-FS-402

NL:4.10E4

m/z= 317.5-318.5 MS CS3-MILK-PCDD-PCDF-FS-402

Nonane Cow’s Milk

2,3,7,8TCDF ???

2,3,7,8TCDF-IS

2,3,7,8TCDF

2,3,7,8TCDF-IS

Page 29: Dioxin/Furan Screening Method

Furans: MS/MS – 10pg/ul in nonaneCS3--PCDD-PCDF-MSMS-403 01/17/2001 06:14:33 PM

1613 CS3 MSMS :: 120 :: WFON

RT: 16.93 - 20.35 SM: 7G

17.0 17.5 18.0 18.5 19.0 19.5 20.0Time (min)

0

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1000

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18.44

17.82 18.7517.5017.31 19.05 19.2217.98 19.81 20.0318.43

18.9017.7917.47 19.2118.22 19.55 19.75 20.0417.32

NL: 1.25E3m/z= 240.50-241.50+242.50-243.50 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS CS3--P CDD-P CDF-MSMS-403

NL: 1.22E4m/z= 251.50-252.50+253.50-254.50 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS CS3--P CDD-P CDF-MSMS-403

CS3--P CDD-P CDF-MSMS-403 #838-895 RT: 18.35-18.54 AV: 11 NL: 3.14E2F: + c SRM ms2 [email protected] [ 237.00-247.00]

237 238 239 240 241 242 243 244 245 246 247m/z

0

5

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Rel

ativ

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bun

danc

e

241

243

245

242

244240

247237 246238 239

2,3,7,8TCDF

2,3,7,8TCDF-IS

Page 30: Dioxin/Furan Screening Method

Furans: MS/MS – 10pg/ul in cow’s milk

CS3-MILK-PCDD-PCDF-MSMS-403 01/17/2001 06:58:07 PM1613 CS3 MILK MSMS :: 120 :: WFON

RT: 16.93 - 20.35 SM: 7G

17.0 17.5 18.0 18.5 19.0 19.5 20.0Time (min)

0

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ance

18.49

17.65

17.9218.6317.24 18.10 19.60 20.0219.5019.08

18.48

18.74 19.0317.84 19.12 19.4817.57 18.30 19.84 20.1717.3117.19

NL: 1.64E3m/z= 240.50-241.50+242.50-243.50 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS CS3-MILK-P CDD-P CDF-MSMS-403

NL: 1.65E4m/z= 251.50-252.50+253.50-254.50 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS CS3-MILK-P CDD-P CDF-MSMS-403

CS3-MILK-P CDD-P CDF-MSMS-403 #1086-1159 RT: 18.41-18.61 AV: 15 NL: 3.85E2F: + c SRM ms2 [email protected] [ 237.00-247.00]

237 238 239 240 241 242 243 244 245 246 247m/z

0

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Rel

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241

243

247

245237

246

244

242238

239240

248

2,3,7,8TCDF

2,3,7,8TCDF-IS

Page 31: Dioxin/Furan Screening Method

Spiked Matrix @ 2pg/ul or 4 pg/g (ppt)

Cow’s milk Soil Coal fly ash

Page 32: Dioxin/Furan Screening Method

Dioxin: 2 pg/ul in 25g Cow’s Milk RT: 15.23 - 20.92 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

80

90

1000

10

20

30

40

50

60

70

80

90

100Re

lative

Abu

ndan

ceNL: 1.95E2

m/z= 256.5-257.5+258.5-259.5 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS CS3-5X-MILK-012101-212

NL: 1.89E3

m/z= 267.5-268.5+269.5-270.5+271.5-272.5 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS CS3-5X-MILK-012101-212

RT: 15.09 - 20.74 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

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1000

10

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50

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100

Rela

tive

Abun

danc

e

NL: 2.08E2

m/z= 240.5-241.5+242.5-243.5 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS CS3-5X-MILK-012101-212

NL: 2.25E3

m/z= 251.5-252.5+253.5-254.5+255.5-256.5 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS CS3-5X-MILK-012101-212

TCDD TCDF

2,3,7,8TCDD

2,3,7,8TCDF

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

2,3,7,8TCDF-IS

Page 33: Dioxin/Furan Screening Method

Dioxin: 2 pg/ul in 25g Soil RT: 15.23 - 20.92 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

80

90

1000

10

20

30

40

50

60

70

80

90

100

Rela

tive

Abun

danc

e

NL: 3.81E2

m/z= 256.5-257.5+258.5-259.5 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS CS3-5X-SOIL-012101-212

NL: 1.99E3

m/z= 267.5-268.5+269.5-270.5+271.5-272.5 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS CS3-5X-SOIL-012101-212

RT: 15.09 - 20.74 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

80

90

1000

10

20

30

40

50

60

70

80

90

100

Rela

tive

Abun

danc

e

NL: 2.39E2

m/z= 240.5-241.5+242.5-243.5 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS CS3-5X-SOIL-012101-212

NL: 2.17E3

m/z= 251.5-252.5+253.5-254.5+255.5-256.5 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS CS3-5X-SOIL-012101-212

2,3,7,8TCDD

2,3,7,8TCDF

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

2,3,7,8TCDF-IS

TCDD TCDF

Page 34: Dioxin/Furan Screening Method

2 pg/ul in 25g Coal Fly Ash RT: 15.23 - 20.92 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

80

90

1000

10

20

30

40

50

60

70

80

90

100Re

lativ

e Ab

unda

nce

NL: 1.87E2

m/z= 256.5-257.5+258.5-259.5 F: + c SRM ms2 [email protected] [ 253.00-263.00] MS CS3-5X-FLYASH-012101-212

NL: 1.83E3

m/z= 267.5-268.5+269.5-270.5+271.5-272.5 F: + c SRM ms2 [email protected] [ 264.00-274.00] MS CS3-5X-FLYASH-012101-212

RT: 15.09 - 20.74 SM: 7G

16 17 18 19 20

Time (min)

0

10

20

30

40

50

60

70

80

90

1000

10

20

30

40

50

60

70

80

90

100

Rela

tive

Abun

danc

e

NL: 2.29E2

m/z= 240.5-241.5+242.5-243.5 F: + c SRM ms2 [email protected] [ 237.00-247.00] MS CS3-5X-FLYASH-012101-212

NL: 2.54E3

m/z= 251.5-252.5+253.5-254.5+255.5-256.5 F: + c SRM ms2 [email protected] [ 248.00-258.00] MS CS3-5X-FLYASH-012101-212

TCDD TCDF

2,3,7,8TCDD

2,3,7,8TCDF

2,3,7,8TCDD-IS

1,2,3,4TCDD-RS

2,3,7,8TCDF-IS

Page 35: Dioxin/Furan Screening Method

Summary of analyte recovery

Matrix Average (pg/ul)

% RSD

(n = 12)

Nonane 2.18 10.2Soil 1.91 9.7Milk 2.28 7.6Coal Fly Ash 2.05 10.2

Matrix Average (pg/ul)

% RSD

(n = 12)

Nonane 1.84 7.8Soil 1.90 11.5Milk 1.92 11.5Coal Fly Ash 1.95 5.6

2,3,7,8-TCDD(2 pg/ul spike)

2,3,7,8-TCDF(2 pg/ul spike)

Page 36: Dioxin/Furan Screening Method

Summary of isotope ratios

Matrix Average (cali = 0.97)

% RSD

(n = 12)

Nonane 0.93 11.6Soil 0.83 17.1Milk 1.06 20.4Coal Fly Ash 0.99 24.3

Matrix Average (cali = 0.81)

% RSD

(n = 12)

Nonane 0.80 20.8Soil 0.82 20.6Milk 0.87 17.6Coal Fly Ash 0.89 19.7

2,3,7,8-TCDD259/257

2,3,7,8-TCDF243/241