Improved Separation and Quantification of Dioxin and Furan Congeners Using an Application-Specific Capillary Gas Chromatographic Column and GC-HRMS

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1 Improved Separation and Quantification of Dioxin and Furan Congeners Using an Application-Specific Capillary Gas Chromatographic Column and GC-HRMS Frank Dorman, Shawn Reese, Gary Stidsen Restek Corporation, Bellefonte, Pennsylvania Jack Cochran LECO Corporation, Las Vegas, Nevada Eric Reiner, Karen MacPherson, Terry Kolic Ministry of Environment, Etobicoke, Ontario

2 Analysis of Dioxins and Furans

3 History GC Analytical Methods All isomers/congeners can be separated from each other with a minimum of two columns (Ryan, J., 1991) and GC HRMS Typically used: 6-M GC column, 5 phenyl liquid phase, separates many congeners, but not with complete resolution HOWEVER.. Confirmation still required, generally with high-cyano liquid phases ex. for 2,3,7,8-TCDF Method 1613 suggests a 225-phase

4 Dioxin and Furan Analysis Dual column method Usually 5 diphenyl column and a high-cyano column (eg Rtx-225) Cyano columns have poorer lifetimes and lower maximum operating temperatures 5 diphenyl phases do not have the selectivity to accurately quantitate most samples USEPA requires 2,3,7,8-tcdf to be confirmed on a X-225 Desirable to have both columns in the same oven, and to improve the separation of the 5, or employ a single column which achieves the necessary separation

5 PCDD and PCDF Target List # of Chlorine #Dioxins #Furans tetra 22(1) 38(1) penta 14(1) 28(2) hexa 1(3) 16(4) hepta 2(1) 4(2) octa 1(1) 1(1) ( ) numbers are 2,3,7,8-substituted congeners

6 Tetra-dioxin resolution check standard on 5 diphenyl / 95 dimethyl stationary phase Jul21_ / : Voltage SIR 2 Channels EI e M X.25 mm i.d. X.25 um d.f. Time

7 How Resolution Affects Quantitation Quantification of 2 ng/ul Reference Standard (Results Based on Multi-level/Multi-component Calibration): Component A Component B Component A & B Rep Rep Rep Component A Rep Rep Rep Component B Rep Rep Rep

8 Achieving Analyte Separation Resolution R = 1/4 L / h x ( k / k+1 ) x ( α-1 1 / α ) Capacity Factor k = t R - t / t Selectivity α = k 2 / k 1 Thermodynamics: G G = H - T S G G = - RT ln K D

9 Modeling - Energies of Interaction F F H 3 C O Si Si O CH 3 F F G G Cl Cl Cl O O O O Cl Cl Cl Cl Cl F Si O F Separation ( α)( = G

10 3-Space Selectivity Model for 3 Compounds Surface=F H S

11 Example Result: Demeton-O on PDMS: Observed G = -1.14E4 J/mol Calculated G = -1.13E4 J/mol

12 Tetra-dioxin resolution check standard on 5 diphenyl / 95 dimethyl stationary phase Jul21_ / : Voltage SIR 2 Channels EI e M X.25 mm i.d. X.25 um d.f. Time

13 Rtx-Dioxin2 Capillary GC Column TCDD Resolution Mix 1238/

14 ay6_cs5 x4 TCDD Dioxin Window Voltage SIR 14 Channels EI e ay6_cs PCDD Voltage SIR 14 Channels EI e ay6_cs HxCDD Voltage SIR 14 Channels EI e ay6_cs HpCDD Voltage SIR 14 Channels EI e ay6_cs5 OCDD Voltage SIR 14 Channels EI e Time

15 ay6_cs TCDF Furan Window Voltage SIR 14 Channels EI e ay6_cs PCDF Voltage SIR 14 Channels EI e ay6_cs HxCDF Voltage SIR 14 Channels EI e ay6_cs HpCDF Voltage SIR 14 Channels EI e ay6_cs5 OCDF Voltage SIR 14 Channels EI e Time

16 GC program for RTX-Dioxin2 Gas Flow - constant 6m x.25mm x.25µm 1.5mL/min Initial Temp. 13 C - hold 1min 1st Temp. Ramp 2nd Temp. Ramp 3rd Temp. Ramp 4 C/min to 2 C, hold 3. C/min to 235 C, hold 5 C /min to 3 C, hold ~5-1min. Total Run Time ~43 min

17 TCDF Resolution on RTX-Dioxin2 TD TF WD may12_res : Voltage SIR 2 Channels EI e6 2347/ may12_res18 1 2: Voltage SIR 2 Channels EI e5 TCDFs 13C Time

18 TCDF ion channel for flyash extract c may12_res15 1 Flyash Extract : Voltage SIR 2 Channels EI e may12_res : Voltage SIR 2 Channels EI e6 13C12-2,3,7,8-tcdf Time

19 TCDF ion channel for sewage sludge c /1 jul4_dx3_s3 Sm (Mn, 2x1) 1 Sewage sludge : Voltage SIR 2 Channels EI e jul4_dx3_s3 Sm (Mn, 2x1) : Voltage SIR 2 Channels EI e6 13C tcdf 13C-2,3,6,7-tcdf Time

20 Table I - 2,3,7,8-TCDF (pg/g) Certified 5 phenyl X-225 Rtx-DIOXIN2 Value WMS ± 16 EC-2(DX-1) 88 n/a (±44) Sediment NIST n/a Flyash Flyash Biota Biota

21 TCDF ion channel for Biota sample c may9_res13 1 2: Voltage SIR 2 Channels EI e4 DPE ion channel may9_res13 1 tcdf 2: Voltage SIR 2 Channels EI e4 may9_res13 1 2: Voltage SIR 2 Channels EI e6 13 C-2378-tcdf Time

22 Potential resolution between DPEs and Furans c may9_res13 1 DPE ion channel 2: Voltage SIR 2 Channels EI e4 may9_res13 1 2: Voltage SIR 2 Channels EI e4 tcdf may9_res13 1 2: Voltage SIR 2 Channels EI e6 13 C-2378-tcdf Time

23 ay6_res TCDD : Voltage SIR 2 Channels EI e ay6_res : Voltage SIR 2 Channels EI e 2378-TCDD Time

24 5 Phenyl Column Resolution Mix Rtx-DIOXIN / tcdd 1237/38-tcdd C-1234-tcdd 13C-2378-tcdd Time

25 Table II - 2,3,7,8-TCDD (pg/g) Certified 5 phenyl X-225 Rtx-Dioxin2 Value WMS ±5.6 EC-2 (DX-1) 24 n/a (± 53) Sediment Flyash Flyash-2 <

26 ay6_res PCDF 3: Voltage SIR 2 Channels EI e ay6_res PCDF PCDF 3: Voltage SIR 2 Channels EI e Time

27 Table III - 1,2,3,7,8-PCDF (pg/g) Certified 5 phenyl Rtx-Dioxin2 Value WMS ± 5 EC-2(DX-1) ± 14 Sediment Flyash Flyash

28 Table IV- 2,3,4,7,8-PCDF (pg/g) Certified 5phenyl Rtx-Dioxin2 Value WMS ± 6.1 EC-2(DX-1) ± 32 Sediment Flyash Flyash

29 ay6_res PCDD 3: Voltage SIR 2 Channels EI e ay6_res : Voltage SIR 2 Channels EI e PCDD Time

30 HxCDF ion channel in Flyash sample c may12_res15 1 4: Voltage SIR 16 Channels EI e6 may12_res HxCDF HxCDF 13 C-HxCDFs 4: Voltage SIR 16 Channels EI e HxCDF HxCDF Time

31 Table V - 1,2,3,4,7,8-HxCDF (pg/g) Certified 5 phenyl Rtx-Dioxin2 Value WMS ± 24 EC-2 (DX-1) (± 276) Sediment Flyash Flyash

32 HxCDD ion channel for sediment EC-2 1uL may14_res3 1 4: Voltage SIR 16 Channels EI e5 may14_res HxCDD 13 C-HxCDDs 4: Voltage SIR 16 Channels EI e HxCDD HxCDD Time

33 Table VI - 1,2,3,7,8,9-HxCDD (pg/g) Certified 5 phenyl Rtx-Dioxin2 Value WMS ± 8 EC-2 (DX-1) (± 24) Sediment Flyash Flyash

34 ay6_res HpCDF 5: Voltage SIR 11 Channels EI e ay6_res HpCDF HpCDF : Voltage SIR 11 Channels EI e Time

35 ay6_res HpCDD : Voltage SIR 11 Channels EI e ay6_res : Voltage SIR 11 Channels EI e HpCDD HpCDD Time

36 ay6_res9 OCDD/OCDF : Voltage SIR 9 Channels EI e OCDF ay6_res : Voltage SIR 9 Channels EI e OCDD ay6_res : Voltage SIR 9 Channels EI e Time

37 Rtx-Dioxin2 Capillary Column Proprietary backbone stabilized polysiloxane designed for toxic dioxin and furan analysis by GC-HRMS 34 maximum operating temperature in standard fused silica tubing Can be used as secondary confirmation column for Rtx-Dioxin, or other primary columns like 5 diphenyl phases Can function as single column for stand-alone dioxin and furan analysis and has been accredited for use as such Clive Robinson ALS Environmental Queensland Australia Chromatographically separates the chlorinated diphenylethers from the furans especially important in biota matrices Columns available: Cat # M X.25 mm i.d. X.25 um d.f. Cat # M X.18 mm i.d. X.18 um d.f.

A new gold standard for Dioxin analysis A combined approach ; automated efficient clean-up together with a new Triple Quadrupole GC-MS/MS

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