Exposure Assessment. Peter Haglund, Conny Danielsson, Erik Spinnel, Karin Wiberg. Umeå University, Sweden

Transcription

1 Use of GC GC in Human Exposure Assessment Peter Haglund, Conny Danielsson, Erik Spinnel, Karin Wiberg Umeå University, Sweden

2 Main Topics Cost-effective analysis of Dioxins in food and feed using GC GC-ECD Assessment of total human exposure through inhalation and ingestion of house dust using GC GC-MS

3 Dioxins by GCxGC-ECD EU-DIAC: Analysis of 17 2,3,7,8-PCDD/F and 12 WHO-PCBs in Food and Feed EU-DIFFERENCE: Certification of CRMs Full congener-specific analysis of PCBs and PCDD/Fs for source tracking Streamlined clean-up

4 Experimental Typical operating conditions First column: 30m x 0.25 x 0.25 DB-XLB Secondcolumn:1mx015x010 column: 0.15 x 0.10 LC50 LC-50 90(2min) C 1 ml/min Helium ECD 300C, 150 ml/min, 50 Hz 6s modulation period

5 Fish oil PCDD/Fs + n-o PCBs 6 s min. No Analyte No. Analyte PCB PeCDF PCB PeCDD PCB HxCDD 2378-TCDF HxCDF 2378-TCDD HpCDD PeCDF 12 OCDD

6 PCB-TEQ x 100 TEQ OCDF PCB Compound feed HxCDD3 HpCDD OCDD TCDF PeCDF1 PeCDF2 HxCDF1 HxCDF2 HxCDF3 HxCDF4 HpCDF1 HpCDF2 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 HxCDD2 PCB 126 x 50 PCB 169 x 50 HxCDD1 PeCDD TCDD PCB 81 x GC-HRMS GCxGC-ECD PCB 77 x 50 pg/g product

7 PCB-TEQ x 100 OCDF TEQ PCB 189 HpCDF Fish oil TCDF PeCDF1 PeCDF2 HxCDF1 HxCDF2 HxCDF3 HxCDF4 HpCDF1 PCB 167 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 OCDD HpCDD HxCDD3 HxCDD2 PCB 126 x 50 PCB 169 x 50 HxCDD1 PCB 81 x 50 PeCDD TCDD All accepted data GCxGC-ECD PCB 77 x 50 pg/g produ uct

8 All tetra - octa PCDF Cl 7Cl 8Cl 4 5Cl Sec conds 3 4Cl Minutes

9 Tetra PCDFs Seco onds / / / / Minutes

10 2378-Coelutions? Tetra s Penta s Hexa s Hepta s Octa s OK OK F/ D F/ D/ D F/ F OK OK

11 Conclusions DBXLB LC50 separates WHO-PCBs and 2,3,7,8- PCDD/Fs from each other and from matrix The WHO-PCBs are separated from other PCBs and 14/ PCDD/Fs are free of non-2378-pcdd/fs The results agree well with GC-HRMS data GC GC has potential as a routine method for the determination of TEQs in food and feed samples The sample prep has to match the speed of GC GC!

12 Streamlined PLE Clean-up Dionex ASE300; 100mL cell Filter paper Fat/ fat retainer ratio of g fish oil or vegetable oil 60 g of fat retainer (40% H 2 SO 4 / Silica) Na 2 SO 4 Matrix / Na 2 SO 4 Filter paper n-heptane, 2x5 min, 100% flush cycles Fat retainer e Na 2 SO C, 100 bar Filter paper p PCBs, PCBs PCDD/Fs

13 P C D D/ F -T EQ Compound Feed HxCD D3 HpC DD OC D D T CDF PeCD CDF1 PeCD CDF2 H xcd F1 HxCD CDF2 HxCD CDF3 H x CD F4 HpCD F1 HpCD F2 O C D F P CB 169 x 5 0 PCB 105 P CB 114 P CB 11 8 P CB 123 PCB 15 6 PCB 157 P C B 167 PCB 189 P CB-TEQ x 100 D D2 H xcd H xcd D1 CDD PeC P CB 12 6 x 50 CDD PCB 8 1 x 50 T CD GC-HRMS MK ASE + GC-HRMS P C B 77 x 5 0 pg/g product t pg/g g product

14 Selective ASE of PCBs/Dioxins Filter paper Na 2 SO 4 Matrix / Na 2 SO 4 Na 2 SO 4 AX21-Carbon / Celite Fr. I Fr. II Na 2 SO 4 Filter paper Fr. III Bulk lipids and PCBs Mono-ortho PCBs PCDD/F and non-ortho PCBs

15 ASE-Carbon Fr 1 (C7) Fr 2 (C7) Fr 3 (Ac/C7) Fr 4 (Tol) 20 0 I-PCB mo-pcb TF PCDD/F More than 99% lipids in Fr 1+2!

16 Modular PLE Step 1 Step 2 Step 3 Sample Filter paper Cell 2 H 2SO 4 Silica Filter paper Cell 1 Filter paper Carbon in Celite (5%) Na 2SO 4 + filter paper Cell 1 Cell 3 KOH Silica Fraction 1 i-pcb, mono -ortho PCBs Fraction 2 non-ortho PCB, PBDD, PCDD/Fs

17 Assessment of human exposure through inhalation and ingestion of house dust using GC GC-MS Example: House dust from Umeå City Hall Full-scan GC GC-ToF-MS Total Ion Chromatograms Overview Selected ion traces Major Contaminants

18 City Hall dust Kommun

19 Phthalates (m/z 149)

20 Phosphate esters (m/z 99)

21 Identifiction Name Similarity Reverse Probability CAS Ethanol, 2-butoxy-, phosphate Ethanol, 2-butoxy-, phosphate Methyl-Z-tetradecen-1-ol acetate

22 Brominated Flame Retardants Tetrabromodiphenyl ether TPP (BDE 47) Pentabromodiphenyl ethers (BDE 99 and 100)

23 Summary: City Hall dust Kommun

24 Summary: City Hall dust Phthalates Kommun

25 Summary: City Hall dust Organophosphates Kommun

26 Summary: City Hall dust PBDEs Kommun

27 Summary: City Hall dust Sterols Kommun

28 Conclusions II The major components in a house dust extract was easily characterized as: Petroleum hydrocarbons Phthalate plasticizers Organophosphate plasticizers/flame retardants Brominated flame retardants Sterols (Semi-)Quantification is straightforward Exposure may be calculated using dust levels and estimated human ventilation and dust ingestion rates

29 Acknowledgements This work was funded by: European Commission (DIFFERENCE and DIAC) The Swedish EPA (POPs screening program and ChEmiTecs: Chemical Emissions from Articles in the Technosphere)