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  • Analysis of Dioxins and POPs using

    Atmospheric Pressure GC/MS

    Ingrid Ericson Jogsten

    MTM research centre, rebro University

    2014-12-16 1

  • 2014-12-16 2

    Outline

    POPs and related environmental pollutants

    POPs analysis

    APGC

    Dioxins

    Other POPs

    APGC vs high res for PCBs and OCPs

    BFRs

    PBDEs

    Other environmental pollutants

  • Progress of scientific knowledge

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    5000

    6000

    7000

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    9000

    10000

    Scientific publications

    Knowledge on effects

    "PCBs and effects"

    "PFOS and effects"

    0

    50

    100

    150

    200

    250

    300

    350

    400 Scientific publications

    Analytical development

    "Analytical Chemistry"

    Slide courtesy of Samira Salihovic

  • Environment and Health Research focussed on POPs

    Health and exposure

    Environmental Levels

    Chemical and Bioassay Analysis

    UNEP reference laboratory

  • Stockholm Convention

    Parties (179), Signatories (152)

  • Chemical Parent POPs Transformation products

    Aldrin aldrin

    Dieldrin dieldrin

    Endrin endrin

    Chlordane cis- and trans-chlordane cis- and trans nonachlor, oxychlordane

    Heptachlor heptachlor -heptachlorepoxide

    DDT 4,4-DDT, 2,4-DDT 4,4-DDE, 2,4 DDE, 4,4-DDD, 2,4-DDD

    HCB hexachlorobenzene

    Mirex mirex

    Toxaphene congeners P26, P50, P62

    PCB 7 marker congeners: #28,#52,#101,#118,#138,#153,#180

    12 congeners with TEFs: #77, #81, #105, #114, #118, #123, #126, #156, #157,

    #167, #169, #189

    PCDD/PCDF 2,3,7,8-PCDD/PCDF (17 congeners)

    New POPs on SC 2009

    HCHs hexachlorocyclohexane

    PCBz pentachlorobenzene

    BFRs PBDEs (not DeBDE #209), PBB

    PFAS PFOS and its salts, POSFs

    Substances to Be Monitored

    Substances to be monitored (GMP guidance)

  • ESI

    APCI

    APPI

    GC/MS

    MALDI PFOS (LC-MS/MS)

    Dioxins (HRGC/HRMS)

    PBDEs (NCI m/z 79/81 non-specific)

    Toxaphene, Drins (large fragmentation EI -> NCI)

    Different Ionization Techniques?

  • Universal MS platform for POPs

    analysis

    2014-12-16 8

  • Atmospheric Pressure Ionisation

    APGC

    Plasma

    Corona Pin

    Analyte Molecules

    Sample Cone

    Make-up gas (N2)

  • Mechanism of Ionization (I)

    N2+

    N2 e-

    2e-

    2N2

    N4+ M+

    M Corona Pin

    M+ M

    Charge Transfer

    Dry source conditions

    Favored by relatively non-polar compounds

    Horning et al. 1973 (Anal. Chem, 1973, 45, 936-943)

  • Mechanism of Ionization (II)

    N2+

    N4+

    H2O

    H2O+

    H2O

    H3O+

    +OH

    [M+H]+

    M

    Protonation

    Modified source conditions eg. with water or methanol present

    Favored by relatively polar compounds

    Corona Pin

    Horning et al. 1973 (Anal. Chem, 1973, 45, 936-943)

  • Analytical difficulties using high

    resolution magnetic sectors

    instruments

  • Dioxin analysis on HRGC-HRMS

    GC separation

    Capillary column

    Ionisation

    EI

    Mass detection

    SIR

    Resolution

    > 10 000

    0.01 amu

  • Sensitivity 100 fg and 10 fg TCDD on

    column

    2014-12-16 14

  • Sensitivity mix; TCDDs

    100 fg, 50 fg, 25 fg, 10 fg, 5 fg, 2 fg

  • Dioxins on APGC

    Congener Concentration (pg/L)

    Name 1/10 CSL* CSL CS0.5 CS1 CS2 CS3 CS4

    TCDD 0.01 0.1 0.25 0.5 2 10 40

    TCDF 0.01 0.1 0.25 0.5 2 10 40

    PCDD 0.05 0.5 1.25 2.5 10 50 200

    PCDF 0.05 0.5 1.25 2.5 10 50 200

    HxCDD 0.05 0.5 1.25 2.5 10 50 200

    HxCDF 0.05 0.5 1.25 2.5 10 50 200

    HpCDD 0.05 0.5 1.25 2.5 10 50 200

    HpCDF 0.05 0.5 1.25 2.5 10 50 200

    OCDD 0.1 1 2.5 5 20 100 400

    OCDF 0.1 1 2.5 5 20 100 400

  • APGC Dioxins

    Dilution 1/10 of CSL (10-100 fg/ul), 1 ul injection

  • Comparing APGC vs HRMS

    APGC HRMS

    EURL 0.85 0.83 2%

    (pg/g lipids) 0.69 0.72 -3%

    1.24 1.31 -6%

    1.07 1.14 -7%

    1.86 1.89 -2%

    3.46 3.39 2%

    MTM 6.1 5.8 5%

    (pg/PUF) 13.9 14.0 -1%

    45.6 47.7 -5%

    63.8 62.0 3%

    172 168 3%

    17.3 16.2 7%

    CSIC/IUPA 2.19 2.12 3%

    (pg/g) 0.40 0.41 -2%

    0.62 0.59 4%

    238 228 4%

    3640 3470 5%

    96.2 89.4 7%

    2014-12-16 20

  • Favorable ionization for OCDD

    2014-12-16 21

    CS4_H2O

    m/z310 320 330 340 350 360 370 380 390 400 410 420 430 440 450

    %

    0

    100

    m/z310 320 330 340 350 360 370 380 390 400 410 420 430 440 450

    %

    0

    100

    DIOXINS0065 6062 (30.654) MS2 AP+ 3.00e7

    443.70

    423.74407.74

    405.74372.04355.01329.08315.08

    301.23342.08 388.90

    439.71445.69

    446.71

    DIOXINS0006 6054 (30.614) MS2 AP+ 3.00e7

    443.68

    441.68

    439.69

    423.73

    422.72407.73

    404.95385.78373.85371.12329.91314.95 333.02 348.96

    436.71

    445.67

    446.69

    448.67

    H2O

    N2

  • 2014-12-16 24

    Additional POPs

    PCBs and organochlorine pesticides

  • 2014-12-16 25

    Instrumental comparison

    APGC vs high resolution GC/MS

    N=8

  • 03-Nov-200910 ng/ul pestmix 13 coneflow at 30

    Time9.00 9.50 10.00 10.50 11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50

    %

    0

    100

    XTQ_021109_010 1: MS2 AP+ TIC

    2.62e8

    11.96

    11.66

    9.26

    9.19

    10.91

    10.47

    9.66

    9.53 10.17

    10.03

    10.67

    11.16

    11.54

    11.70

    12.48

    12.14

    12.38

    13.39

    13.0812.88

    12.75

    14.2314.06

    13.95

    14.75

    Pest mix 13, 10 ng/ul, no modifier, fullscan APGC

    Stockholm Convention POP mix (APCI) Pesticide-Mix 13

    PCB No. 28

    PCB No. 52

    PCB No. 101

    PCB No. 138

    PCB No. 153

    PCB No. 180

    Aldrin

    cis-Chlordane

    trans-Chlordane

    oxy-Chlordane

    2,4-DDD

    4,4-DDD

    2,4-DDE

    4,4-DDE

    2,4-DDT

    4,4-DDT

    Dieldrin

    alpha-Endosulfan

    beta-Endosulfan

    Endrin

    alpha-HCH

    beta-HCH

    gamma-HCH

    delta-HCH

    epsilon-HCH

    Heptachlor

    cis-Heptachlor

    http://www.google.se/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRw&url=http%3A%2F%2Fwww.larslundmark.se%2Fwordpress%2Ftag%2Ffiskgjuse%2F&ei=ky-KVPy2Osf8UIKHgogN&psig=AFQjCNEEVxdhJskg-BWCL2Xypr3trTDFAw&ust=1418428669851768

  • Several halogenated Non-BDE Replacement Flame Retardants were

    analysed using APGC by Reiner et al. (2010)

    2014-12-16 27

    Brominated flame retardants (BFRs)

    - 2,2',4,4',5,5'-Hexabromobiphenyl (BB-153)

    - Hexabromocylcododecane (HBCD) (, , )

    - Tetrabromobisphenyl-A (TBBPA)

    - Allyl 2,4,6-tribromophenyl ether (ATE)

    - 2-Bromoallyl-2,4,6-tribromophenyl ether (BATE)

    - 2,3-Dibromopropyl-2,4,6-tribromophenyl ether (DPTE)

    - Octabromotrimethylphenylindane (OBIND)

    - Pentabromoethylbenzene (PBEB)

    - Hexabromobenzene (HBB)

    - 1,2-Bis(2,4,6-tribromophenoxy) ethane (BTBPE)

    - Decabromodiphenylethane (DBDPE)

    - Dechlorane Plus (DP) (anti, syn)

    - Hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO)

    - 2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB)

    - Bis(2-ethly-1-hexyl)tetrabromophthalate (BEHTBP)

    - 2,2',3,3',4,5,5',6,6'-Nonabromo-4'-chlorodiphenyl ether (4PC-BDE208)

    - Dechloranes 602, 603, 604

    http://www.google.se/url?sa=i&rct=j&q=bromerade%20flamskyddsmedel&source=images&cd=&cad=rja&docid=rxo5E9glOAN3LM&tbnid=Lf3fQx2xfQ6TAM:&ved=0CAUQjRw&url=http%3A%2F%2Fekoliv.wordpress.com%2F2010%2F01%2F07%2Fflamskyddsmedel-i-elektronik-och-plastvaror-kan-ge-prostatacancer%2F&ei=7McUUqbnJ8LB0QXVkoCoAg&bvm=bv.50952593,d.ZGU&psig=AFQjCNE2bjffMzVDdM3lOPZbAXFuRe_xgA&ust=1377179763289209

  • Polybrominated diphenyl ethers (PBDEs)

    Optimization of collision energy

    2014-12-16 28

    CE 20 V CE 45 V

  • Total ion chromatogram by

    APGC-MS/MS

  • RRF and r2 of the calibration curve

    0.04pg/uL 0.6pg/uL 4pg/uL 12pg/uL 60pg/uL average STD RSD(%) r r2

    BDE#28 8.247 7.233 7.507 7.536 8.415 7.788 0.51 6.6 0.9990 0.9980

    BDE#47 5.57 4.89 4.586 5.096 4.559 4.940 0.42 8.4 0.9991 0.9982

    BDE#66 4.526 4.049 4.167 4.761 4.612 4.423 0.30 6.8 0.9996 0.9992

    BDE#100 2.026 2.177 2.205 2.26 2.34 2.202 0.12 5.3 0.9998 0.9997

    BDE#99 2.477 2.094 2.211 2.13 2.506 2.284 0.19 8.5 0.9981 0.9963

    BDE#85 5.44 5.372 5.447 5.591 6.693 5.709 0.56 9.7 0.9973 0.9945

    BDE#154 2.175 2.432 2.42 2.478 3.312 2.563 0.43 17 0.9938 0.9876

    BDE#153 2.694 2.184 2.233 2.522 3.001 2.527 0.34 13 0.9965 0.9930

    BDE#138 1.692 1.731 1.663 1.877 2.074 1.807 0.17 9.4 0.9984 0.9969

    2014-12-16

  • 2014-12-16

    Comparison on PBDEs concentrations

    analyzed by APGC-MS/MS and HRGC/HRMS

  • Important to include BDE# 209

    2014-12-16 J. Muoz-Arnanz et al. / Environment International 37 (2011) 572576

  • 2014-12-16 33

    PBDE analysis on APGC

    Problems in sample transfer GC