The APGC-Xevo G2-XS QToF as a Tool for Targeted, Suspected and Non-Targeted Screening of Raw and Drinking Water

Transcription

1 The APGC-Xevo G2-XS QToF as a Tool for Targeted, Suspected and Non-Targeted Screening of Raw and Drinking Water Michael Petri Zweckverband Bodensee-Wasserversorgung Qulitätssicherung und Forschungslabor Süßenmühle1 D Sipplingen Tel.: / Fax: / Mail: michael.petri@bodensee-wasserversorgung.de

2 Drinking Water Treatment Plant Microstraining Filtration Ozonation Sandfiltration Disinfection Chlorination

3 Distribution System pipeline system of 1700 km 29 reservoirs (total volume about m³) 34 pumping stations 130 Mio m³ drinking water per year 320 towns and municipalities with about 4 Mio people

4 Laboratory of Lake Constance Water Supply

5 APGC-Xevo-G2 XS-QToF Nitrogen APGC Xevo-G2XS-QToF GC

6 APGC-Xevo-G2 XS-QToF APGC for a soft and unselective ionization High resolution-tof to get the exact mass Q-ToF to get a mass spectrum/fragmentation pattern for confirmation and/or identification (MS E ) 1. function: low energy collision - no fragmentation 2. function: high energy collision - fragmentation 3. function: lock mass Software: MassLynx (contolling), UNIFi (screening aproaches) 6

7 GC-MS is still a very important techique: EU-WD and D-SWD EU-DWD Atrazin Azinphos-ethyl Anilin Aldrin Chlorfenvinphos Azinphos-methyl Chlorbenzol Dieldrin Chlorpyrifos Parathion-ethyl Chlornitrobenzole Endrin Dichlorvos Parathion-methyl Tetrachlorbenzole Heptachlor Cypermetrin Diazinon Nitrobenzol Heptachlorepoxid Ethrimphos Aldrin DDT PCB-28 Benzo-(b)-fluoranthen Dieldrin Endosulfan PCB-52 Benzo-(k)-fluoranthen Endrin Heptachlor PCB-101 Benzo-(a)-pyren Isodrin Heptachlorepoxid PCB-138 Benzo-(ghi)-perylen Bis(2-ethyl-hexyl)phtalat Nonylphenol PCB-153 Indeno-(1,2,3-dc)-pyren Hexachlorbenzol Octylphenol PCB-180 Hexachlorbutadien Hexachlorcyclohexan Benzol Trihalogenmethane Anthracen Naphtalin Phenanthren 1,2-Dichlorethan Flouranthen PAKs Trichlorethen Bromierte Diphenylether C10-C13 Chloralkane Trichlosan Tetrachlorethen Hexabromcyclodecan Dioxine Pentachlorbenzol Pentachlorphenol Tributylzinn Triphenylzinn GC-MS cannot replaced completely by LC-MS

8 APGC Ionization chamber Inlet GC column Holder for modifier and calibration compound Corona needle Ionization chamber

9 APGC - Ionisation APGC: dry" APGC: wet"

10 Organic compounds with APGC-HRMS Sample preparation by LLE or SPE with internal standardization ( 2 H-PAHs) Column Rxi-5Sil MS - 30m x 0,25mm x 0,25µm Transfer Temp 320 C Transfer Column Deactivated glass column Transfer Flow 100 ml/min Carrier gas He 5.0 1,2 ml/min constant flow Collision gas Ar 5.0 Corona Current 3.0 Oven Source Temp 150 C Temp. programm Temp. C Ramp Hold Cone Gas Flow N L/h 1 70 C min Aux Gas N L/h C 20 C/min C 5 C/min - Scan Range Scan Time 0.4 s Injection Data Formate continuum Mode pulsed splitless MS MS E Volume 1 µl Lock Mass Temperature 280 C LE 4V Pulsed Time 1.0 min HE Ramp 10-40V Pulsed Pressure 50 psi Analyser Mode sensitive

11 Organic compounds with APGC-HRMS About 250 organic compounds were tested so far: pesticides polycyclic aromatic hydrocarbons, polychlorinated biphenyls chlorinated naphtalens and other GC-amenable compounds LLE SPE (disk-system) continuous SPE (24h) 11

12 APGC - soft ionization EI hard ionization APGC EI (NIST 2014) low energy high energy

13 APGC: PAHs - low fragmentation APGC EI (NIST 2014) low energy high energy

14 APGC: in-source-fragmentation: 4,4-DDT (C 14 H 9 Cl 5 accurate mass: 351,9147) APGC low energy EI (NIST 2014) high energy

15 C12 C13 C14 C15 C16 C10 C11 C17 C18 C19 C20 C21 C32 C22 C23 C24 C25 C31 C30 C26 C28 C29 C27 APGC: unexpected ionization of n-alkanes

16 Dotriacontane (C 32 H 66 ): predicted mass: measured mass: EI (NIST 2014) Composition i-fit Confidence (%) Predicted m/z m/z error (PPM) m/z error (mda) Chemspider NIST C32H66N C31H64N C33H

17 APGC: Dotriacontane (C 32 H 66 ) M+N C 32 H 66 N mda? (M+N)-NH C 32 H mda (M+N)+H 2 O C 32 H 68 NO mda

18 Tinorganic compound with APGC-HRMS Sample preparation by direct in-situ derivatization with NaBEt 4 in water sample and extraction with n-hexane Column Rxi-5Sil MS - 30m x 0,25mm x 0,25µm Transfer Temp 320 C Transfer Column Deactivated glass column Transfer Flow 100 ml/min Carrier gas He 5.0 1,2 ml/min constant flow Collision gas Ar 5.0 Corona Current 3.0 Oven Source Temp 150 C Temp. Programm Temp. C Ramp Hold Cone Gas Flow N L/h 1 70 C min Aux Gas N L/h C 20 C/min C 5 C/min - Scan Range Scan Time 0.4 s Injection Data Formate continuum Mode pulsed splitless MS MS E Volume 1 µl Lock Mass Temperature 280 C LE 4V Pulsed Time 1.0 min HE Ramp 10-40V Pulsed Pressure 50 psi Analyser Mode sensitive 18

19 DBu-Sn TrBu-Sn Oct-Sn TeBu-Sn DiOct-Sn Bu-Sn TrPh-Sn TrCyHx-Sn Tinorganic compounds with APGC-HRMS TIC (50-700) XIC (119.85) 19

20 Analyte: Tri-n-butyl-tin Derivatization product: Tri-n-butyl-ethyl-tin C 14 H 32 Sn (exact mass: ) 20

21 APGC LE EI NIST APGC HE Analyte: Triphenyl-tin Derivatization product: Ethyl-triphenyl-tin C 20 H 20 Sn (exact mass: ) 21

22 Brominated flame retardants with APGC-HRMS Sample preparation liquid-liquide-extraction with n-hexane and internal Standardization ( 13 C-PBDEs and 13 C-PCBs) Column Rtx m x 0,25mm x 0,1µm Transfer Temp 3520 C Transfer Column Deactivated glass column Transfer Flow 100 ml/min Carrier gas He ml/min constant flow Collision gas Ar 5.0 Corona Current 3.0 Oven Source Temp 150 C Temp. Programm Temp. C Ramp Hold Cone Gas Flow N L/h 1 75 C min Aux Gas N L/h C 21 C/min C 9 C/min 5.0 min Scan Range Scan Time 0.4 s Injection Data Formate continuum Mode pulsed splitless MS MS E Volume 1 µl Lock Mass Temperature 280 C LE 4V Pulsed Time 1.0 min HE Ramp 20-50V Pulsed Pressure 65 psi Analyser Mode sensitive 22

23 Brominated flame retardants with APGC-HRMS TIC Calibration Standard PBDEs 20ng/L TIC ( Da) 23

24 Brominated flame retardants with APGC-HRMS XICs Calibration Standard PBDEs 20ng/L 13 C-PCBs 13C-PBDE PBDE Deca-PBDE Hepta-PBDE Hexa-PBDE Penta-PBDE Tetra-PBDE Tri-PBDE

25 PBDE-209 (C 12 Br 10 O) 13 C-PBDE-209 ( 13 C 12 Br 10 O) Isotopic pattern C 12 Br 10 O 25

26 Brominated flame retardants with APGC-HRMS PBDE-47 C 12 H 6 Br 4 O 13 C-PBDE C 12 H 6 Br 4 O Monoisotopic mass of C 12 H 6 Br 4 O (predicted mass) 26

27 Brominated flame retardants with APGC-HRMS PBDE fragmentation pattern with different HE-Ramps HE 40-70V HE 30-60V HE 20-50V HE 10-40V LE 4V 27

28 Targeted, suspected and non-targeted screening: Targeted screening: compounds are known reference compounds RT, RI, type of ionization, mass spectra, recovery are known qualification and quantification is validated (MDL, MQL, uncertainty ) Suspected screening: suspected compounds are known (list: composition, predicted mass) no reference compounds RT, RI, type of ionization, mass spectra, in-source fragmentation are unknown Sample preparation (recovery is unknown) Non-targeted screening: nothing is known - we have no idea what we are looking for 28

29 Targeted / Suspected Screening List of Targets and Suspects (excel sheet for import into UNIFI) Name Formula Structure Filename Adduct Retention time Fragment 1 Fragment 2 Fragment Tetrachlorobenzol C6H2Cl Tetrachlorobenzene 1234-Tetrachloronaphtalin C10H4Cl Tetrachloronaphtalene 1235-Tetrachlorobenzol C6H2Cl Tetrachlorobenzene 1235-Tetrachloronaphtalin C10H4Cl Tetrachloronaphtalene 123-Trichlorobenzol C6H3Cl3 123-Trichlorobenzene 5, Trichloronaphtalene C10H4Cl4 123-Trichloronaphtalene 1245-Tetrachlorobenzene C6H2Cl Tetrachlorobenzene 7, Trichlorobenzol C6H3Cl3 124-Trichlorobenzene 5, Tetrachloronaphtalin C10H4Cl Tetrachloronaphtalene 1257-Tetrachloronaphtalin C10H4Cl Tetrachloronaphtalene 1258-Tetrachloronaphtalin C10H4Cl Tetrachloronaphtalene 12-Dichlorobenzol C6H4Cl2 12-Dichlorobenzene 4, Trichlorobenzol C6H3Cl3 135-Trichlorobenzene 6,15 13-Dichlorobenzol C6H4Cl2 13-Dichlorobenzene 4,37 14-Dichlorobenzol C6H4Cl2 14-Dichlorobenzene 4,44 15-Dichloronaphtalin C10H6Cl2 15-Dichloronaphtalene 2,3,5,6-Tetrachloroanilin C6H3Cl4N 2356-Tetrachloroanilin 11,30 230, , ,9591 2,4-Methoxychlor C16H15Cl3O2 24-Methoxychlor 23,89 227, , Pentachloro-p-terphenyl C18H9Cl Pentachloro-p-terphenyl 30, Tetrachloro-p-terphenyl C18H10Cl Tetrachloro-p-terphenyl 30,37 29

30 Targeted Screening (with quantification) 30

31 Targeted / Suspected Screening 31

32 Targeted / Suspected Screening 32

33 Non-targeted screening no idea what to look for.. TIC ( Da) 33

34 TIC ( Da) XIC (canditate mass: Da) response : > is unique in sample - not in blank 34

35 Non-targeted screening eludication tool - elemental composition 35

36 Non-targeted screening eludication tool - elemental composition Sample: Leiblach Candidate mass: ( ) at 5.44 min Elemental composition composition predicted m/z m/z error NIST 2014 ChemSpider C16H20O C10H21N4P C6H16N C11H20N2O For any further investigations you will definitely need: time statistic tools (PCA) a high level of tolerance towards frustration and often some stroke of luck. 36

37 APGC-HRMS APGC is a soft and unselective ionization method and it works. APGC with high resolution mass spectrometry is a perfect tool for targeted, suspected and non-targeted screening APGC-HRMS is very sensitive (low MDLs) reliable and flexible useable for targeted, suspected and non-targeted screening in one run 37

38 Some challenging tasks are still left for Waters What do we need for screening aproaches with APGC-HRMS/UNIFI? 1. Implementation of a retention-index 2. Connection to a mass spectra search programm for GC-amenable compounds (e.g. NIST MS Search) 3. Some more "intelligence" for the identification and confirmation via isotopic pattern: e.g. bromine isotopic pattern: PBDE, PBB calculation of the number of chlorine- and bromine atomes in a molecule via isotopic pattern consideration of a possible in-source fragmentation of higher chlorinated non-aromatic compounds (e.g. HCH, ) or non aromatic parts (e.g. DDT) Consideration of other in-source fragmentations (e.g. loss of H 2 O, CO, CO 2 ) Calculation/prediction of fragmentation from protonated compounds 38

39