Dr. Esteban Abad. Laboratorio de Dioxinas Laboratorio de Espectrometría de Masas Dept. Química Ambiental, IDÆA-CSIC, Barcelona (España)

Transcription

1 Developments in HRMS in Spain 40 years of experience Dr. Esteban Abad Laboratorio de Dioxinas Laboratorio de Espectrometría de Masas Dept. Química Ambiental, IDÆA-CSIC, Barcelona (España)

2 Developments in HRMS in Spain 40 years of experience and the study of Organic Pollutants Dr. Esteban Abad Laboratorio de Dioxinas Laboratorio de Espectrometría de Masas Dept. Química Ambiental, IDÆA-CSIC, Barcelona (España)

3 Mass Spectrometry The Origin J.J. Thomson Experiment (1912) Parabolic Spectrograh Anode Catode Electrodes Ne Ne y 20 Ne Ne Discharges tube Fluorescent Screen J.J. Thomson Magnet z z 2 = (B 2 l 2 /2 V) (q/m) y Stables isotopes of NE!!!

4 Mass Spectrometry The Origin Improvements on Thomson's Experiment (1925) Mass Spectrograph Collimating Slits Photographic Plate Ions Magnet field H Electrodes Natural occurring elements are composed of a combination of isotopes!!! Aston

5 Extraordinary Researchers in the Mass Spectrometry World were recognized with Nobel Price Joseph John Thomson 1906 Nobel Prize for Physics "in recognition of the great merits of his theoretical and experimental investigations on the conduction of electricity by gases" Francis William Aston 1922 Nobel Prize for Chemistry "for his discovery, by means of his mass spectrograph, of isotopes, in a large number of nonradioactive elements, and for his enunciation of the whole-number rule" Wolfgang Paul 1989 Nobel Prize for Physics "for the development of the ion trap technique" John Bennet Fenn 2002 Nobel Prize for Chemistry "for the development of soft desorption ionisation methods hd (ESI) for mass spectrometric analyses of biological macromolecules" Koichi Tanaka 2002 Nobel Prize for Chemistry "for the development of soft desorption ionisation methods hd (MALDI) for mass spectrometric analyses of biological macromolecules"

6 High Resolution Mass Spectrometry Magnetic Sector Analyzer Ion Source Accelerating Voltage 4 10 kv R Detector m 1 m 2 R = 1 B 2 m V q

7 High Resolution Mass Spectrometry Magnetic Sector Analyzer Prof. Josep Rivera XB1 (Croix de Berny) Rivera s Mass Spectrometer MS-9 París, Two patents: Housing source on the top position Magnet Radius < 8cm Special magnetic sector design

8 High Resolution Mass Spectrometry Magnetic Sector Analyzer R = M M CO + = 27, N 2+ = 28, Nominal mass: 28 C 2 H 4+ = 28, Baja resolución Cuadrupolo Resolución Unidad High Resolution Para separar CO + yn + 2 Para separar N 2 + yc 2 H 4 + R = R = M 28 = = 2545 M M M 28 = =

9 High Resolution Mass Spectrometry Magnetic Sector Analyzer R = M M CO + = 27, N 2+ = 28, Nominal mass: 28 C 2 H 4+ = 28, XB1 Baja resolución Cuadrupolo Resolución Unidad High Resolution Para separar CO + yn + 2 Para separar N 2 + yc 2 H 4 + R = R = M 28 = = 2545 M M M 28 = =

10 Mass Spectrometry The Origin Spain, 1970 Several Institutions supported an initiative to build the National Service for Mass Spectrometry

11 Mass Spectrometry The Origin Spain, 1970 SERVICIO NACIONAL DE ESPECTROMETRÍA DE MASAS ESPECTROMETRíA DE MASAS DE ALTA RESOLUCIÓN

12 Mass Spectrometry The Origin Spain, 1970 Several Institutions supported an initiative to build the National Service for Mass Spectrometry Servicio Nacional de Espectrometría de Masas

13 Mass Spectrometry The Origin MS-9 AEI, 1970 (Associated Electrical Industries) )

14 Mass Spectrometry The Origin MS-9 AEI (1970) Mass Spectrometry Direct mass spectrometric analysis

15 Mass Spectrometry The Origin On the 80 s an important project between the Laboratory of Mass Spectrometry and the Barcelona Water Company motivated a new Laboratory of Organic Pollutants in Aquatic Environment Servicio Nacional de Espectrometría de Masas

16 Organic pollutants or Re-emerging emerging compounds Direct Mass-Spectrometric Analysis NO Gas Chromatography Separation

17 First GC-MS coupling MS-9 VG Updated (1983)

18 Organic pollutants or Re-emerging emerging compounds Mass spectrometry 30 years later, trihalomethanes (DBPs) become to be a new topic

19 Mass Spectrometry The Origin

20 First analysis on FAB for surfactants, 1987 MS-9 and ZAB-HF (Zero Alpha Beta aberrations High Field)

21 AUTOSPEC Q (1990) EBEqQ

22 8557 congeners Chromatographic Separation? Hepta CTs Monitored Mass C 18 H 35 7 Cl 37 6 Cl 1 m/z Nona CTs C 18 H 35 5 Cl 37Cl 7 2 m/z Cl R= C 18 H 35 5 Cl 37Cl 6 3 m/z Cl, 37 Cl C 18 H 35 5 Cl 37Cl 5 2 m/z Interfering Mass C 18 H 35 5 Cl 37Cl 5 4 m/z Cl Interference of non-cts on the hepta-cts

23 LRMS vs. HRMS Resolving power: (10% valley definition) VG AutoSpec-Q (EBEqQ instrument), EI 70 ev, SIM, dwell time 80 ms, delay time 20 ms VG TS-250 (EBE cofiguration), EI 70 ev, SIM mode, dwell time 50 ms delay time 10 ms, Resolution: 500 LRMS HeptaCTs m/z HRMS HeptaCTs m/z HRMS NonaCTs-2Cl m/z J. Caixach, J. Rivera, M.T. Galceran and F.J. Santos J. Chromatogr. A 675 (1994)

24 exo exo * * endo endo * * * * endo endo endo exo exo Toxaphene mixtures (>670 compounds) Structure of bornane skeleton with numbering of carbon atoms and endo and exo positions. * indicates chirality carbon atom

25 Analysis of Toxaphene in Dolphin liver by GC-HRMS Standard #26 m/z Standard #50 #58 m/z #59 #63 #56 #62 Dolphin Liver #26 m/z Dolphin Liver #58 m/z #50 VG AutoSpec Q (EBEqQ instrument) EI 70 ev, SIM, dwell time 80 ms, delay time 20 ms Resolving power 21,000 (10% valley definition)

26 Mass Spectrometry The Origin Laboratori de Contaminants Organics en Medi Aquatic HRMS re-visited Dr. Caixach team Servicio Nacional de Espectrometría de Masas

27 Ultra High Resolution Mass Spectrometry

28 Ultra high resolution mass spectrometry RESOLUTION or Resolving Power HRMS MAGNETIC SECTOR : UP TO ( 10%) TOF : ; 2009 : UP TO ~ (FWHM o 50%) ORBITRAP : (FWHM) U-HRMS FT- ICR MS : (FWHM)

29 LTQ-FT ICR-MS LTQ-Orbitrap Δm 50% m/δm 50% 1000K K 400K m/z m/z 100K 60K 40K 20K 10K

30 Re elative Abundance ESI (-) FT-ICR MS Spectrum of SRFA RP: (m/z:400) Relative Abundance 6 Da window m/z Spectrum m/z: more than signals Relative A bundance C 20 H 13 O 14 C 21 H 17 O Da window C 22 H 21 O C 23 H 25 O C 24H 29O m/z 20 C 25 H 33 O m/z

31 Mass Spectrometry The Origin Laboratori de Contaminants Organics en Medi Aquatic Laboratori de Dioxines Servicio Nacional de Espectrometría de Masas

32 AUTOSPEC ULTIMA (1994) EBE

33 MWI - 1 (ng/nm 3 ) MWI - 2 (ng/nm 3 ) MWI - 3 (ng/nm 3 ) MWI - 4 (ng/nm 3 ) IWI - 1 (pg/nm 3 ) IWI - 2 (pg/nm 3 ) No. Samples Mean (I-TEQ ng/nm 3 ) Range (I-TEQ ng/nm 3 ) I-TEQ (g/year) ** 1.5** Output Flow Gas (m 3 /h)

34 Campaig INPUT g I-TEQ/yr OUTPUT g I-TEQ/yr BALANCE g I-TEQ/yr 1ª ª ª

35 Thermal Urban Waste Management contributes with approx. 1 g I-TEQ/yr Remarkable decrease after APCS upgrading 20 to 1 g I-TEQ/yr Other important t source are already under study

36 Other POPs: the polychlorinated naphthalenes AutoSpec Ultima (EBE instrument) EI+ 35 ev, SIM, dwell time 50 ms, delay time 10 ms Resolving power 10,000 (10% valley definition) 100% MonoCN DiCN TriCN TetraCN PentaCN HexaCN HeptaCN OctaCN :00 20:00 25:00 30:00 35:00 40:00 45:00 Time

37 HxCDDs HpCDFs Soil Initial Soil Final Sludge

38 UNEP-CSIC Project Stockholm Convention POPs Training and capacity Building Antigua and Barbuda Brazil Chile Cuba Ecuador Jamaica Mexico Peru Uruguay Barbados Haiti

39 EUROPEAN STANDARD EN-1948 EN : 1: Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs - Part 1: Sampling EN : Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs - Part 2: Extraction and clean up EN : Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs - Part 3: Identification and quantification EN : 4: Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs - Part 4: Analysis of Dioxin-like PCBs EN : Continuous Monitoring sampling.????

40 Quality Control and Quality Assurance Long-Term Worldwide QA/QC of Dioxins and Dioxin-like PCBs in Environmental Samples Bert van Bavel and Esteban Abad June 1, 2008 / Analytical Chemistry 11,

41 ACREDITED by ENAC

42 A new laboratory was built up 1999 Belgium crisis

43 Daily Intake PCDD/Fs: 1.35±0.11 pg WHO-TEQ/ kg b.w. per day PCDD/Fs+DL-PCBs: 3.22±0.75 pg WHO-TEQ/ kg b.w. per day WHO: 1-4 pg WHO-TEQ/ kg peso corporal y día 258 samples (mainly animal origin) Analites: PCDD/Fs, DL-PCBs Period: Body weigh: 70 kg Data source: INE-ENNA, MAPYA Fish and fish products Vegetable oils 19% eggs 11% 4% 29% Meat and meat product 37% Milk and milk products

44 BIOACCUMULATION STUDIES Gilthead seabream juveniles ( g initial weight) were stocked for 13 months (May 2004 June 2005) in 4 tanks Exposed group: 2 tanks Fish feed with dry feed coated with olive oil spiked with PCDD/Fs ~ 23 ng WHO-TEQ/kg feed Stocking conditions in the tanks: Control group: 2 tanks Volume: 1500 l (50 juveniles per tank) Temperature: 18 1ºC Salinity: 35 1 ppt Oxygen: 6 1 mg/l Photoperiod: 12hL: 12hD Fish feed with dry feed coated with the same amount of the non-spiked olive oil

45 DIFFERENCE PROJECT V EU Framework Coord.. Prof. Jacob de Boer pg WHO-TEQ/ Total g pg product; WHO-TEQ/g upperbound Clean Fish extract (n=2) Milk(n=6) Fish oil (n=6) Vegetable oil (n=1) GC-HRMS GC-ITMS/MS GC-HRMS GC-ITMS/MS GC-HRMS GC-ITMS/MS GC-HRMS GC-ITMS/MS LRMS/MS,RSD% < 8.5% PCDD/Fs Dioxin-like PCBs

46 GC-Ion trap MS/MS Poor clean-up Suitable clean-up RT: SM:7G ,2,3,4,6,7,8-HpCDF?1,2,3,4,7,8,9-HpCDF? Relative Abund dance C 12-1,2,3,4,7,8,9-HpCDF RT: SM:7G Relative Abund dance 13 C 12-1,2,3,4,6,7,8-HpCDF H 1,2,3,4,6,7,8-HpCDD? 13 C 12-1,2,3,4,6,7,8-HpCDD ,2,3,4,6,7,8-HpCDF 1,2,3,4,7,8,9-HpCDF C 12-1,2,3,4,7,8,9-HpCDF 13 C 12-1,2,3,4,6,7,8-HpCDF ,2,3,4,6,7,8-HpCDD 13 C 12-1,2,3,4,6,7,8-HpCDD Time (min) Time (min)

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48 Promising adventure AUTOSPEC ULTIMA NT (2003) EBE Split detector

49 Promising adventure Detector 1+2 PCDD vs. PCB R: Detector 1 Compatibility 71% Coeluting interferences Detector 2 Required: AUTOSPEC ULTIMA NT (2003) EBE M R = 358 = = M Split detector

50 Promising adventure AUTOSPEC ULTIMA NT (2003) EBE Split detector

51 New Challenges THERMO DFS (2007) BE Toroidal ESA

52 New Challenges Prof. Beynon 1960 Toroidal ESA

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54 New Challenges THERMO DFS (2007) BE

55 El laboratori de Dioxines BARCELONA

56 From Thermo: Helmut Muenster Dirk Krumwiede Heinz Mehlmann Hans-Joachim Hübschmann Josep María Sangenís Jorge Parreño Acknowledgments Other: Prof. Josep Rivera Dr. J. Caixach Mrs. Nuria Cortés Dr. F.J. Santos Dr. Encarna Moyano Mr. Juan Sole Mr. Luis Esteban Prof. Bert van Bavel Thank you very much for your attention!!! All my colleagues in the lab!!!!

57 Developments in HRMS in Spain 40 years of experience Dr. Esteban Abad Laboratorio de Dioxinas Laboratorio de Espectrometría de Masas Dept. Química Ambiental, IDÆA-CSIC, Barcelona (España)