1. Finnish Custom Lab., Pekka Ravio
Experiences on developing a screening method for Orbitrap mass spectrometer
Esitys käsittelee kemiallista kvalitatiivista orgaanista analytiikkaa tänä päivänä nestekromatografia-massaspektrometrian näkökulmasta.
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

2. Finnish Custom Lab., Pekka Ravio
Orbitrap Elite ETD
Hankinta: olemassa olevasta 15 vuotta vanhasta ioniloukusta > ioniloukku-orbiloukkuun >> hinta >> FIMEAn mukaan tulo
Laitteen osien kuvaus: neste – interface –ioniloukku – orbiloukku - ETD
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

3. Orbitrap Elite ETD: schematic
Toimintaperiaatteen ero verrattuna moneen muuhun massaspektrometriin: analysoidaan ionipaketteja, ei jatkuvaa ionivirtaa
Sähkösumutus interface – kaksiosainen ioniloukku – korkea paine loukussa erilaiset operaatiot – matalapaineloukusta skannataan – omat detektorit
– C-trap - Orbitrap toimintaperiaate – HCD cell - ETD

4. Finnish Custom Lab., Pekka Ravio
Pesticide residues screening with Orbitrap Elite
Primary instrumental parameters to choose:
1. Mass resolution
15 000, , , or (at m/z 400)
2. Fragmention technique
In-source CID, ion trap, HCD
all ion fragmentation
3. Collision energy
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

5. Finnish Custom Lab., Pekka Ravio
Measurement
Alternating scanning
Full scan, mass range 130 – 900 amu
All ion fragmentation in-source CID, mass range amu, collision energy 45 V
Cycle time around 0.5 s (R = )
> 15 or more scans over UPLC peak
External mass calibration
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

6. Finnish Custom Lab., Pekka Ravio
Alternating scan run, full scan – in source CID scan
Zoom
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

7. Finnish Custom Lab., Pekka Ravio
EUPT-SM , pepper + around 30 pestisides
Furathiocarb, C18H26N2O5S, M
∆ m =1,6 ppm
Full scan
C10H11O2S ,
∆ m = 4.1 ppm
In-source CID
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

8. Finnish Custom Lab., Pekka Ravio
Screening tests at the moment against a database and MS/MS library only, no validation with pesticide standards
Database bought and collected from literature, 450 compounds
Data processing software TraceFinder 3.2
Processing against database and
MS/MS spectral library (bought)
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

9. Tullilaboratorio, Pekka Ravio
Details in compound database
Tullilaboratorio, Pekka Ravio

10. Tullilaboratorio, Pekka Ravio
TraceFinder processing parameters
Tullilaboratorio, Pekka Ravio

11. Finnish Custom Lab., Pekka Ravio
Processing with TraceFinder software
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

12. Finnish Custom Lab., Pekka Ravio
Finding correct fragments ” fragment soup” +
library search
in-source CID scan
0.019 mg/kg
fenhexamid
in raspberry
Mass resolution
60 000
Fenhexamid
MS/MS-library spectra
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

13. Tullilaboratorio, Pekka Ravio
Evaluating isotopic pattern, red=meas., blue=theor.
Fenhexamid 0,019 mg/kg
Tullilaboratorio, Pekka Ravio

14. Tullilaboratorio, Pekka Ravio
Screening results, EUPT-SM06
Tullilaboratorio, Pekka Ravio

15. Tullilaboratorio, Pekka Ravio
Screening results EUPT-SM07
Tullilaboratorio, Pekka Ravio

16. Finnish Custom Lab., Pekka Ravio
Conclusions
Orbitrap Elite
Easy to use
Stable mass calibration
Same mass calibration may be used 1- 3 days (error < 3 ppm)
All ion fragmentation with HCD-cell would be nice
Data processing with TraceFinder 3.2
Visual outlook very informative
Should be able to use several collision energies
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

17. Finnish Custom Lab., Pekka Ravio
Principle how the isotopic pattern is evaluated is unclear
Overall conclusions
Encouraging results
All depends on the database
A lot of work to build up the database, ”fine tune” it and ”fine tune” the processing parameters + MS/MS library
The more compounds you have in database, the more false positives you get
The software needs some upgrading and better manuals
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio

18. Finnish Custom Lab., Pekka Ravio
”Our newest weapon”
Customs moneydog Massi
Thank You
11. NPRW , Tallinn
Finnish Custom Lab., Pekka Ravio