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Bologna 23 Giugno 2016 Dott. Luca Gerardo IC/SP Application Specialist, Thermo Fisher Scientific, Rodano (MI)
Novità in Cromatografia Ionica: Potenzialità delle Tecniche Accoppiate
3
IC-MS System Configuration
Thermo Scientific™ Q Exactive™ Focus™ GC-MS/MS system
Diverter Valve
Thermo Scientific™ Dionex™ ICS-5000+
system Pump 1
Pump 2
Pump 3
Pump 4
Waste Ground
250 ul/min
300 ul/min
80 ul/min
250 ul/min
Ion Chromatogrphy - System
4
Divert To Waste, Eliminates Salts From Matrix
Laboratory synthetic sample matrix; simulated matrix, high in the interfering salts as a test of the method
6
IC-MS: Key Points
• IC vs. LC • Greater specificity and selectivity for ionic compounds • Metal-free flow path reduces fouling of ion-exchange columns
• MS vs. conductivity detection (CD) • Increased sensitivity and selectivity • Identification and quantification of small polar analytes that have the same retention times
using single ion monitoring (SIM) or selective reaction monitoring (SRM) for MS/MS
• On-line desalting for high ionic strength matrices • Reduces MS signal suppression and possible detector damage
• Analyte confirmation • Combines the confirmation of analyte identification into one method
• Total integrated solution: IC, MS and data management
7
• MS single quadrupole analyzer • Molecular ion • Some fragmentation
• Triple Quadrupole MS-MS (TSQ or QqQ) • Composed of a quadrupole (Q1), followed by a collision cell (q2),
another quadrupole (Q3), and detector • Provides high specificity and focus of molecular ion by eliminating all
background ions • Fragmentation to ensure improved signal to noise and specificity
• Q Exactive Orbitrap MS
• Ultra High resolution
MS Analyzers
9
• Single quad enhanced low-mass response for analytes below 60 m/z
• High-sensitivity, self-cleaning quadrupole, low mass detector, 17–2000 m/z range
• ESI ionization source
• Controlled and software: • Thermo Scientific™ Dionex™ Chromeleon™ CDS software • Thermo Scientific™ Xcalibur™ software
• Compact design
Thermo Scientific™ MSQ™ Plus MS is designed for IC
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River Meuse (Perchlorate 0.28 µg/L)
12.5 16.0 18.0 20.0 22.0 24.0 26.0 29.50
10 000
20 000
30 000
40 0001 - Test_CB2 #14 [time corrected by -0.170 min] SIM_012 - Test_CB2 #14 [time corrected by -0.170 min] SIM_02counts
min
2
1
198.84-99.15 m/z
m/z 101.0
m/z 99.0
12
Calibration Solution 1 µg/L ClO4 in CD Detector
12.5 16.0 18.0 20.0 22.0 24.0 26.0 29.5-0.0100
-0.0050
0.0000
0.0050
0.0120 Test_CB2 #18 Std 1 ug/l ECD_1_MA_033_001µS
min
1
2 3
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Column: Thermo Scientific™ Dionex™ IonPac™ AS11, 2 × 250 mm Eluent (EG): KOH Gradient: 0.5–38 mM KOH (0 –18 min) Flow Rate: 0.5 mL/min Temp: 30 oC Suppressor: Thermo Scientific™ Dionex™ ASRS™ Anion Self Regenerating Suppressor, external water mode MS Conditions: MSQ Plus MS, -ESI 50 V, 400 oC, SIM Inj. Vol.: 25 µL SIM Peaks: µg/L SIM 1. Fluoride 130 19 2. Acetate 300 59 3. Formate 300 45 4. Bromate 100 127 5. Chloride 30 35 6. Nitrite 100 46 7. Bromide 100 81 8. Nitrate 100 62 9. Sulfate 150 97/99 10. Phosphate 150 97 11. Citrate 300 191
Optimized for Detection of very Low Mass Ions N
orm
aliz
ed R
espo
nse
0 5 10 15
Citrate
H2PO4-
HSO4-
Br-
NO3- NO2
-
Minutes
BrO3-
Acetate
Cl-
F- Formate
HSO4-
Application Note AN 243
14
IC-MS of Sodium and Small Amines
Column: Dionex IonPac CS12A-MS, 2 × 100 mm
Eluent (EG): MSA Gradient: 4–10 mM MSA (0–6 min),
10 mM (6–8 min) Flow Rate: 0.25 mL/min Temperature: 30 ºC Suppressor: Dionex CSRS cation self
regenerating suppressor, external water mode
Inj. Vol.: 25 µl MS Conditions: MSQ Plus MS, +ESI, 50 V, 350 ºC, SIM as indicated SIM Peaks: 1. Sodium, m/z 23 (contaminant) 2. Methylamine, m/z 32 50 µg/L (ppb) 3. Dimethylamine, m/z 46 40 4. Trimethylamine, m/z 60 150
0 8 Minutes
1 2
3
4
4
Nor
mal
ized
Res
pons
e
16
Thermo Scientific™ TSQ Endura™ MS
Extreme Quantitative Value • Best-in-class performance
• Unprecedented usability
• Exceptional robustness
TSQ Quantiva and Endura Mass Spectrometer
Thermo Scientific™ TSQ Quantiva™ MS
Extreme Quantitative Performance • Attogram sensitivity
• Unprecedented usability
• Exceptional robustness
18
Hi Resolution MS
Exactive
Thermo Scientific LTQ Orbitrap XL Q Exactive
Thermo Scientific™ Orbitrap Velos™ Pro
Thermo Scientific™ Orbitrap Elite™
Perf
orm
ance
and
flex
ibili
ty
Orbitrap product portfolio
Thermo Scientific™ Orbitrap Fusion™
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Untarget Analysis
Chloral Hydrate 1.5%
Unknown Halogenated
Organics 62.4%
Haloacetonitrile 2.0%
Haloacetic Acids
13.0%
Cyanogen Chloride
1.0% Trihalomethane 20.1%
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Glyphosate In Wheat Fluor
Wheat fluor extract (QuPPe method)
injected directly after 1/10 dilution
Wheat fluor extract (QuPPe method)
injected directly after 1/10 dilution spiked with 500 ppt Glyphosate
22
IC-MS Advantages
Determination of several analytes in a single anionic run:
- Glyphosate, AMPA, Glufosinate, Anionic Polar Pesticides - Aloacetic Acid HAA9
- Bromate (at ppt level)
- Perclorate (at ppt level)
- Anions
Determination of several analytes in a single cationic run:
- Diquat, Paraquat, Chlormequat, Cationic Polar Pesticides - Amines - Cations
24
Thermo Scientific™ iCAP™ RQ ICP-MS
- Thermo Scientific QCell Technology
- Best in class performance
- Sub PPT Detection Limits
- Improved robustness RF generator (Hi TDS Matrix)
- Enached performance at Low operating flow in order to preserve MS Cone
25
IC-ICP MS IN FOOD
Regolamento (UE) 2015/1006 Sulla Gazzetta Europea è stato pubblicato il Regolamento (UE) 2015/1006 della Commissione, del 25 giugno 2015, recante modifica del regolamento (CE) n. 1881/2006 per quanto riguarda i tenori massimi di arsenico inorganico nei prodotti alimentari. Il regolamento entra in vigore il 16 luglio 2015 e i nuovi valori si applicano dal 1 gennaio 2016.
Regolamento (UE) 2015/1005 Sulla Gazzetta Europea è stato pubblicato il Regolamento (UE) 2015/1005 della Commissione, del 25 giugno 2015, che modifica il regolamento (CE) n. 1881/2006 per quanto concerne i tenori massimi di piombo in taluni prodotti alimentari (mieli.) Il regolamento entra in vigore il 16 luglio 2015 e i nuovi valori si applicano dal 1 gennaio 2016.
26
Arsenic Speciation: ICS-5000 + iCAP Q IC-ICP-MS
• 0.45 ppb of each As standard
• 6 species
• ~8000 cps / ppb
•~15 minute analysis
• Anion Exchange: • Thermo Scientific™ Dionex™ IonPac™ AS-7
(2x250mm)
• Gradient elution with 20-200 mM ammonium carbonate
• Flow rate: 0.3 mL/min
• Injection volume: 20 µL
27
Mercury Speciation
• MeHg+ and Hg2+ standards Column: IonPac CS-5A Mobile phase: 10mM NaCLO4, 10mM acetic acid, 10 mM cysteine Flow rate: 0.5 ml min-1
Injection volume: 20µL MeHg+ 0.19 ng g-1
Hg2+ 0.25 ng g-1
28
Detection Sensitivity And Recovery
MeHg+
Sensitivity 61,000 cps ppb-1
LOD 8 pg g-1
Hg2+
Sensitivity 61,000 cps ppb-1
LOD 3 pg g-1
MeHg+
Hg2+
30
Thermo Scientific™ Delta V™ Isotope Ratio MS
Determination of country of origin or adulteration (Honey, olive oil, ecc)
32
The Dionex Ion Chromatography Product Line
RFIC
HPIC
Dionex Aquion Dionex Integrion Dionex ICS-4000 Dionex ICS-5000+