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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

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Analytical Techniques

IC-MS

IC-IRMS

IC-ICP-MS

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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

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Divert To Waste, Eliminates Salts From Matrix

Laboratory synthetic sample matrix; simulated matrix, high in the interfering salts as a test of the method

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Overlaid Chromatograms With Divert Windows

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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

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• 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

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Ion Chromatography coupled with Single Quadrupole MS

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• 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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EPA Method 332.0

U.S. EPA website (www.epa.gov)

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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

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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

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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

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Triple Quadrupole MS-MS and Orbitrap HRMS

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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

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EPA Method 557

U.S. EPA website (www.epa.gov)

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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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20 ppt Glyphosate, AMPA, Glufosinate

Gentile Concessine: Gruppo Veritas S.p.A.

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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

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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

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IC-ICP-MS

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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

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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.

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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

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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

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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+

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IC-IRMS

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Thermo Scientific™ Delta V™ Isotope Ratio MS

Determination of country of origin or adulteration (Honey, olive oil, ecc)

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Potential Of IC-IRMS For Beverage Authentication

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The Dionex Ion Chromatography Product Line

RFIC

HPIC

Dionex Aquion Dionex Integrion Dionex ICS-4000 Dionex ICS-5000+

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Continued…