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Advances in Trace Element Analysis

Advances in Trace Element Analysis. 2013 ACS Spring Meeting Workshop Art Fitchett and Fergus Keenan. Agenda. Ion Chromatography (IC) High Pressure Ion Chromatography (HPIC) Inductively Coupled Plasma (ICP) ICP-OES ICP-MS IC-ICP-MS Speciation. Why High Pressure Ion Chromatography.

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Advances in Trace Element Analysis

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  1. Advances in Trace Element Analysis 2013 ACS Spring Meeting Workshop Art Fitchett and Fergus Keenan

  2. Agenda • Ion Chromatography (IC) • High Pressure Ion Chromatography (HPIC) • Inductively Coupled Plasma (ICP) • ICP-OES • ICP-MS • IC-ICP-MS • Speciation

  3. Why High Pressure Ion Chromatography • Remember UHPLC? • As the particle size decreases from 8µm to 4µm, column efficiency doubles • This drop in particle size increases the column pressure by 4x • Like HPLC, IC is moving toward smaller particle column technology • HPIC Instrumentation can now handle the pressure of these smaller particle columns, even at higher flow rates.

  4. HPIC Theory Influence of the Particle Diameter on Pressure and Efficiency 100 1200 1000 10 µm particles 5 µm particles 800 3 µm particles 2 µm particles Column pressure [bar] Theoretical Plate Height [µm] 600 Optimal flow rate for maximum separation efficiency / resolution 400 200 0 0 0 2 4 6 8 10 0 2 4 6 8 10 Linear Velocity u [mm/s] Linear Velocity u [mm/s] Faster Flows for Faster Separations generate Higher Pressure Smaller Particles for Higher Efficiency generate Higher Pressure

  5. HPIC System Specifications

  6. HPIC System Advantage • HPIC systems + 4 µm particle-size columns deliver significant performance advantages • Smaller resin particle columns • Produce more efficient peaks • Impact chromatographic speed and resolution • Easier integration – more accurate and reliable results • Increase sample throughput without compromising data quality • Improved quality of analytical results

  7. New High Efficiency Dionex IonPac 4µm IC Columns in Analytical and Capillary Formats • Ion-exchange columns with 4 µm particle-size • Benefits • Smaller particles provide better performance • Faster run times with higher flow rates using 150 mm columns • Better resolution with standard flow rates using 250 mm columns • Applications • Anions in environmental • waters • Organic acids in foods and beverages • Amines in chemical process solutions 4 µm 5.5 10 5 µS µS µS SEM Image of 4 µm Supermacroporous Bead 0 -0.5 1 Minutes Minutes 40 0 40 0 0 Minutes 3 Fast Run using the Dionex IonPac AS18-4µm High Resolution using the Dionex IonPac AS11-HC-4µm High Resolution using the Dionex IonPac CS19-4µm Improved Resolution Provides Faster Runs and Better Results

  8. Improved Separations using 4 µm Particle Size Capillary Columns Eluent Source: Thermo Scientific Dionex EGC-KOH Eluent Generator Cartridge (Capillary) Gradient: Potassium hydroxide: 1 mM from 0 to 5 min, 1–15 mM from 5 to 14 min, 15–30 mM from 14 to 23 min, 30–60 mM from 23 to 31 min Flow Rate: 15 µL/min Inj. Volume: 0.40 µL Temperature: 30 °C Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ACES™ 300 Anion Capillary Electrolytic Suppressor, recycle mode 25 Thermo Scientific™ Dionex™ IonPac™ AG11-HC-4µm/AS11-HC-4µm 3600 psi 21 22 20 13 17 µS 8 16 26 24 6 14 12 27 23 29 9 19 11 25 2 15 Peaks: mg/L mg/L 1. Quinate 5.0 16. Bromide 5.0 2. Fluoride 1.5 17. Nitrate 5.0 3.Lactate 5.0 18. Carbonate --- 4.Acetate 5.0 19. Malonate 7.5 5. Propionate 5.0 20. Maleate 7.5 6. Formate 5.0 21. Sulfate 7.5 7. Butyrate 5.0 22. Oxalate 7.5 8. Methylsulfonate 5.0 23. Tungstate 10.0 9. Pyruvate 5.0 24. Phosphate 10.0 10. Valerate 5.0 25. Phthalate 10.0 11. Monochloro- 5.0 26. Citrate 10.0 acetate 27. Chromate 10.012. Bromate 5.0 28. cis-Aconitate --- 13. Chloride 2.5 29. trans-Aconitate 10.0 14. Nitrite 5.0 15. Trifluoroacetate 5.0 7 5 4 18 10 3 28 1 0 Dionex IonPac AG11-HC/AS11-HC 2200 psi µS -15 0 6 12 18 24 30 36 Minutes

  9. Faster Run Times without Sacrificing Resolution • Inorganic anions separation using a 4 µm capillary column Column: Dionex IonPac AS18-4µm, 0.4 × 150 mm Eluent Source: Dionex EGC-KOH (Capillary) Eluent: 30 mM KOH Col. Temp.: 30 °C Inj. Volume: 0.4 µL Detection: Suppressed Conductivity, Dionex ACES 300 Peaks: 1. Fluoride 0.2 mg/L 2. Chloride 1 3. Nitrite 1 4. Sulfate 1 5. Bromide 1 6. Nitrate 1 7. Phosphate 2 20 2 3 4 30 µL/min, 2820 psi 1 5 6 7 25 µL/min, 2430 psi 20 µL/min, 2030 psi µS 15 µL/min, 1570 psi 10 µL/min, 1140 psi -15 10 5 0 Minutes

  10. Fast Run on the Dionex IonPac AS18-4µm Column 2 Column: Dionex IonPac AS18-4µm, 0.4 × 250 mm Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 35 mM KOH Flow Rate: 30 µL/min Inj. Volume: 0.4 µL Col. Temp.: 30 °C IC Cube Temp.: 15 C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Peaks: 1. Fluoride 0.2 mg/L (ppm) 2. Chloride 0.5 3.Nitrite 1.0 4. Sulfate 1.0 5. Bromide 1.0 6. Nitrate 1.0 7. Phosphate 2.0 5.5 3 4 1 5 6 µS 7 -0.5 0 1 2 5 4 3 Minutes

  11. Faster Run Times without Sacrificing Resolution • Inorganic anions separation using a 4 µm Microborecolumn 3 Column: DionexIonPac AS18-4µm, 2 150 mm Instrument: Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ System Eluent Source: Dionex EGC 500 KOH Eluent: 23 mM Potassium hydroxide Flow Rate: 0.25, 0.40, 0.45, and 0.50 mL/min Inj. Volume: 5 µL Column Temp.: 30 °C Detection: Thermo Scientific™ Dionex™ ASRS™ 300 Anion Self-Regenerating Suppressor™, 2 mm, recycle Peaks: 1. Fluoride 0.5 mg/L 2. Chlorite 5.0 3. Chloride 3.0 4. Nitrite 5.0 5. Carbonate 20.0 6. Bromide 10.0 7. Sulfate 10.0 8. Nitrate 10.0 9. Chlorate 10.0 70 7 8 4 6 2 9 0.50 mL/min, 4200 psi 1 5 0.45 mL/min,3800 psi µS 0.40 mL/min, 3300 psi 0.25 mL/min, 2200 psi -20 1 9 5 6 8 7 0 2 3 4 Minutes

  12. Isocratic Separation of Common Anions Using the Dionex IonPac AS18-4µm Column (4 ×150 mm) at Various Flow Rates • Inorganic anions separation using a 4 µm Standard bore column 7 6 3 1.0 mL/min 2574 psi Column: Dionex IonPac AG18-4µm/AS18-4um (4 × 150 mm) Eluent: 23 mM KOH Eluent Source: Dionex EGC III KOH Cartridge Flow Rate: See chromatograms Inj. Volume: 10 µL Temperature: 30 °C Detection: Suppressed conductivity, Dionex ASRS300, AutoSuppression, recycle mode Peaks: 1. Fluoride 0.5 mg/L 2. Chlorite 5 3.Chloride3 4.Nitrite5 5. Carbonate 20 6. Bromide 10 7.Sulfate10 8. Nitrate10 9. Chlorate 10 6 8 4 2 9 µS 1 5 0 0 2 4 6 8 10 Minutes 6 7 1.25 mL/min 3332 psi 3 4 8 6 µS 2 9 1 5 0 0 2 4 6 8 10 Minutes 6 7 1.5 mL/min 3891 psi 3 8 6 4 µS 2 9 5 1 0 0 2 4 6 8 10 Minutes

  13. Fast Analysis of Drinking Water Using High-Pressure IC Column: DionexIonPac AS18-4µm, 2  150 mm Instrument: Dionex ICS-5000+ HPIC system Eluent Source: Dionex EGC 500 KOH Eluent: 23 mM Potassium hydroxide Flow Rate: 0.50 mL/min Inj. Volume: 5 µL Column Temp.: 30 °C Detection: Dionex ASRS 300, 2 mm, 15 mA, recycle Sample: Municipal City A Sample Prep.: 5-fold dilution with deionized water Peaks: 1. Fluoride 0.4 mg/L 2. Chloride2.3 3. Nitrite< 0.1 4. Carbonate --- 5. Sulfate 3.5 6. Nitrate < 0.1 7. Chlorate< 0.1 1.8 2 µS 5 4 1 3 6 7 0.8 3 4 5 0 1 2 Minutes

  14. High Resolution Cation Analysis on IonPac CS16at Different Flow Rates Column: IonPac CS16, 2 x 250 mm x 0.5 mm ID Eluant: 30 mmol/L MSA (EG) Flow rate: A: 10 µL/min B: 20 µL/min C: 30 µL/min Inj. volume: 0.4 µL Temperature: 40 °C Detection: Suppressed conductivity CCES 300, AutoSuppression, Recycle mode Peaks: 1. Lithium 0.5 mg/L 2. Sodium 2.0 3. Ammonium 2.5 4. Potassium 5.0 5. Magnesium 2.5 6. Calcium 5.0 7 30 µL/min 3600 psi 20 µL/min 2400 psi 4 10 µL/min 1200 psi C 5 µS 6 B 2 1 3 A -1 0 40 20 Minutes

  15. Increased Capabilities: Faster separations with higher flow rates (left) Higher resolution with longer columns (right) 5 1 Two Dionex IonPac CS16in series 2 µS Single Dionex IonPac CS16 2 1 -2 16 0 Minutes Capabilities of HPIC in Capillary Format 4.5 15,16 24 µL/min – 3900 psi 17 19 11 12 µS 3 7 6 8 13 14 1 9 2 18 5 4 10 B Thermo Scientific™ Dionex™IonSwift™MAX-100: 11 minutes -0.5 10000:1 Na : Ammonia 0 15 10 5 Minutes

  16. Using HPIC to Identify Spoilage in Beverages 7 6 Column: Dionex IonPac AS11-HC-4µm Capillary (0.4  250 mm) Eluent Source: Dionex EGC-KOH (Capillary) Gradient:Potassium hydroxide, 1 mM from 0 to 8 min, 1-30 mM from 8-28 min, 30-60 mM from 28-38 min, 60 mM from 38-42 min Flow Rate: 15 µL/min Inj. Volume: 0.4 µL Column Temp.: 30 °C Detection: Suppressed conductivity Dionex ACES 300, recycle Mode Sample Prep.:1:40 dilution with deionized water Peaks: 1. Quinate 11. Maleate 2. Fluoride 12. Sulfate 3. Lactate  13. Oxalate 4. Acetate  14. Unknown*  5. Formate 15. Phosphate 6. Unknown16. Citrate 7. Chloride 17. cis-Aconitate 8. Unknown 18. trans-Aconitate 9. Malate-Succinate19. Unknown 10. Carbonate 15 µL/min, 3600 psi 15 9 3 µS 4 10 16 6 13 1 11 2 12 8 14 17 19 18 5 0 42 0 30 10 20 Minutes

  17. The Dionex ICS-5000+HPIC • High Pressure Ion Chromatography • High pressure capable with both capillary and standard flow rates • Continuous operation up to 5000 psi when configured as a Reagent-Free (RFIC™) system • Increased productivity with fast run times • Improved separations and higher resolution with 4 µm particle columns • HPIC- High Resolution, Fast Analyses

  18. Dionex ICS-4000 Capillary HPIC System • Dedicated Capillary HPIC • New level of resolution and speed • Delivering best in class sensitivity • Simplifies workflows • Increases analytical efficiency and productivity • Small footprint • Electrochemical, Conductivity, or Charge detection Thermo Scientific™ Dionex™ IC Cube™ Cartridge • HPIC - High Resolution, Fast Analyses

  19. High-Pressure Ion Chromatography • HPIC systems provide better performance • HPIC systems allow for continuous operation up to 5000 psi • HPIC systems - High-pressure ion chromatography in an all PEEK™plastic IC • High-pressure Reagent-Free ready • Smaller 4 µm particle-size ion-exchange columns in a variety formats

  20. Advances in Trace Element Analysis Fergus Keenan Field Marketing Manager

  21. Agenda • Advances in ICP-OES technology • High speed analysis • Advances in ICP-MS • Intelligent Auto-dilution • QCell technology • Trace element speciation by IC-ICP_MS

  22. iCAP 7600 ICP-OES • Powerful analytical detection & resolution • Choice of plasma orientation to enable enhanced application suitability • Intelligent software for powerful auto-optimization of the sample intro system • Advanced data acquisition including ‘Sprint’ modes for ultimate productivity & versatility • Comprehensive accessory compatibility for liquid & solid sampling Who’s it for • Labs requiring the extreme productivity • Labs who perform highly variable & demanding research-based applications • Labs who require solid sampling capability

  23. Open Access Sample Introduction Compartment • Large fully opening outer door • Improved user access • Clear view of plasma source • Simplifies optimization • Easy access to sample introduction • Simple change of components • Peri-pump • 12 roller for smooth flow, micro tension control • Better stability allows shorter dwell times • Sprint Valve System • Highest Sample Throughput of any ICP • Drain Sensor • Monitors drain, detects leaks or blockages • Accessories • Easy connection of Argon Humidifier, Hydride Generation and Laser Ablation accessories “Better user access, compatible with all accessories”

  24. Sprint valve system – How does it work?

  25. Sprint valve system – How does it work?

  26. Why segmented stream? Uptake / Washout Profile with Contiguous Flow Raised baseline Long transients Uptake / Washout Profile with Segmented Stream Discrete washout steps True baseline Sharp transients

  27. Sprint Valve Oil Method Case-study– Wear Oil Analysis Typical Oil Method (already speed-optimized)

  28. Intelligently Monitored Wash • Software automatically detects washout to baseline for selected analytes • Non-productive time reduced; analysis time optimized • Washout completed sooner • Maybe no wash is needed?

  29. The soil samples were dried and ground 5 g of sample 20 ml of the 1M ammonium acetate solution was added. Samples shaken vigorously for at least 5 minutes and left to react overnight. Samples were then shaken again and filtered before being made up to 250 ml with de-ionized water. Sample extracts were analysed directly using the Sprint acquisition mode which further enhances the speed of the instrument. A locally sourced soil sample was extracted 5 times & each extract was analysed 10 times The total time required for these 50 repeats was 11 minutes and 35 seconds or 13.9 seconds per sample. CASE STUDY: Ultra-Fast Agricultural Soil Analysis

  30. Ultra-Fast Agricultural Soil Analysis

  31. Ultra-Fast Agricultural Soil Analysis

  32. Ultra-Fast Agricultural Soil Analysis

  33. Advances in Interference Removal in ICP-MS

  34. iCAP Q - Dramatically Different ICP-MS

  35. Easy to use and learn Reliability New interface cone design giving less memory effects and less drift Lower service costs and new longer life detector supplied as standard Productivity Single mode analysis capability for high throughput and quick flush times with the QCell Cost of ownership Lower gas consumption per analysis reduces running cost Longer life components (cones, detector) reduces lifetime cost Service contracts reduced by 30% over XSERIES2 Performance Best Signal /Noise of any Quadrupole ICP-MS on the Market Best interference removal with unique QCell technology New Leading Edge Design Smallest bench space requirements by unique ion optics design QCell Flatapole technology for the best in interference removal The only quadrupole MS to offer singe mode analysis iCAP Q - Dramatically Different ICP-MS

  36. Spectral Interferences Caused by molecular species formed in plasma overlapping with analyte isotope Ar, Air (O, N, C) ArAr, ArO, ArN, ArC, ArH, ArCa, ArNa, ArK, ArMg, ArCl, ClO, NO, CO, CaO, NaO, etc H2O, Ca, Na, K, Mg, Cl, etc ProductsReactionReactants

  37. Collision/Reaction Cell Technology Collision/Reaction Cell Technology • A multipole enclosed in a cylinder • Controlled flow of gas into the cell • Interaction of ions with the gas • If reactive gas used, reactions occur • All cells are reaction cells M+ only out M+ and XnYn’+

  38. The Basis of KED Operation 51V+~140 pm 51[ClO]+~250 pm

  39. Energy Barrier Small collision cross-section M+ Larger collision cross-section MO+ Collisional Energy Loss and Filtering: KED Pre-Cell Cell Post-Cell X Bolder shades indicate higher energy for M+ and MO+ ions Key: He atom M+ ion MO+ ion Increasing exit energy

  40. Improving Collision Cell Design • QCell with low mass cut-off • Flatapole technology for improved transmission • Non-consumable, zero-maintenance • 50% smaller volume for faster mode switching, <10s • Single mode interference removal with He • Can also use reactive mode with O2, H2 or NH3 mixes

  41. QCell – Low Mass Cut-Off KED mode QCell Mass Cut-OffRegion (here all masses below 39) 2 Measuring 56Fe 3 1

  42. QCell: Effect of Low Mass Cut-Off on in-cell Interference Formation

  43. 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4 QCell Comparative Performance– He KED mode, No spike

  44. 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4 + 10ppb Spike of Li, Be, B, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Ni, Cu, Zn, Ga, Ge, As, Se Note Co sensitivity 41,000cps/ppb QCell Comparative Performance– He KED mode, 10ppb Spike

  45. 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4, 200ppm Na, 200ppm Ca, 500ppm P QCell Comparative Performance– He KED mode, No spike

  46. 5%HNO3, 5%HCl, 1%IPA, 1%H2SO4, 200ppm Na, 200ppm Ca, 500ppm P + 10ppb Spike of Li, Be, B, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Ni, Cu, Zn, Ga, Ge, As, Se QCell Comparative Performance– He KED mode, 10ppb Spike

  47. Analysis of Selenium 78Se Sensitivity 8441 cps/ppb IDL 5ppt 7%H2/He KED

  48. Analysis of Vanadium without reactive gases Sensitivity 2,100 cps/ppb BEC 24ppt 0.5% HCl, He KED mode

  49. Collisional Focusing for High Sensitivity Uranium Measurement Sensitivity 1223 cps/ppt IDL 16ppq Collisional focusing with 7.8mL/min He

  50. IC-ICP-MS for Elemental Speciation

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