Capillary Ion Chromatography, Sample Analysis on Demand Salt Lake City, UT May 2012

2 Agenda What is Ion Chromatography Typical IC Configuration Reagent Free Ion Chromatography Technology Why Capillary IC? Hardware overview

3 Ion Chromatography Ion Chromatography is an analytical technique that utilizes ion exchange mechanisms to separate ionic substances followed by detection utilizing conductivity, amperometry, UV/Vis, fluorescence, mass spectrometry or the new charge detectors. Analyte classes include: Anions Cations Organic Acids Amines Transition Metals Carbohydrates & Amino Acids

4 Ion Chromatography Supports a Broad Diversity of Application Areas Environmental Chemical & Petrochemical Pharmaceutical & Biotechnology Power & Energy Production Electronics, Semiconductors & Plating Pulp & Paper Foods & Beverages, Nutrition Personal Care & Household Products Agricultural Products Forensics

5 Typical Ion Chromatographic System - Anion Analysis Eluent Bottle (CO 3 /HCO 3 or NaOH) Pump Guard Column Analytical Column Suppressor Regen In (H 2 SO 4 ) Conductivity Cell Chromatography Software Ion Exchange Separation Post- Suppression Conductivity Data Handling and Instrument Control Sample Injection Regen Out (H 2 SO 4 )

6 The Role of Suppression using Hydroxide Eluents Without Suppression Counter Ions -µS F–F– SO 4 2 – Cl – F–F– SO 4 2 – Time With Chemical Suppression Cl – Eluent (NaOH) Sample F –, Cl –, SO 4 2 – Analytical Column (Anion Exchanger) Anion Suppressor (Cation Exchanger) HF, HCl, H 2 SO 4 in H 2 O NaF, NaCl, Na 2 SO 4 in NaOH Waste H+H+ Na + RFIC Manual Prep µS

7 Separation of Common Anions and Oxyhalides: (A) IonPac AS9-HC (Isocratic) µS Minutes – µS (B) IonPac AS19 (Gradient) Column:(A) IonPac AG9-HC, AS9-HC (B) IonPac AG19, AS19, 4 mm Eluent:(A) 9 mM sodium carbonate (B) Potassium hydroxide: 10 mM 0 to 10 min, 10–45 mM 10 to 25 min Eluent Source:(B) ICS-2000 EG with CR-ATC Temperature:(B) 30 °C Flow Rate:1.0 mL/min Inj. Volume:25 µL Detection:ASRS ® ULTRA II, 4 mm, recycle mode, 130 mA Peaks: 1. Fluoride3 mg/L 2. Chlorite10 3.Bromate20 4. Chloride5 5. Nitrite15 6.Chlorate25 7.Bromide25 8. Nitrate25 9. Carbonate— 10.Sulfate Phosphate40

8 Making Ion Chromatography Easy! ● What if you did not have to make up any mobile phases, eluents, or mix reagents? ● What if day to day operation of the system was not dependent on weighing, dilution, or preparation of chemical reagents. ● What if you knew with 100% accuracy and reliability that the chemistry you ran yesterday, is the same as it is today, and will be the same as it is tomorrow?

9 Reagent-Free Ion Chromatography (RFIC) Systems ● RFIC enables fully automated preparation of eluents eliminating the need to manually prepare mobile phases. ● Fully isocratic and gradient capable. ● Uses only de-ionized water

10 Typical Ion Chromatographic System - Anion Analysis Eluent Bottle (CO 3 /HCO 3 or NaOH) Pump Guard Column Analytical Column Suppressor Regen In (H 2 SO 4 ) Conductivity Cell Chromatography Software Ion Exchange Separation Post- Suppression Conductivity Data Handling and Instrument Control Sample Injection Regen Out (H 2 SO 4 )

11 Typical Ion Chromatographic System - Anion Analysis Eluent Bottle (DI Water) Pump Guard Column Analytical Column Suppressor Regen In (H 2 SO 4 ) Conductivity Cell Chromatography Software Ion Exchange Separation Post- Suppression Conductivity Data Handling and Instrument Control Sample Injection Regen Out (H 2 SO 4 )

12 Reagent-Free ™ Ion Chromatography System Electrolytic Eluent Generator High-Pressure Non-Metallic Pump Sample Injector (Autosampler) H20H20 Separation Column Degasser Waste Conductivity Detector Data Management Cell Effluent Electrolytic Suppressor Continuously Regenerated Trap Column

13 Electrolytic Generation of KOH Eluents Using an EGC-KOH Cartridge Pt Cathode (2H 2 O + 2e – 2OH – + H 2 ) Cation Exchange Connector Hydroxide Generation Chamber Pump H2OH2O Pt anode (H 2 O 2H + + ½O 2 + 2e – ) K + Electrolyte Reservoir K+K+ KOH + H 2 KOH H2H2 Degas Unit [KOH]  Current Flow rate Vent CR-ATC Anion Trap

14 Separation of Common Anions on an IonPac 4 mm AS18 Column Using an ICS-2100 RFIC-EG ™ System Column: IonPac ® AS18, 4 mm Eluent Source:EGC-KOH cartridge with CR-ATC Eluent:22–30 mM KOH: 7–8 min Flow Rate:1.0 mL/min Temperature:30 °C Inj. Volume:25 µL Suppressor:ASRS ® ULTRA II at 100 mA Detection:Suppressed conductivity Sample:Anion Standard Peaks:1. Fluoride2.0 mg/L 2. Acetate10 3. Formate10 4. Chlorite Chloride Nitrite10 7. Carbonate— 8. Bromide10 9. Sulfate Nitrate Chlorate Phosphate µS Minutes Overlay of 20 consecutive runs Retention time RSD: 0.012% (NO 3 – ) to 0.035% (PO 4 3 – )

15 Separation of Common Cations on a 2 mm IonPac CS12A Column Using an ICS-5000 RFIC-EG ™ System Column:IonPac ® CG12A, CS1S12A, 2  250 mm Eluent Source: EGC II MSA cartridge Eluent:20 mM MSA Temperature:30 °C Flow Rate:0.25 mL/min Inj. Volume:5 µL Detection:Suppressed conductivity, CSRS ® ULTRA II, recycle mode Peaks: 1. Lithium1.0 mg/L 2. Sodium Ammonium Potassium10 5. Magnesium Calcium10 Overlay of 30 consecutive runs Retention time RSD: 0.043% (Li + ) to 0.051% (K + ) Peak area RSD: 0.09% (Ca 2+ ) to 0.12% (K + )

16 Benefits of RFIC-EG ™ Systems Use EGC cartridges to generate high purity acid, base, or carbonate eluents on-line using deionized water as the carrier Produce eluents of precise and reproducible concentrations through the convenient control of electrical current Improve retention time reproducibility for both isocratic and gradient separations Compatible with a wide range of high-performance detection methods including conductivity, UV-Vis, electrochemical, and MS Improve the ease of use, sensitivity, and performance of IC methods (day-to- day and lab-to-lab) for the determination of target analytes in a wide variety of sample matrices Simplify system operation and reduce overall operating cost

17 Capillary IC Khalil Divan and Jason S. Wood

18 The Most Important Values of Capillary IC “IC on Demand” Permanent availability of the system Higher laboratory productivity, reduced equilibration/start-up time Less/fewer calibration runs Isocratic and gradient elution with RFIC Higher mass sensitivity High sensitivity with less sample volume 100-fold increase in absolute sensitivity in comparison to 4 mm systems IC × IC (2D-IC) – detection limits in the ppt range with only 1 mL of sample Lower cost of ownership Lower eluent consumption, less waste 18 months lifetime of the EG cartridges Operates on just 5.25 L of DI water per year

19 Capillary IC – The Dimension of Scale AnalyticalCapillary Column I.D. 4 mm0.4 mm Flow Rate 1.0 mL/min 10  L/min Injection Volume 25  L0.4  L Eluent Consumption / Waste Generated 43.2 L/month0.432 L/month EGC Lifetime mM) 28 Days18 months Mass Detection Limits 7000 fg70 fg

20 Typical Workflow: Traditional IC (IonPac AS19 Gradient Analysis) Results Start-up: Equilibration: Total Time = 1 Hour Run 3 Standards: Total Time = 1 h 30 min Total Analysis Time: Total Time = 6 hours Run 5 Samples: Total Time = 2 h 30 min Eluent Preparation Total Time = 1 Hour

21 Typical Workflow: Capillary IC Always On – Always Ready (IonPac AS19 Gradient Analysis) “IC on Demand” Results Run Check Standard: Total Time = 30 min Run 5 Samples: Total Time = 2 h 30 min Total Analysis Time: Total Time = 3 hours

22 Capillary IC Value: Best Results Overlay of 50 Consecutive Analysis FluorideChloriteChlorideNitriteChlorateBromideNitrateSulfate Retention Time (% RSD) Peak Area (% RSD) AS19 – Isocratic (10 mL/min) 0.4 mm x 250 mm

23 Ion Chromatography Family ICS-2100 ICS-900 ICS-1100 ICS-1600 ICS-5000 Integral ™

24 Ion Chromatography Family ICS-2100 ICS-900 ICS-1100 ICS-1600 ICS-5000 ICS-4000 NEW

25 Capillary IC allows you to reduce operational costs by running a full year on 5 L of water. It is “Always Ready” allowing you to start running samples whenever you want, and continue to run them without compromise. Configurations for both capillary and analytical formats, including isocratic and gradient capabilities. It is the most flexible IC system in the world making it ideal for a broad variety of analytes. Summary Capillary IC is a quantum leap ahead!

26 Thank you!