Rapid Determination of Inorganic Ions in Wastewater by Ion Chromatography

Science

chromatography-mass-spectrometry-solutions
  • 1. 1 The world leader in serving science Peter Bodsky Field Marketing Manager March 26, 2014 Rapid Determination of Inorganic Ions in Wastewater by Ion Chromatography
  • 2. 2 Agenda • Wastewater sources • Regulations and methods • Analytes of interest in wastewater • Challenge of wastewater analysis • Ion Chromatography system innovations • Inline conductivity and automated dilution • Reagent-Free™ Ion Chromatography (RFIC™) • High-Pressure™ Capillary IC (HPIC™) • Conclusions
  • 3. 3 Examples of Wastewater Sources • Manufacturing • Oil and gas extraction • Petroleum refining • Mining • Power generation • Household sewage • Agriculture
  • 4. 4 Reasons to Perform Wastewater Analysis • Monitoring discharge • Regulatory limits • Nutrient Analysis • Excessive plant growth in aqueous environments • Known samples • Historical analysis • E.g., High chloride level from a treatment facility with a water inlet near the sea/estuary • Unknown samples • Investigative, pollution incident, farm run-off, milk spill, or industrial discharge plant failure
  • 5. 5 International Wastewater Regulations • ISO • International Organization for Standardization • ASTM International • “American Society for Testing and Materials” • DIN • Deutsches Institut für Normung • German Standard • U.S. EPA • Environmental Protection Agency
  • 6. 6 Controlling Water Pollution in the U.S. • National Pollutant Discharge Elimination System (NPDES) requirements • EPA • Industrial or municipal facilities must obtain a permit to discharge to surface water • Discharge limits • Monitoring and reporting requirements • Ensure that surface waters stay safe for marine life, surrounding vegetation, recreational use, and as a drinking water source
  • 7. 7 Regulatory Method for Anions: EPA Method 300.0 • Revision 2.1 Parts A and B published in 1993 • Outlines the method for determination of inorganic anions by ion chromatography • Specifies use of suppressed conductivity for determination of: • Bromide (Part A) • Ortho-Phosphate-P (Part A) • Chloride (Part A) • Sulfate (Part A) • Fluoride (Part A) • Bromate (Part B) • Nitrate (Part A) • Chlorate (Part B) • Nitrite (Part A) • Chlorite (Part B) • Applies to: • Drinking water • Ground and surface water • Wastewater (domestic and industrial) • Raw water (unfinished drinking water)
  • 8. 8 Column: Thermo Scientific™ Dionex™ IonPac™ AG4A-SC, AS4A-SC, 4 mm i.d. Eluent: 1.7 mM sodium bicarbonate/ 1.8 mM sodium carbonate Flow Rate: 2.0 mL/min Injection: 50 µL Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ ASRS™ ULTRA Anion Self-Regenerating Suppressor™, recycle mode Peaks: 1.Fluoride 2 mg/L 2.Chloride 3 3.Nitrite 5 4.Bromide 10 5.Nitrate 10 6.Phosphate 15 7.Sulfate 15 0 2 4 6 8 Minutes 0 µS 10 10 1 2 3 4 5 6 7 EPA Method 300.0 (A)
  • 9. 9 EPA Method 300.1 • Published in 1997 • Refinement of Method 300.0 • Greater sensitivity for ions • Single, higher capacity Dionex IonPac AG9-HC column • 2 mm or 4 mm i.d. • Different injection volumes allowed depending on analytes and columns
  • 10. 10 Regulatory Method for Cations: ASTM D6919-03 • Outlines the method for determination of cations by ion chromatography • Specifies use of suppressed and nonsuppressed conductivity for determination of: • Lithium • Sodium • Ammonium • Potassium • Magnesium • Calcium • Applies to: • Drinking water • Reagent water • Wastewaters
  • 11. 11 0 5 10 15 20 Separation of Alkali and Alkaline Earth Metals and Ammonium Column: Dionex IonPac CS12A, 4 mm i.d. Eluent: 18 mN Methanesulfonic acid Flow Rate: 1.0 mL/min Inj. Volume: 25 µL Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ CSRS™ 300 Cation Self- Regenerating Suppressor, recycle mode Peaks: 1. Lithium 1 mg/L 2. Sodium 4 3. Ammonium 5 4. Potassium 10 5. Rubidium 10 6. Cesium 10 7. Magnesium 5 8. Calcium 10 9. Strontium 10 10. Barium 10 1 4 6 2 3 Minutes 25 10 µS 0 9 8 5 7 20
  • 12. 12 Common Ions in Wastewater Measured by IC • Inorganic anions • Chloride • Disrupts nitrification processes • Sulfate • Disrupt anaerobic digestion processes • Nitrate, nitrite, phosphate • Plant nutrients; algal blooms and deoxygenation • Bromide • Ozonation, chlorination -> Disinfection By-Products: brominated trihalomethanes, bromate  Carcinogenic • Organic acids • Formic and acetic acids • pH balance
  • 13. 13 Common Ions in Wastewater Measured by IC • Cations • Potassium, sodium • Disrupts osmotic balance of plants • Lithium • Human toxicity • Ammonium • Corrosive • Magnesium, calcium, barium • Scale buildup • Strontium • Radioactive
  • 14. 14 Challenge of Wastewater Analysis High concentrations of dissolved salts: • Exceed column capacity • Poor chromatography • Peak suppression • Inaccurate reporting • Exceed linear calibration range • Analyte-specific • Inaccurate results • Decrease column lifetime 0 2 4 11 0 12,000 µS Minutes 6 8 10 0 50 µS 0 2 4 116 8 10 Minutes Undiluted Diluted
  • 15. 15 Obtaining Accurate Data From Wastewater • Manual analysis • Post-run • Determine concentration from chromatogram peak area  Exceed limit → dilute → re-run sample • Pre-run • Manual conductivity measurement  Exceed limit → dilute → run sample • Tedious • Dilutions prone to errors
  • 16. 16 Increasing Accuracy With Automation • Automated analysis • “AutoDilution” • Post-run analysis using ion chromatograph software to determine if too much sample was loaded • In-line Conductivity • Conductivity measured prior to loading sample onto column • Exceeding upper limit triggers loading of less sample • Less sample injected • Smaller sample loop • Partial loop • Automated sample dilution • Loading of much lower sample amounts
  • 17. 17 Automated Analysis: AutoDilution Wastewater Centrifugation Filtration Automated Sample Dilution Report Chromatogram Thermo Scientific Dionex AS-AP Autosampler No Yes Does peak area or height exceed cut-off? AutoDilution Thermo Scientific™ Dionex™ Chromeleon™ CDS Software IC System Thermo Scientific™ Dionex™ ICS-2100 RFIC™ System
  • 18. 18 Automated Analysis: In-line Conductivity and Automated Dilution Wastewater Centrifugation Filtration Automated Sample Dilution Does conductivity exceed cutoff? Yes No Report Chromatogram Thermo Scientific Dionex AS-AP Autosampler Thermo Scientific™ Dionex™ Chromeleon™ CDS Software IC System Dionex ICS-2100 RFIC System Thermo Scientific Dionex Sample Conductivity and pH Accessory
  • 19. 19 Analysis of Anions in Automatically Diluted Fracking Flowback Wastewater Peaks: Measured Undiluted 1. Acetate < 0.05 mg/L < 5 2. Formate < 0.05 < 5 3. Chloride 940.0 94,000 4. Sulfate 0.12 12 5. Bromide 8.90 890 0.0 0.65 µS Minutes 0 2 4 8 0 2,400 µS Minutes 3 1 2 3 4 5 6 0 2 4 86 5 4 1 2 Column: Dionex IonPac AG18/AS18, 4 mm i.d. Eluent Source: Thermo Scientific Dionex EGC III KOH cartridge Eluent: 39 mM KOH Flow Rate: 1 mL/min Inj. Volume: 25 µL Col. Temp.: 30 °C Detection: Suppressed conductivity, DionexASRS 300 Anion Self-Regenerating Suppressor, recycle mode Sample: 100-fold diluted fracking flowback, filtered, 0.2 µm
  • 20. 20 Analysis of Cations in Automatically Diluted Fracking Flowback Wastewater Peaks: Measured Undiluted 1. Lithium < 0.05 mg/L < 5 2. Sodium 28.0 28,000 3. Ammonium 0.35 350 4. Potassium 0.50 500 5. Magnesium 1.1 1,100 6. Calcium 10.0 10,000 0.0 8.2 µS Minutes 0 5 10 23 0 80 µS Minutes 3 Column: Dionex IonPac CG16/CS16, 0.4 mm i.d. Eluent Source: Dionex EGC-MSA (capillary) cartridge Eluent: 30 mM MSA Flow Rate: 0.01 mL/min Inj. Volume: 0.4 µL Col. Temp.: 40 °C Detection: Suppressed conductivity, Dionex CCES 300 Cation Self- Regenerating Suppressor, recycle mode Sample: 1000-fold diluted fracking flowback, filtered, 0.2 µm 1 2 3 4 5 15 5 4 1 2 6 20 6 0 5 10 2315 20
  • 21. 21 Innovations That Have Made IC Easier • Packed Bed Suppression • Reduced background due to mobile phase for improved signal • Electrolytic Suppression • Greater flexibility in mobile phase selection/strength; no chemical regeneration • Reagent-Free IC (RFIC) • Electrolytic eluent generation makes gradient separations as easy as isocratic; just add water • Capillary IC • 18 months continuous operation, infrequent calibration; IC on Demand • High-pressure IC (HPIC) • Higher flow rate, faster runs; use of 4 µm particle columns for improved efficiency, resolution, and chromatographic flexibility
  • 22. 22 • High purity eluents generated on line • Accurate, precise, reproducible • Just add water Precise, Contamination Free Eluents Day after Day, Analyst to Analyst, Lab to Lab Pump H2O K+ Purified KOH [KOH]  Current Flow Rate Pt Cathode (2H20 + 2e- 20H- + H2) - Reagent-Free IC with Eluent Generation (RFIC-EG)
  • 23. 23 RFIC Dionex ICS-900 System Dionex ICS-1100 System Dionex ICS-4000 System Dionex ICS-2100 System Dionex ICS-1600 System Dionex ICS-5000+ System HPIC The Dionex Ion Chromatography Product Line
  • 24. 24 Capillary HPIC Advantages • “IC on Demand” • System is always ready for your samples • Higher laboratory productivity • Less labor needed for calibration • High-pressure • Up to 5000 psi • Faster runs • Lower cost of ownership • Less eluent consumed and waste generated
  • 25. 25 Thermo Scientific Dionex ICS-5000+ HPIC System Thermo Scientific Dionex ICS-4000 Capillary HPIC System Capillary HPIC Systems
  • 26. 26 Capillary Technology – The Dionex IC Cube Module Guard and Separation Column Suppressor CRD 200 Injection Valve EG Degas Side View of Cap Suppressor 8.9 cm 16.5 cm
  • 27. 27 5 25 -1.0 60 µS Minutes Column: Dionex IonPac AG19/AS19, 0.4 mm i.d. Eluent Source: Dionex EGC-KOH cartridge (Capillary) Gradient: 10 to 25 mM KOH (0–10 min) 25 to 70 mM KOH (10–20 min) 10 mM KOH (20–25 min) Flow Rate: 0.010 mL/min Inj. Volume: 0.4 µL Column Temp.: 30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Sample: Treated wastewater, filtered, 0.2 µm Peaks: 0.4 mm i.d. 4 mm i.d.* 1. Fluoride 1.76 mg/L 1.69 2. Chloride 180.00 180.00 3. Bromide 0.42 0.51 4. Nitrate 11.80 11.90 5. Sulfate 96.90 96.8 6. Phosphate 0.94 1.25 *Data from 4 mm i.d. column using appropriate run conditions (Dionex ICS-1100 System) 1 2 3 4 5 6 10 15 200 Determination of Common Anions in Treated Wastewater
  • 28. 28 Fast Determination of Inorganic Ions Using the Dionex IonPac AS18-4µm Column Column: Dionex IonPac AG18-4µm/ AS18-4µm, 0.4  150 mm Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 23 mM KOH Flow Rate: A: 0.010, B: 0.015, C: 0.025 mL/min Inj. Volume: 0.4 µL Column Temp.:30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Peaks: 1. Fluoride 0.1 mg/L 2. Chlorite 1.0 3. Chloride 0.6 4. Nitrite 1.0 5. Carbonate -- 6. Bromide 2.0 7. Sulfate 2.0 8. Nitrate 2.0 9. Chlorate 2.0 3 64 750 Minutes 4321 0 13 µS 7 8 6 9 5 2 1 C: 0.025 mL/min 3800 psi B: 0.015 mL/min 2400 psi A: 0.010 mL/min 1600 psi
  • 29. 29 Fast Determination of Inorganic Anions in Municipal Wastewater Peaks (Total): A B C D 1. Chloride 76.5 146 154 130 mg/L 2. Nitrite 1.5 2.1 37.4 1.6 3. Carbonate -- -- -- -- 4. Sulfate 41.6 88.9 84.8 91.8 5. Nitrate 28.8 7.2 31.7 128 3 4 40 Minutes 321 0 1.7 µS B A 5 2 1 C D Column: Dionex IonPac AG18-4µm/ AS18-4µm, 0.4 mm i.d. Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 23 mM KOH Flow Rate: 0.025 mL/min Inj. Volume: 0.4 µL Column Temp.: 30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Sample Prep: Diluted 1000-fold, filtered, 0.2 µm Samples: A: Influent B: Primary effluent C: Trickling effluent D: Final effluent
  • 30. 30 Fast Determination of Cations in Municipal Wastewater Column: Dionex IonPac CG16/CS16, 0.5 mm i.d. Eluent Source: Dionex EGC-MSA Cartridge (Capillary) Eluent: 30 mM MSA Flow Rate: A: 0.010 mL/min, B: 0.030 mL/min Inj. Volume: 0.4 µL Column Temp.: 40 °C Detection: Suppressed Conductivity, Dionex CCES 300, recycle mode Sample: Wastewater diluted 50-fold, filtered, 0.2 µm Peaks: 1. Sodium 195.9 mg/L 2. Ammonium --- 3. Potassium 11.6 4. Magnesium 38.0 5. Calcium 52.9 Minutes µS 30 µL/min 3720 psi A B 0 10 30 -2 14 10 µL/min 1250 psi 1 2 4 4 1 2 3 5 5 3 20
  • 31. 31 Conclusions • The high ion concentrations typical of wastewater presents a challenge to analysis • In-line conductivity measurement and automated sample dilution combine to ensure that what is loaded onto an IC column is within the calibration range • Reagent-Free IC removes the inconvenience and variability of manual eluent preparation • High-pressure capillary IC allows the use of faster flow rates for quick run times, while producing very little waste
  • 32. 32 Thank you! WS71012_E 03/14S
    Please download to view
  • 32
    All materials on our website are shared by users. If you have any questions about copyright issues, please report us to resolve them. We are always happy to assist you.
    Description
    Wastewater is produced by multiple sources, including chemical manufacturing, power generation, petroleum product extraction, and private residences. Specific industries can use knowledge of around the analytes present in wastewater to make decisions on reuse, treatment, or whether disposal is the most cost effective option. Prior to any discharge into ground or surface waters, the level of specific analytes must be determined to ensure that they do not exceed regulated limits. If these limits are being exceeded, treatment will be required. Ion Chromatography (IC) is the primary technique used for measuring the concentration of ions in wastewater and numerous methods have been developed that meet regulatory requirements. Learn about IC methods that enable accurate, consistent, and rapid measurement of both anions, such as chloride, sulfate, and bromate, and cations, such as sodium and magnesium.
    Text
    • 1. 1 The world leader in serving science Peter Bodsky Field Marketing Manager March 26, 2014 Rapid Determination of Inorganic Ions in Wastewater by Ion Chromatography
  • 2. 2 Agenda • Wastewater sources • Regulations and methods • Analytes of interest in wastewater • Challenge of wastewater analysis • Ion Chromatography system innovations • Inline conductivity and automated dilution • Reagent-Free™ Ion Chromatography (RFIC™) • High-Pressure™ Capillary IC (HPIC™) • Conclusions
  • 3. 3 Examples of Wastewater Sources • Manufacturing • Oil and gas extraction • Petroleum refining • Mining • Power generation • Household sewage • Agriculture
  • 4. 4 Reasons to Perform Wastewater Analysis • Monitoring discharge • Regulatory limits • Nutrient Analysis • Excessive plant growth in aqueous environments • Known samples • Historical analysis • E.g., High chloride level from a treatment facility with a water inlet near the sea/estuary • Unknown samples • Investigative, pollution incident, farm run-off, milk spill, or industrial discharge plant failure
  • 5. 5 International Wastewater Regulations • ISO • International Organization for Standardization • ASTM International • “American Society for Testing and Materials” • DIN • Deutsches Institut für Normung • German Standard • U.S. EPA • Environmental Protection Agency
  • 6. 6 Controlling Water Pollution in the U.S. • National Pollutant Discharge Elimination System (NPDES) requirements • EPA • Industrial or municipal facilities must obtain a permit to discharge to surface water • Discharge limits • Monitoring and reporting requirements • Ensure that surface waters stay safe for marine life, surrounding vegetation, recreational use, and as a drinking water source
  • 7. 7 Regulatory Method for Anions: EPA Method 300.0 • Revision 2.1 Parts A and B published in 1993 • Outlines the method for determination of inorganic anions by ion chromatography • Specifies use of suppressed conductivity for determination of: • Bromide (Part A) • Ortho-Phosphate-P (Part A) • Chloride (Part A) • Sulfate (Part A) • Fluoride (Part A) • Bromate (Part B) • Nitrate (Part A) • Chlorate (Part B) • Nitrite (Part A) • Chlorite (Part B) • Applies to: • Drinking water • Ground and surface water • Wastewater (domestic and industrial) • Raw water (unfinished drinking water)
  • 8. 8 Column: Thermo Scientific™ Dionex™ IonPac™ AG4A-SC, AS4A-SC, 4 mm i.d. Eluent: 1.7 mM sodium bicarbonate/ 1.8 mM sodium carbonate Flow Rate: 2.0 mL/min Injection: 50 µL Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ ASRS™ ULTRA Anion Self-Regenerating Suppressor™, recycle mode Peaks: 1.Fluoride 2 mg/L 2.Chloride 3 3.Nitrite 5 4.Bromide 10 5.Nitrate 10 6.Phosphate 15 7.Sulfate 15 0 2 4 6 8 Minutes 0 µS 10 10 1 2 3 4 5 6 7 EPA Method 300.0 (A)
  • 9. 9 EPA Method 300.1 • Published in 1997 • Refinement of Method 300.0 • Greater sensitivity for ions • Single, higher capacity Dionex IonPac AG9-HC column • 2 mm or 4 mm i.d. • Different injection volumes allowed depending on analytes and columns
  • 10. 10 Regulatory Method for Cations: ASTM D6919-03 • Outlines the method for determination of cations by ion chromatography • Specifies use of suppressed and nonsuppressed conductivity for determination of: • Lithium • Sodium • Ammonium • Potassium • Magnesium • Calcium • Applies to: • Drinking water • Reagent water • Wastewaters
  • 11. 11 0 5 10 15 20 Separation of Alkali and Alkaline Earth Metals and Ammonium Column: Dionex IonPac CS12A, 4 mm i.d. Eluent: 18 mN Methanesulfonic acid Flow Rate: 1.0 mL/min Inj. Volume: 25 µL Detection: Suppressed conductivity, Thermo Scientific™ Dionex™ CSRS™ 300 Cation Self- Regenerating Suppressor, recycle mode Peaks: 1. Lithium 1 mg/L 2. Sodium 4 3. Ammonium 5 4. Potassium 10 5. Rubidium 10 6. Cesium 10 7. Magnesium 5 8. Calcium 10 9. Strontium 10 10. Barium 10 1 4 6 2 3 Minutes 25 10 µS 0 9 8 5 7 20
  • 12. 12 Common Ions in Wastewater Measured by IC • Inorganic anions • Chloride • Disrupts nitrification processes • Sulfate • Disrupt anaerobic digestion processes • Nitrate, nitrite, phosphate • Plant nutrients; algal blooms and deoxygenation • Bromide • Ozonation, chlorination -> Disinfection By-Products: brominated trihalomethanes, bromate  Carcinogenic • Organic acids • Formic and acetic acids • pH balance
  • 13. 13 Common Ions in Wastewater Measured by IC • Cations • Potassium, sodium • Disrupts osmotic balance of plants • Lithium • Human toxicity • Ammonium • Corrosive • Magnesium, calcium, barium • Scale buildup • Strontium • Radioactive
  • 14. 14 Challenge of Wastewater Analysis High concentrations of dissolved salts: • Exceed column capacity • Poor chromatography • Peak suppression • Inaccurate reporting • Exceed linear calibration range • Analyte-specific • Inaccurate results • Decrease column lifetime 0 2 4 11 0 12,000 µS Minutes 6 8 10 0 50 µS 0 2 4 116 8 10 Minutes Undiluted Diluted
  • 15. 15 Obtaining Accurate Data From Wastewater • Manual analysis • Post-run • Determine concentration from chromatogram peak area  Exceed limit → dilute → re-run sample • Pre-run • Manual conductivity measurement  Exceed limit → dilute → run sample • Tedious • Dilutions prone to errors
  • 16. 16 Increasing Accuracy With Automation • Automated analysis • “AutoDilution” • Post-run analysis using ion chromatograph software to determine if too much sample was loaded • In-line Conductivity • Conductivity measured prior to loading sample onto column • Exceeding upper limit triggers loading of less sample • Less sample injected • Smaller sample loop • Partial loop • Automated sample dilution • Loading of much lower sample amounts
  • 17. 17 Automated Analysis: AutoDilution Wastewater Centrifugation Filtration Automated Sample Dilution Report Chromatogram Thermo Scientific Dionex AS-AP Autosampler No Yes Does peak area or height exceed cut-off? AutoDilution Thermo Scientific™ Dionex™ Chromeleon™ CDS Software IC System Thermo Scientific™ Dionex™ ICS-2100 RFIC™ System
  • 18. 18 Automated Analysis: In-line Conductivity and Automated Dilution Wastewater Centrifugation Filtration Automated Sample Dilution Does conductivity exceed cutoff? Yes No Report Chromatogram Thermo Scientific Dionex AS-AP Autosampler Thermo Scientific™ Dionex™ Chromeleon™ CDS Software IC System Dionex ICS-2100 RFIC System Thermo Scientific Dionex Sample Conductivity and pH Accessory
  • 19. 19 Analysis of Anions in Automatically Diluted Fracking Flowback Wastewater Peaks: Measured Undiluted 1. Acetate < 0.05 mg/L < 5 2. Formate < 0.05 < 5 3. Chloride 940.0 94,000 4. Sulfate 0.12 12 5. Bromide 8.90 890 0.0 0.65 µS Minutes 0 2 4 8 0 2,400 µS Minutes 3 1 2 3 4 5 6 0 2 4 86 5 4 1 2 Column: Dionex IonPac AG18/AS18, 4 mm i.d. Eluent Source: Thermo Scientific Dionex EGC III KOH cartridge Eluent: 39 mM KOH Flow Rate: 1 mL/min Inj. Volume: 25 µL Col. Temp.: 30 °C Detection: Suppressed conductivity, DionexASRS 300 Anion Self-Regenerating Suppressor, recycle mode Sample: 100-fold diluted fracking flowback, filtered, 0.2 µm
  • 20. 20 Analysis of Cations in Automatically Diluted Fracking Flowback Wastewater Peaks: Measured Undiluted 1. Lithium < 0.05 mg/L < 5 2. Sodium 28.0 28,000 3. Ammonium 0.35 350 4. Potassium 0.50 500 5. Magnesium 1.1 1,100 6. Calcium 10.0 10,000 0.0 8.2 µS Minutes 0 5 10 23 0 80 µS Minutes 3 Column: Dionex IonPac CG16/CS16, 0.4 mm i.d. Eluent Source: Dionex EGC-MSA (capillary) cartridge Eluent: 30 mM MSA Flow Rate: 0.01 mL/min Inj. Volume: 0.4 µL Col. Temp.: 40 °C Detection: Suppressed conductivity, Dionex CCES 300 Cation Self- Regenerating Suppressor, recycle mode Sample: 1000-fold diluted fracking flowback, filtered, 0.2 µm 1 2 3 4 5 15 5 4 1 2 6 20 6 0 5 10 2315 20
  • 21. 21 Innovations That Have Made IC Easier • Packed Bed Suppression • Reduced background due to mobile phase for improved signal • Electrolytic Suppression • Greater flexibility in mobile phase selection/strength; no chemical regeneration • Reagent-Free IC (RFIC) • Electrolytic eluent generation makes gradient separations as easy as isocratic; just add water • Capillary IC • 18 months continuous operation, infrequent calibration; IC on Demand • High-pressure IC (HPIC) • Higher flow rate, faster runs; use of 4 µm particle columns for improved efficiency, resolution, and chromatographic flexibility
  • 22. 22 • High purity eluents generated on line • Accurate, precise, reproducible • Just add water Precise, Contamination Free Eluents Day after Day, Analyst to Analyst, Lab to Lab Pump H2O K+ Purified KOH [KOH]  Current Flow Rate Pt Cathode (2H20 + 2e- 20H- + H2) - Reagent-Free IC with Eluent Generation (RFIC-EG)
  • 23. 23 RFIC Dionex ICS-900 System Dionex ICS-1100 System Dionex ICS-4000 System Dionex ICS-2100 System Dionex ICS-1600 System Dionex ICS-5000+ System HPIC The Dionex Ion Chromatography Product Line
  • 24. 24 Capillary HPIC Advantages • “IC on Demand” • System is always ready for your samples • Higher laboratory productivity • Less labor needed for calibration • High-pressure • Up to 5000 psi • Faster runs • Lower cost of ownership • Less eluent consumed and waste generated
  • 25. 25 Thermo Scientific Dionex ICS-5000+ HPIC System Thermo Scientific Dionex ICS-4000 Capillary HPIC System Capillary HPIC Systems
  • 26. 26 Capillary Technology – The Dionex IC Cube Module Guard and Separation Column Suppressor CRD 200 Injection Valve EG Degas Side View of Cap Suppressor 8.9 cm 16.5 cm
  • 27. 27 5 25 -1.0 60 µS Minutes Column: Dionex IonPac AG19/AS19, 0.4 mm i.d. Eluent Source: Dionex EGC-KOH cartridge (Capillary) Gradient: 10 to 25 mM KOH (0–10 min) 25 to 70 mM KOH (10–20 min) 10 mM KOH (20–25 min) Flow Rate: 0.010 mL/min Inj. Volume: 0.4 µL Column Temp.: 30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Sample: Treated wastewater, filtered, 0.2 µm Peaks: 0.4 mm i.d. 4 mm i.d.* 1. Fluoride 1.76 mg/L 1.69 2. Chloride 180.00 180.00 3. Bromide 0.42 0.51 4. Nitrate 11.80 11.90 5. Sulfate 96.90 96.8 6. Phosphate 0.94 1.25 *Data from 4 mm i.d. column using appropriate run conditions (Dionex ICS-1100 System) 1 2 3 4 5 6 10 15 200 Determination of Common Anions in Treated Wastewater
  • 28. 28 Fast Determination of Inorganic Ions Using the Dionex IonPac AS18-4µm Column Column: Dionex IonPac AG18-4µm/ AS18-4µm, 0.4  150 mm Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 23 mM KOH Flow Rate: A: 0.010, B: 0.015, C: 0.025 mL/min Inj. Volume: 0.4 µL Column Temp.:30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Peaks: 1. Fluoride 0.1 mg/L 2. Chlorite 1.0 3. Chloride 0.6 4. Nitrite 1.0 5. Carbonate -- 6. Bromide 2.0 7. Sulfate 2.0 8. Nitrate 2.0 9. Chlorate 2.0 3 64 750 Minutes 4321 0 13 µS 7 8 6 9 5 2 1 C: 0.025 mL/min 3800 psi B: 0.015 mL/min 2400 psi A: 0.010 mL/min 1600 psi
  • 29. 29 Fast Determination of Inorganic Anions in Municipal Wastewater Peaks (Total): A B C D 1. Chloride 76.5 146 154 130 mg/L 2. Nitrite 1.5 2.1 37.4 1.6 3. Carbonate -- -- -- -- 4. Sulfate 41.6 88.9 84.8 91.8 5. Nitrate 28.8 7.2 31.7 128 3 4 40 Minutes 321 0 1.7 µS B A 5 2 1 C D Column: Dionex IonPac AG18-4µm/ AS18-4µm, 0.4 mm i.d. Eluent Source: Dionex EGC-KOH Cartridge (Capillary) Eluent: 23 mM KOH Flow Rate: 0.025 mL/min Inj. Volume: 0.4 µL Column Temp.: 30 °C Detection: Suppressed conductivity, Dionex ACES 300, recycle mode Sample Prep: Diluted 1000-fold, filtered, 0.2 µm Samples: A: Influent B: Primary effluent C: Trickling effluent D: Final effluent
  • 30. 30 Fast Determination of Cations in Municipal Wastewater Column: Dionex IonPac CG16/CS16, 0.5 mm i.d. Eluent Source: Dionex EGC-MSA Cartridge (Capillary) Eluent: 30 mM MSA Flow Rate: A: 0.010 mL/min, B: 0.030 mL/min Inj. Volume: 0.4 µL Column Temp.: 40 °C Detection: Suppressed Conductivity, Dionex CCES 300, recycle mode Sample: Wastewater diluted 50-fold, filtered, 0.2 µm Peaks: 1. Sodium 195.9 mg/L 2. Ammonium --- 3. Potassium 11.6 4. Magnesium 38.0 5. Calcium 52.9 Minutes µS 30 µL/min 3720 psi A B 0 10 30 -2 14 10 µL/min 1250 psi 1 2 4 4 1 2 3 5 5 3 20
  • 31. 31 Conclusions • The high ion concentrations typical of wastewater presents a challenge to analysis • In-line conductivity measurement and automated sample dilution combine to ensure that what is loaded onto an IC column is within the calibration range • Reagent-Free IC removes the inconvenience and variability of manual eluent preparation • High-pressure capillary IC allows the use of faster flow rates for quick run times, while producing very little waste
  • 32. 32 Thank you! WS71012_E 03/14S
  • Comments
    Top