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Peter Bodsky
Field Marketing Manager
March 26, 2014
Rapid Determination of Inorganic Ions in Wastewater by Ion Chromatography
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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
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Examples of Wastewater Sources
• Manufacturing• Oil and gas extraction• Petroleum refining• Mining• Power generation• Household sewage• Agriculture
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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
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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
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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
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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)
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Column: Thermo Scientific™ Dionex™ IonPac™ AG4A-SC, AS4A-SC,
4 mm i.d.Eluent: 1.7 mM sodium bicarbonate/
1.8 mM sodium carbonateFlow Rate: 2.0 mL/minInjection: 50 µLDetection: Suppressed conductivity,
Thermo Scientific™ Dionex™ ASRS™ ULTRA Anion Self-Regenerating
Suppressor™, recycle mode
Peaks: 1. Fluoride 2 mg/L2. Chloride 33. Nitrite 54. Bromide 105. Nitrate 106. Phosphate 157. Sulfate 15
0 2 4 6 8Minutes
0
µS
10
10
1
23 4 5
6
7
EPA Method 300.0 (A)
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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
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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
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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 acidFlow Rate: 1.0 mL/minInj. Volume: 25 µLDetection: 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 1010. Barium 10
1
4
6
2
3
Minutes
25
10
µS
0
9
8
5
7
20
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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
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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
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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 4 110
12,000
µS
Minutes6 8 10
0
50
µS
0 2 4 116 8 10
Minutes
Undiluted
Diluted
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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
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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
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Automated Analysis: AutoDilution
Wastewater
Centrifugation
Filtration
Automated Sample Dilution
Report
Chromatogram
Thermo Scientific Dionex AS-APAutosampler
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
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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-APAutosampler
Thermo Scientific™ Dionex™
Chromeleon™ CDS Software
IC System
Dionex ICS-2100
RFIC System
Thermo Scientific Dionex
Sample Conductivity and pH Accessory
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Analysis of Anions in Automatically Diluted Fracking Flowback Wastewater
Peaks: Measured Undiluted
1. Acetate < 0.05 mg/L < 52. Formate < 0.05 < 53. 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 cartridgeEluent: 39 mM KOHFlow Rate: 1 mL/minInj. Volume: 25 µLCol. Temp.: 30 °CDetection: Suppressed conductivity,
Dionex ASRS 300 Anion Self-Regenerating Suppressor, recycle mode
Sample: 100-fold diluted fracking flowback, filtered, 0.2 µm
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Analysis of Cations in Automatically Diluted Fracking Flowback Wastewater
Peaks: Measured Undiluted
1. Lithium < 0.05 mg/L < 52. Sodium 28.0 28,0003. 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
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Column: Dionex IonPac CG16/CS16,0.4 mm i.d.
Eluent Source: Dionex EGC-MSA (capillary) cartridgeEluent: 30 mM MSAFlow Rate: 0.01 mL/minInj. Volume: 0.4 µLCol. Temp.: 40 °CDetection: Suppressed conductivity,
Dionex CCES 300 Cation Self-Regenerating Suppressor,
recycle modeSample: 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
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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
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• 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)
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RFIC
Dionex ICS-900System
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
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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
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Thermo ScientificDionex ICS-5000+
HPIC System
Thermo ScientificDionex ICS-4000
Capillary HPIC System
Capillary HPIC Systems
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Capillary Technology – The Dionex IC Cube Module
Guard and Separation Column
Suppressor
CRD 200
Injection ValveEG Degas
Side View of CapSuppressor
8.9 cm
16.5 cm
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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/minInj. Volume: 0.4 µLColumn Temp.: 30 °CDetection: Suppressed conductivity,
Dionex ACES 300, recyclemodeSample: 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 180.00 180.003. Bromide 0.42 0.514. Nitrate 11.80 11.905. Sulfate 96.90 96.86. Phosphate 0.94 1.25
*Data from 4 mm i.d. column using appropriate run conditions (Dionex ICS-1100 System)
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2
3
4 5
6
10 15 200
Determination of Common Anions in Treated Wastewater
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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/minInj. Volume: 0.4 µLColumn Temp.:30 °C Detection: Suppressed conductivity,
Dionex ACES 300, recycle mode
Peaks:1. Fluoride 0.1 mg/L2. Chlorite 1.03. Chloride 0.6
4. Nitrite 1.05. Carbonate --6. Bromide 2.07. Sulfate 2.08. Nitrate 2.09. Chlorate 2.0
3
64
750
Minutes
4321
0
13
µS
78
6
9
5
2
1 C: 0.025 mL/min3800 psi
B: 0.015 mL/min2400 psi
A: 0.010 mL/min1600 psi
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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 37.41.6
3. Carbonate -- -- -- --
4. Sulfate 41.6 88.9 84.891.8
5. Nitrate 28.8 7.2 31.7128
3
4
40
Minutes
3210
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/minInj. Volume: 0.4 µLColumn Temp.: 30 °C Detection: Suppressed conductivity,
Dionex ACES 300, recyclemodeSample Prep: Diluted 1000-fold, filtered, 0.2 µmSamples: A: Influent
B: Primary effluentC: Trickling effluentD: Final effluent
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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 MSAFlow Rate: A: 0.010 mL/min,
B: 0.030 mL/minInj. Volume: 0.4 µLColumn Temp.: 40 °CDetection: Suppressed Conductivity,
Dionex CCES 300, recycle mode
Sample: Wastewater diluted 50-fold, filtered, 0.2 µm
Peaks:1. Sodium 195.9 mg/L2. Ammonium ---3. Potassium 11.6
4. Magnesium 38.05. Calcium 52.9
Minutes
µS30 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
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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
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Thank you!
WS71012_E 03/14S
