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The world leader in serving science

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

3

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)

1

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