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.

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