The importance of clean drinking water is recognized worldwide. In the U.S., the Environmental Protection Agency (EPA) has established Maximum Contamination Limits (MCL) for monitoring toxic contaminants that may cause adverse health effects. Other ions, such as chloride and sulfate are monitored for aesthetic characteristics under the U.S. National Secondary Drinking Water Standards guidelines. Similar regulations for clean drinking water have been implemented in other industrialized countries. Ion Chromatography (IC) methods have been approved for compliance monitoring including U.S. EPA 300.0 in 1993. Learn about using ion chromatography for the determination of inorganic anions, perchlorate and chromate for compliance monitoring according to U.S. EPA Methods 300.0, 314 and 218.6.

1. 1
The world leader in serving science
Arthur W. Fitchett, Ph.D.
Thermo Fisher Scientific
April 29, 2014
Analysis of Perchlorate, Chromate and
Inorganic Anions in Drinking Water

2. 2
Agenda
• Innovation and Ease of Use
• IC Systems
• Inorganic Anions EPA Method 300.0 (A),(B)
• Bromate
• EPA 314.0 Perchlorate
• EPA Method 218.6 (Hexavalent Chromium)
• Automated Sample Preparation
• Organic Contaminants
• Summary & Questions

3. 3
Ease of Use and Innovation – Prepared Eluents
Manually prepared carbonate eluents
• Just dilute from carbonate concentrate solutions
• Developed the first methods in 1980s
• EPA 300.0 approved Thermo Scientific™ Dionex™ IonPac™
AS4A Column
• 1980 – 2010 – Developed two new generations of carbonate
optimized columns
• From microporous to macroporous, supermacroporous
• 2013 – Supported on the new formats, developed capillary
format columns (EPA approved)

4. 4
Ease of Use and Innovation – Eluent Generation
Just Add Water
• Allows both isocratic and gradient separations
• Eliminates manually prepared eluents
• Increased sensitivity (S/N) because of improved suppression
of hydroxide eluents
• Approved for EPA methods
• Introduced two generations of hydroxide optimized columns
• 2010 – 2014 Introduced the capillary size columns, capillary
capable IC systems (EPA approved)
• Introduced smaller particle columns and high-pressure
capable systems

5. 5
Data
Management
Conductivity
Detector
High-Pressure
Non-Metallic
Pump
Eluent
Generator
(OH– or H+)
Waste
Sample Inject
(Autosampler) Recycle
Mode
Detection
Water/
Eluent
CR-TC
Cell
Effluent
Electrolytic
Eluent
Suppressor
Separation Column
Ion Chromatography System
RFIC, Innovation
and Ease-of-Use
Behind the Curtain

6. 6
A Complete Family of Ion Chromatography Systems
Thermo Scientific
Dionex ICS-1100
Basic Integrated
Ion Chromatography
System
Thermo Scientific
Dionex ICS-900
Starter Line Ion
Chromatography
System
Thermo Scientific
Dionex ICS-1600
Standard
Integrated Ion
Chromatography
System
Thermo Scientific™
Dionex™ ICS-2100
Reagent-Free™ Ion
Chromatography
(RFIC™) System
Thermo Scientific™ Dionex™
ICS-5000+ HPIC™ Ion
Chromatography System
Thermo Scientific
Dionex ICS-4000
Capillary HPIC Ion
Chromatography
System
RFIC
HPIC

7. 7
New High Efficiency Dionex IonPac 4 µm IC Columns
Dionex IonPac ion-exchange columns with 4 µm
particle-size resin
Require high-pressure capable IC systems
Benefits
• Smaller particles provide better performance
• Faster run times with higher flow rates using
150 mm columns
• Better resolution with standard flow rates using
250 mm columns
Improved resolution provides faster runs and better results
SEM Image of 4 µm Supermacroporous Bead
High Resolution using the
Dionex IonPac AS11-HC-4µm
Fast Run using the
Dionex IonPac AS18-4µm
0 401
10
Minutes
µS
0 3
-0.5
5.5
µS
Minutes 0 40
0
5
µS
Minutes
Applications
• Anions in environmental waters
• Organic acids in foods and
beverages
• Amines in chemical process
solutions
High Resolution using the
Dionex IonPac CS19-4µm

8. 8
Advantages of Suppressed Conductivity
Time
F
-
Cl - SO4
2-
F - Cl -
SO4
2-
Time
-µS
µS
Without Suppression
With Suppression
Eluent (KOH)
Sample F-, Cl-, SO4
2-
Ion-Exchange
Separation Column
Anion Electrolytically
Regenerating
Suppressor
in H2O
KF, KCI, K2SO4
in KOH
Injection Valve
Counter ions
HF, HCI, H2SO4

9. 9
KOH, H2
Dionex Electrolytically Regenerated Suppressors
WasteWaste
Anode
Detector
H
+
+ O2 H2 + OH–
H2O H2O
H2O H2O
Cation-
Exchange
Membranes
OH–
Cathode
K+, X– in KOH
H+
+ OH–
H2O
H+
+ X–
H+
, X–
in H2O
H+
H2O, O2
H2O 2H
+
+ ½ O2 + 2e
–
K+
2 H2O + 2e
–
2OH
–
+ H2

10. 10
Determination of Inorganic Ions in Drinking Water
• Regulatory requirements
• Public health – primary
• Acceptable taste – secondary
• Disinfection byproducts
• Chlorination – chlorite, chlorate, haloacetic acids
• Ozonation – bromate
• Associated with health issues
• Regulated under Safe Drinking Water Act
• EPA, promulgated to the states

11. 11
Determination of Hexavalent Chromium
Using Optimized EPA Method 218.6
Columns: Dionex IonPac NG1, Dionex
IonPac AS7, 4 mm
Eluent: 250 mM (NH4)2SO4
100 mM NH4OH
Flow Rate: 1.0 mL/min
Inj. Volume: 1000 µL
Postcolumn Reagent: 2 mM Diphenylcarbizide
10% CH3OH
1N H2SO4
0.33 mL/min
Reaction Coil: 750 µL
Detector: UV-Vis (530 nm)
Sample: 1.0 µg/L Cr(VI)
0 2 4 6 8
Minutes
0
2
Cr(VI)
mAU

12. 12
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

13. 13
0 2 4 6 8
Minutes
0
µS
10
10
1
2
3 4 5
6
7
1993 EPA Method 300.0 (A): Dionex IonPac AS4A
Column
Column: Dionex IonPacAG4A-SC, Dionex
IonPac AS4A-SC, 4  250 mm
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 Suppressor,
recycle mode
Peaks: 1. Fluoride 2 mg/L (ppm)
2. Chloride 3
3. Nitrite 5
4. Bromide 10
5. Nitrate 10
6. Phosphate 15
7. Sulfate 15

14. 14
Column: Dionex IonPac AG22, Dionex
IonPac AS22, 4  250 mm
Eluent: 4.5 mM sodium carbonate/
1.4 mM sodium bicarbonate
Flow Rate: 1.2 mL/min
Injection: 5 µL
Detection: Suppressed conductivity,
AutoSuppression ,
Thermo Scientific™ Dionex™
AERS™ 500 Anion Electrolytically
Regenerated Suppressor, 31 mA,
recycle mode
Peaks: 1. Fluoride 5 mg/L
2. Acetate 20
3. Chloride 10
4. Nitrite 15
5. Bromide 25
6. Nitrate 25
7. Phosphate 40
8. Sulfate 30
Minutes
1
2
3
4
5
6
7
8
0 2 4 6 10 128
-1
µS
4
Improved Separation of Eight Anions

15. 15
Minutes
2
4 5
South San Jose Drinking Water
Column: Dionex IonPacAG22, Dionex
IonPac AS22, 4  250 mm
Eluent: 4.5 mM sodium carbonate/
1.4 mM sodium bicarbonate
Flow Rate: 1.2 mL/min
Injection: 5 µL
Detection: Suppressed conductivity,
Dionex AERS 500 suppressor,
31 mA, recycle mode
Peaks: 1. Fluoride 0.20 mg/L
2. Chloride 37.7
3. Nitrate 5.05
4. Carbonate ---
5. Sulfate 37.3
1
3
-2
0 2 4 6 10 128
µS
20

16. 16
Determination of Anions in Surface Water Samples
Column: Dionex IonPacAG22, Dionex
IonPac AS22, 4  250 mm
Eluent: 4.5 mM Sodium carbonate/
1.4 mM Sodium bicarbonate
Flow Rate: 1.2 mL/min
Injection: 5 µL
Detection: Suppressed conductivity,
Dionex AERS 500 Suppressor,
31 mA, recycle mode
Sample Prep.: Filtered, 0.2 µm
Samples: A: White Water River
(Palm Springs)
B: Lake Tahoe
Peaks:
A B
1. Fluoride 0.23 mg/L 0.09 mg/L
2. Chloride 49.3 2.2
3. Nitrate 19.3 ---
4. Phosphate 1.9 ---
5. Sulfate 82.0 1.8
Minutes
1 3
-2
0 2 4 6 10 128
µS
5
20
2
Minutes
1
5
2
-0.4
0 2 4 6 10 128
µS
5
B
A
4

17. 17
Reagent-Free High Pressure IC for 6 min Run Times
System: Dionex ICS-5000+ Reagent-Free
HPIC system
Column: Dionex IonPac AG18-4µm/
Dionex IonPac AS18-4µm,
(2 × 250 mm)
Eluent: 23 mM KOH
Eluent Source: Thermo Scientific Dionex EGC 500
KOH cartridge
Flow Rate: A: 0.25, B: 0.31, C: 0.38 mL/min
Pressure: A: 2400, B: 3000, C: 3500 psi
Inj. Volume: 2.5 µL
Temperature: 30 C
Detection: Suppressed Conductivity,
Dionex ASRS 300 suppressor,
AutoSuppression,
recycle mode
Peaks: 1. Fluoride 0.5 mg/L
2. Chlorite 5
3. Chloride 3
4. Nitrite 5
5. Carbonate 20
6. Bromide 10
7. Sulfate 10
8. Nitrite 10
9. Chlorate 10
16
1
2
3
4
5
6
7
8
9
0 2 4 6 8 10
0
µS
Minutes
1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
9
A
B
C

18. 18
Trace Nitrite and Nitrate in High Ionic Strength Matrix Using Eluent
Generation, 4 µm Particle Column, and a High-Pressure IC System
Instrument: Dionex ICS-5000+ Reagent-Free
HPIC system
Column: Dionex IonPac AG19-4µm/Dionex
IonPac AS19-4µm (2  250 mm)
Gradient: 10 mM KOH from 0 to 10 min,
10–45 mM KOH from 10 to 25 min
Eluent Source: Dionex EGC 500 KOH Cartridge
Flow Rate: 0.25 mL/min
Inj. Volume: 2.5 µL
Temperature: 30 ˚C
Detection: Suppressed Conductivity,
Dionex AERS 500 suppressor,
2 mm, AutoSuppression, recycle
mode
Peaks: 1. Chloride 800 mg/L
2. Nitrite 0.1
3. Nitrate 0.1
4. Carbonate ---
5. Sulfate 100
6. Phosphate 100
0 8 16 24 32
-0.2
2
µS
1
2
3
5 6
4
0 8 16 24 32-200
1,800
µS
Minutes
1
2 3
5
6
4

19. 19
Oxyhalides

20. 20
Disinfection Byproducts
• Chlorination Processes
• Generate chlorite, chlorate, halomethanes and haloacetic acids
• Ozonation Processes
• Generates bromate from bromide, and halomethanes and haloacetic
acids
• Highly regulated due to associated health issues
• Chlorite: nervous system, affect fetal development, anemia
• Bromate: carcinogenic
• Chlorate: produce gastritis, a late toxic nephritis, hemolysis,
methemoglobinemia, hemoglobinuria, and acute renal failure

21. 21
Bromate Regulatory History
• 1998 – U.S. EPA, Stage I disinfectants/disinfection by-
products (D/DBP) rule
• MCL 10 µg/L bromate
• MCL Goal (MCLG) of zero
• 1998 – European Union Directive
• 10 µg/L bromate by 2008
• 2006 – U.S. EPA, Stage II D/DBP Rule leaves MCL at
10 µg/L bromate
• Maximum Contamination Level (MCL)
• Chlorite: 1 mg/L (ppm)
• Chlorate: 500 µg/L (ppb)
• Bromate: Most toxic, lowest allowed level, 5 to 10 µg/L (ppb)

22. 22
Bromate Method Summary
IC Technique
EPA
Method
Dionex IonPac
Columns
Eluent
Thermo
Scientific
Dionex
Application
MDL
(ppb)
Suppressed Cond.
300.0
(B)
Dionex IonPac AS9-HC or
Dionex IonPac AS23
Dionex IonPac AS19
Carbonate
Hydroxide
AN167,
AN184
CD
5.0, 1.63
0.32
Suppressed Cond. 300.1
Dionex IonPac AS9-HC or
Dionex IonPac AS23
Dionex IonPac AS19
Carbonate
Hydroxide
AN167,
AN184
5.0, 1.63
0.32
2D-IC Suppressed
Cond.
302.0
4 mm Dionex IonPac
AS19 to 2 mm Dionex
IonPac AS24
4 mm Dionex IonPac
AS19 to 0.4 mm Dionex
IonPac AS20
Hydroxide
Hydroxide
AN187
---
0.036,
~ 0.004
Suppressed Cond. +
Postcolumn ODA
317.0
Dionex IonPac AS9-HC
Dionex IonPac AS19
Carbonate
Hydroxide
AN168
UV/vis
0.14
Suppressed Cond. +
Postcolumn acidified KI
326.1
Dionex IonPac AS9-HC
Dionex IonPac AS19
Carbonate
Hydroxide
AN171
---
0.17
IC-ICP/MS 321.8
Thermo Scientific™
Dionex™ CarboPac PA100
Nitric Acid +
Ammonium
nitrate
MS
0.010

23. 23
0 5 10 15 20 25 30
–0.1
0.3
µS
Minutes
67 9 10
2
3
4 5 8 11
1
–50
500
µS
0 5 10 15 20 25 30
Minutes
11
4
81 67 95
Determination of Trace Concentrations of Bromate
Using Prepared Eluents (Isocratic)
Columns: Dionex IonPac AG23, Dionex IonPac
AS23, 4 mm
Eluents: 4.5 mM Sodium carbonate/
0.8 mM Sodium bicarbonate
Temperature:30 C
Flow Rate: 1.0 mL/min
Inj. Volume: 200 µL
Detection: Suppressed conductivity,
Dionex ASRS ULTRA II, 4 mm,
AutoSuppression,
external water mode
Peaks: 1. Fluoride 1.0 mg/L (ppm)
2. Chlorite 0.01
3. Bromate 0.005
4. Chloride 50
5. Nitrite 0.1
6. Chlorate 0.01
7. Bromide 0.01
8. Nitrate 10
9. Carbonate 50
10. Phosphate 0.1
11. Sulfate 50

24. 24
Determination of Bromate in Drinking Water Using
Reagent-Free Eluent Generation (Gradient)
Column: Dionex IonPac AS19 set, 4  250 mm
Eluent Source: Dionex EGC III KOH cartridge
Gradient: Potassium hydroxide:
10 mM from 0 to 10 min,
10–45 mM from 10 to 25 min
Flow Rate: 1.0 mL/min
Column Temp.:30 C
Suppressor: Thermo Scientific™ Dionex™ ASRS
300 Anion Self-Regenerating
Suppressor, 4 mm, external water
mode
Injection Vol.: 500 µL
Peaks: 1. Fluoride 1.0 mg/L
2. Formate –
3. Chlorite 0.005
4. Bromate 0.005
5. Chloride 50
6 Nitrite 0.005
7. Chlorate 0.005
8. Bromide 0.005
9. Nitrate 10
10. Carbonate 25
11. Sulfate 50
12. Phosphate 0.2MDL = SD x ts (n = 7), ts = 3.14
Minutes
-0.035
0.350
0 5 10 15 20 25 30
µS
6
9
10,11
12
1
5
7
8
3
4
2
Bromate MDL = 0.2 µg/L

25. 25
Bromate in Simulated Drinking Water Using Eluent
Generation, 4 µm Particle Column, and HPIC System
System: Dionex ICS-5000+ HPIC system
Column: Dionex IonPac AG19-4µm/
Dionex IonPac AS19-4µm
(4  250 mm)
Eluent : 10 mM KOH from 0 to 10 min,
10–45 mM KOH from 10 to 25 min
Eluent Source: Dionex EGC 500 KOH Cartridge
Flow Rate: 1.0 mL/min
Inj. Volume: 200 µL
Temperature: 30 ˚C
Detection: Suppressed Conductivity,
Dionex AERS 500 Suppressor,
4 mm, AutoSuppression, recycle
mode
Sample: Simulated Drinking Water
Peaks: 1. Fluoride 1.0 mg/L
2. Chlorite 0.005
3. Bromate 0.005
4. Chloride 50.0
5. Nitrite 0.005
6. Chlorate 0.005
7. Bromide 0.005
8. Nitrate 10.0
9. Carbonate 25.0
10. Sulfate 50.0
11. Phosphate 0.20
-0.2
0
0.5
µS
Minutes
1
23
4
5 6 7
8 9 10 11
0 8 16 24 32
-50
500
µS
Minutes
1 23
4
5 6 7
8
9
10
11

26. 26
Large Loop Injection of Anions in Municipal Drinking
Water Spiked with Surrogate Anion
0 8 16 24 32
-0.2
2
µS
Minutes
1
2
3
4
5
67 8
9
10
11
12
13 14
15
16
0 8 16 24 32-10
80
µS
Minutes
1
2 34
5
67 8 9 10 11 12 13
14
15 16
System: Dionex ICS-5000+ HPIC System
Column: Dionex IonPac AG19-4µm/
Dionex IonPac AS19-4µm (2  250 mm)
Gradient: 10 mM KOH from 0 to 13 min,
10–45 mM KOH from 13 to 28 min
Eluent Source: Dionex EGC 500 KOH Cartridge
Flow Rate: 0.25 mL/min
Inj. Volume: 50 µL
Temperature: 30 ˚C
Detection: Suppressed Conductivity,
Dionex AERS 300 Suppressor
AutoSuppression, recycle mode
Sample: Spiked with 1 ppm trichloroacetate
Peaks: 1. Fluoride 0.736 mg/L
2. Acetate 0.033
3. Formate 0.026
4. Chlorite 0.009
5. Chloride 5.94
6. Unknown ---
7. Nitrite 0.009
8. Unknown ---
9. Chlorate 0.110
10. Bromide 0.004
11. Nitrate 0.140
12. Trichloroacetate 0.993
13. Carbonate ---
14. Sulfate 2.70
15. Oxalate 0.029
16. Phosphate 0.059

27. 27
Perchlorate

28. 28
Perchlorate Background
• Perchlorate (ClO4
-)
• Strong oxidizing agent
• Stable in the environment as a Persistent Contaminant
• Naturally occurring -- nitrate minerals in Peru
• Manmade sources:
• Solid propellant –rockets, fireworks, and missiles
• Production of explosives, munitions, road flares, matches
• Hazardous waste

29. 29
Perchlorate Found in Concentrations > 1 ppb
• Drinking and ground water, > 30 states
• Aquifers associated with
disposal sites
• Lake Mead (NV)
• Colorado River (NV, CA, AZ)
• CA: Los Angeles, San Bernadino
counties
• Crops irrigated by contaminated water
• Other foods (e.g., milk)
http://www.epa.gov/ncea/perchlorate/references/documents/ref008.pdf

30. 30
Perchlorate Health Issues*
• Interferes with thyroid hormone production and
metabolism regulation. May cause tumors
• Interferes with neurological development of fetus and
newborn
• Behavior changes, delayed development, decreased learning
capability
• Regulated under Safe Drinking Water Act (2011)
• Maximum Contamination Level of 6 µg/L (ppb) by 2013
• Promulgated to the states
• MA (2 µg/L); CA (6 to 1 µg/L)
• Other states have health screening limits of 4 to 51 µg/L
U.S. EPA website (www.epa.gov)

31. 31
Perchlorate EPA Method Summary
Technique EPA
Dionex
Columns
Application
MDL
(Water)
(ppb)
LCMRL
(ppb)
IC Suppressed Conductivity
314.0
9058
Dionex IonPac AS16 or
Dionex IonPac AS20
AU 148, AU 145
AN 144
0.5 na
IC-Suppressed Conductivity
Matrix Rinse-Elimination
Primary and Confirmation
314.1
Dionex IonPac AS16 + Dionex
IonPac AS20
AN 176
AN 356
0.030 0.150
2-D IC Suppressed
Conductivity
Matrix Rinse-Elimination
Primary and Confirmation 314.2
2 mm to 0.4 mm: Dionex
IonPac AS20 + Dionex IonPac
AS16 with Thermo Scientific™
Dionex™ IonSwift™ MAC-200
AN 1024 0.005
--
4 mm to 2 mm: Dionex IonPac
AS16 + Dionex IonPac AS20
with Dionex IonPac TAC-ULPC AN 178
0.06 0.19
IC-MS
SIM 99 and 101 m/z
332.0
6860
Dionex IonPac AS16 or Dionex
IonPac AS20
AN 151
Applications
Guide
0.010 0.050
IC-MS/MS
SRM 99/83 and 101/85 m/z
332.0
6860
Dionex IonPac AS16 or Dionex
IonPac AS20
Poster
Applications
Guide
0.005 0.020
LC-MS
SIM 99 and 101 m/z
6850 Dionex IonPac AS21 0.010 0.050
LC-MS/MS
SRM 99/83 and 101/85 m/z
331.0
6850
Dionex IonPac AS21 0.005 0.020
Notes: SIM = Selected Ion Monitoring
SRM = Selective Reaction Monitoring
LCMRL = Lowest Concentration Method Reporting Limit
22481

32. 32
1 µg/L Perchlorate in Deionized Water
Columns: Dionex IonPac AG16, Dionex
IonPac AS16, 4 mm
Eluent: 65 mM KOH
Eluent Source: Dionex EGC III KOH cartridge
Temperature: 30 C
Flow Rate: 1.2 mL/min
Inj.Volume: 1000 µL
Detection: Suppressed conductivity,
Dionex ASRS ULTRA II
suppressor, external water mode
Peaks: 1. Perchlorate 1 µg/L

33. 33
0.5 µg/L Perchlorate in Deionized Water
22481
Columns: Dionex IonPac AG16, Dionex
IonPac AS16, 4 mm
Eluent: 65 mM KOH
Eluent Source: Dionex EGC III KOH cartridge
Temperature: 30 C
Flow Rate: 1.2 mL/min
Inj.Volume: 1000 µL
Detection: Suppressed conductivity,
Dionex ASRS ULTRA II
suppressor, external water mode
Peaks: 1. Perchlorate 0.5 µg/L (ppb)

34. 34
5 µg/L Perchlorate in 200 mg/L each of Chloride,
Sulfate, and Carbonate
22481
Columns: Dionex IonPac AG16, Dionex
IonPac AS16, 4 mm
Eluent: 65 mM KOH
Eluent Source: Dionex EGC III KOH cartridge
Temperature: 30 C
Flow Rate: 1.2 mL/min
Inj. Volume: 1000 µL
Detection: Suppressed conductivity,
Dionex ASRS ULTRA II
suppressor, external water mode
Peaks: 1. Perchlorate 5 µg/L

35. 35
Chromate
(Hexavalent Chromium)

36. 36
Cr-proposed ruling 10 ppb 2013
• Sources: industrial, minerals
• Hexavalent Chromium (Cr(VI)) is potentially mutagenic and
carcinogenic
• Mixed regulations
• Federal MCL total chromium 100 ppb
• 2013 EPA Ruled that Cr VI is an unregulated contaminant
• Assessing contamination levels and risk assessment
• State of California: Proposed MCL of 5 ppb Cr(VI), MCLG of 0.02 ppb

37. 37
IC Technique
EPA
Method
Dionex IonPac
Columns
Eluent
Thermo
Scientific
Dionex
Application
MDL
(ppb)
LCMRL
(ppb)
Postcolumn
Diphenylcarbazide /
methanol / sulfuric acid
218.6
4 mm Dionex
IonPac
CG5A/Dionex
IonPac CS5A
+ 375 µL reaction
coil
PDCA/
phosphate
buffer, sodium
iodide,
ammonium
acetate, lithium
hydroxide
AU165
Cr (III)
Cr(VI)
Same
218.6
Modified
4 mm Dionex
IonPac NG1/Dionex
IonPac AS7 +
750 µL reaction coil
NH4SO4
NH4OH
AU144 0.02
Same 218.7
2 mm Dionex
IonPac AG7/Dionex
IonPac AS7 + 125
µL reaction coil
NH4SO4
NH4OH AU179 0.001 0.019
2D-IC Suppressed Cond.
4 mm Dionex
IonPac AS24 to
0.4 mm Dionex
IonPac AS20 +
Dionex IonSwift
MAC- 200
Hydroxide poster
CD
0.005
IC-ICP/MS with Digestion 3060
Chromate Method Summary

38. 38
Determination of Hexavalent Chromium
Using Optimized EPA Method 218.6
Columns: Dionex IonPac NG1, Dionex
IonPac AS7, 4 mm
Eluent: 250 mM (NH4)2SO4
100 mM NH4OH
Flow Rate: 1.0 mL/min
Inj. Volume: 1000 µL
Postcolumn Reagent: 2 mM Diphenylcarbizide
10% CH3OH
1N H2SO4
0.33 mL/min
Reaction Coil: 750 µL
Detector: UV-Vis (530 nm)
Sample: 1.0 µg/L Cr(VI)
0 2 4 6 8
Minutes
0
2
Cr(VI)
mAU

39. 39
Determination of Cr(VI) in Drinking Water
Using Optimized EPA Method 218.6
0
0 2 4 6 8
Cr(VI)
mAU
Minutes
Cr(VI)
Columns: Dionex IonPac NG1, Dionex
IonPac AS7, 4 mm
Eluent: 250 mM (NH4)2SO4
100 mM NH4OH
Flow Rate: 1.0 mL/min
Inj. Volume: 1000 µL
Postcolumn Reagent:2 mM Diphenylcarbizide
10% CH3OH
1N H2SO4
0.33 mL/min
Reaction Coil: 750 µL
Detector: UV-Vis (530 nm)
Sample: A: Sunnyvale municipal
drinking water
B: Sample A + 0.2 µg/L Cr(VI)
Peak: A B
Cr(VI)) 0.055 0.245 µg/L
B
A
2

40. 40
Organic Contaminants

41. 41
Importance of Sample Preparation
“Eighty percent of the variance in an assay usually arises
from the sample prep.”
Stevenson, R. The World of Separation Science - Pittcon® 98 - Part 3 -
Sample Prep - The Place to Make a Difference. Am. Lab. 1998 30 (14).

42. 42
Dionex SolEx Solid-Phase Extraction Cartridges
• Cartridges designed for fast, and easy preconcentration of contaminants prior to
analysis
• Offered in a variety of chemistries and sizes to fit your sample extraction needs
• Thermo Scientific™ Dionex™ SolEx SPE Cartridges
• Silica-Based SPE Cartridges
Dionex SolEx C8 Cartridge
Dionex SolEx C18 Cartridge
Dionex SolEx C8-Clean (Phthalate-Free) Cartridge
Dionex SolEx C18-Clean (Phthalate-Free) Cartridge
Dionex SolEx C18-525 Cartridge
Dionex SolEx Unbonded Silica Cartridge
• Carbon-Based SPE Cartridges
Dionex SolEx Activated Carbon Cartridge
Dionex SolEx Graphatized Carbon Cartridge
• New Polymeric-Based Cartridges
Dionex SolEx HRPHS Cartridge
Dionex SolEx SAX Cartridge
Dionex SolEx SCX Cartridge
Dionex SolEx WAX Cartridge
Dionex SolEx WCX Cartridge

43. 43
Dionex SolEx SPE Cartridge Product Line
with Associated Chemistries and Recommended Applications
Cartridge Sorbent Media Example Applications
HRPHS
Divinylbenzene (DVB)
/Polyvinylpyrrolidone
Concentration: hydrophobic targets such as
triclosan polyphenols, azo compounds
SAX
DVB-Quaternary
Ammonium
Concentration: weak anions such as carboxylates
SCX DVB-Sulfonate Concentration: weak cations such as amines
WAX DVB-Amine
Concentration: strong inorganic and organic anions,
sulfonates, and sulfates
WCX DVB-Carboxylate
Concentration: strong inorganic and organic cations,
quaternary ammonium ions
Polymer-Based SPE Cartridges
Uniquely Grafted Phases to Isolate and Concentrate

44. 44
EPA Method Analytes Extraction/Analytical Methods Chemistry Used
8330 Nitroaromatics and Nitramines--explosives SPE and LC HRPHS
506 Pthalate and Adipate Esters SPE and GC/PID C18
507 N and P-Containing Pesticides SPE and GC C18
508.1 Chlorinated Pesticides, Herbicides & Organohallides SPE and GC-ECD C18
521 Nitrosamines SPE and GC/MS/MS Carbon
522 Dioxane SPE and GC/MS Carbon
525.2 Semivolatile Organic Compounds (SVOC) SPE and GC/MS C18
525.3 Semivolatile Organic Compounds (SVOC) SPE and GC/MS C18
526 Semivolatile Organic in Drinking Water SPE and GC/MS HRPHS
527 Flame Retardants SPE and GC/MS HRPHS
528 Phenols SPE and GC/MS HRPHS
529 Explosives SPE and GC/MS HRPHS
532 Phenylurea SPE and HPLC C18
535 Acetic Herbicides SPE and LC/MS/MS Graphitized Carbon
548 Endothal SPE and GC/ECD C18
539 Hormones SPE and LC/MS/MS HRPHS
553 Benzidines and N-Containing Pesticides SPE and LC/MS C18
554 Carbonyl Compounds SPE and LC C18
U.S. EPA SPE 500 Series Methods

45. 45
Explosives (EPA Method 8330)
• Munitions disposed through combustion
• Soil and groundwater contaminated
• Target compounds are carcinogens, mutagens
Analytical
Column: Thermo Scientific™ Acclaim™
Explosives E2, 3 µm,
3.0  250 mm
Mobile Phase: 48/52 v/v MeOH/H2O
Temperature: 25 C
Flow Rate: 0.3 mL/min
Inj. Volume: 5 µL
Detection: UV at 254 nm
Samples: EPA 8330 Mix, 2 ppm each)
Peaks: 1. HMX
2. RDX
3. 1,3,5-trinitrobenzene
4. 1,3-Dinitrobenzene
5. Nitrobenenze
6. 2,4,6-trinitrobenzene
7. Tetryl
8. 2,6-Dinitrotoluene
9. 2,4-Dinitrotoluene
10. 2-Nitrotoluene
11. 4-Nitrotoluene
12. 3-Nitrotoluene
13. 4-Amino-2,6-Dinitrotoluene
14. 2-Amino-4,6-Dinitrotoluene
0 5 10 15 20 25 30 35 40 45 50
-2
0
1.3
2.5
3.8
5.0
6.3
8.0
Absorbance[mAU]
Minutes
1
2
3
4
5
6
7 8
9
10
11 12
13
14
Sample Prep
Instrument: Thermo Scientific™ Dionex™
AutoTrace™ 280 (6 mL) cartridge
Cartridge: 6 mL, 500 mg Resin HRPHS
Eluent: Acetonitrile
Flow Rate: 10 mL/min
Sample: 100 mL, 2 ppb 14 Explosive Standard

46. 46
Hormones in Drinking Water (EPA Method 539)
• Hormones in pharmaceuticals end up in the sewage
• Hormones from livestock waste into drinking water
• Endocrine disruptors
7
6.18 7.00 8.0 9.0 10.0 10.7
6.7
10
14
18
22
1
2
3
4
5 6
Minutes
Sample Prep
Instrument: Dionex AutoTrace 280 for 6 mL Cartridge
Cartridge: 6 mL, 200 mg of Resin HRPHS
Sample: 10 mL, 5 mg/L Harmone Standard
Flow Rate: 5 mL/min
Elution: Acetonitrile
Analytical
Column: Acclaim RSLC 120 C18, 2.1 × 150 mm
Mobile phase: A: Water
B: Acetonitrile
Gradient : 10–54% B (0–4 min); 54% B (4–12 min);
100% B (12–16 min); 10% B (16–20 min)
Flow Rate: 0.20 mL/min
Inj. Volume: 2 µL
Column Temp.:20 C
Detection: UV, 214 nm
Peaks: 1. Estriol
2. Estradiol
3. Testosterone
4.Ethynylestradiol
5. Equilin
6. Estrone
7. Androstenedione

47. 47
Conclusion
• Dionex Ion Chromatography methods have provided easy
and innovative regulatory methods
• Many of these methods were developed with the EPA
• Methods using manually prepared eluents can be used on
any Dionex IC system and take advantage of new
advancements in column technology
• Reagent-Free Eluent Generation provides greater sensitivity,
method flexibility, and ease-of-use
• New innovations have added to analytical capabilities:
• Advancements in column chemistry
• 4 µm particle columns and high-pressure capable systems (HPIC)
• Capillary IC
• Dionex AutoTrace applications automate sample preparation

48. 48
Thank You!