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
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
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
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
Data Management
ConductivityDetector
High-Pressure Non-Metallic Pump
Eluent Generator
(OH– or H+)
Waste
Sample Inject(Autosampler) Recycle
Mode
Detection
Water/Eluent
CR-TC
CellEffluent
Electrolytic Eluent
Suppressor
Separation Column
Ion Chromatography System
RFIC, Innovation and Ease-of-Use Behind the Curtain
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
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 0 400
5
µS
Minutes
Applications • Anions in environmental waters
• Organic acids in foods and beverages
• Amines in chemical process solutions
High Resolution using theDionex IonPac CS19-4µm
8
Advantages of Suppressed Conductivity
Time
F -Cl - SO4
2-
F - Cl - SO42-
Time
-µS
µS
Without Suppression
With Suppression
Eluent (KOH)
Sample F-, Cl-, SO42-
Ion-ExchangeSeparation Column
Anion Electrolytically RegeneratingSuppressor
in H2O
KF, KCI, K2SO4
in KOH
Injection Valve
Counter ions
HF, HCI, H2SO4
9
KOH, H2
Dionex Electrolytically Regenerated Suppressors
WasteWasteAnode
Detector
H+ + O2 H2 + OH–
H2O H2O
H2O H2O
Cation- Exchange
Membranes
OH–
CathodeK+, 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
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
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 Diphenylcarbizide10% CH3OH1N 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
2Cr(VI)
mAU
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
0 2 4 6 8Minutes
0
µS
10
10
1
23 4 5
6
7
1993 EPA Method 300.0 (A): Dionex IonPac AS4A Column
Column: Dionex IonPac AG4A-SC, Dionex IonPac AS4A-SC, 4 250 mmEluent: 1.7 mM sodium bicarbonate/
1.8 mM sodium carbonateFlow Rate: 2.0 mL/minInjection: 50 µLDetection: Suppressed conductivity,
Thermo Scientific™ Dionex™ ASRS™ ULTRA Suppressor, recycle mode
Peaks: 1. Fluoride 2 mg/L (ppm)2. Chloride 33. Nitrite 54. Bromide 105. Nitrate 106. Phosphate 157. Sulfate 15
14
Column: Dionex IonPac AG22, Dionex IonPac AS22, 4 250 mmEluent: 4.5 mM sodium carbonate/
1.4 mM sodium bicarbonateFlow Rate: 1.2 mL/minInjection: 5 µLDetection: Suppressed conductivity,
AutoSuppression , Thermo Scientific™ Dionex™ AERS™ 500 Anion Electrolytically
Regenerated Suppressor, 31 mA,recycle mode
Peaks: 1. Fluoride 5 mg/L2. Acetate 203. Chloride 104. Nitrite 155. Bromide 256. Nitrate 257. Phosphate 408. Sulfate 30
Minutes
1
2
3
45
6
7
8
0 2 4 6 10 128
-1
µS
4
Improved Separation of Eight Anions
15
Minutes
2
4 5
South San Jose Drinking Water
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/minInjection: 5 µLDetection: Suppressed conductivity,
Dionex AERS 500 suppressor, 31 mA, recycle mode
Peaks: 1. Fluoride 0.20 mg/L2. Chloride 37.73. Nitrate 5.054. Carbonate ---5. Sulfate 37.3
1
3
-2
0 2 4 6 10 128
µS
20
16
Determination of Anions in Surface Water Samples
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/minInjection: 5 µLDetection: Suppressed conductivity,
Dionex AERS 500 Suppressor, 31 mA, recycle mode
Sample Prep.: Filtered, 0.2 µmSamples: A: White Water River
(Palm Springs) B: Lake Tahoe
Peaks:A B
1. Fluoride 0.23 mg/L 0.09 mg/L2. Chloride 49.3 2.23. Nitrate 19.3 --- 4. Phosphate 1.9 --- 5. Sulfate 82.0 1.8
Minutes
1 3
-20 2 4 6 10 128
µS5
20
2
Minutes
15
2
-0.40 2 4 6 10 128
µS
5
B
A
4
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Reagent-Free High Pressure IC for 6 min Run Times
System: Dionex ICS-5000+ Reagent-FreeHPIC system
Column: Dionex IonPac AG18-4µm/Dionex IonPac AS18-4µm, (2 × 250 mm)
Eluent: 23 mM KOHEluent Source: Thermo Scientific Dionex EGC 500
KOH cartridgeFlow Rate: A: 0.25, B: 0.31, C: 0.38 mL/minPressure: A: 2400, B: 3000, C: 3500 psiInj. Volume: 2.5 µLTemperature: 30 CDetection: Suppressed Conductivity,
Dionex ASRS 300 suppressor, AutoSuppression,recycle mode
Peaks: 1. Fluoride 0.5 mg/L2. Chlorite 53. Chloride 34. Nitrite 55. Carbonate 206. Bromide 107. Sulfate 108. Nitrite 109. Chlorate 10
16
1
2
34
5
6
7
8
9
0 2 4 6 8 10
0
µS
Minutes
1
2
34
5
6
7
89
1
2
34
5
6
7
89
A
B
C
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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-FreeHPIC 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 CartridgeFlow Rate: 0.25 mL/minInj. Volume: 2.5 µLTemperature: 30 ˚CDetection: Suppressed Conductivity,
Dionex AERS 500 suppressor,2 mm, AutoSuppression, recycle mode
Peaks: 1. Chloride 800 mg/L2. Nitrite 0.13. Nitrate0.14. Carbonate ---5. Sulfate 1006. Phosphate 100
0 8 16 24 32-0.2
2
µS
1
23
5 6
4
0 8 16 24 32-200
1,800
µS
Minutes
1
2 3
5
64
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Oxyhalides
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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
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
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 AS23Dionex IonPac AS19
CarbonateHydroxide
AN167, AN184
CD
5.0, 1.630.32
Suppressed Cond. 300.1Dionex IonPac AS9-HC or
Dionex IonPac AS23Dionex IonPac AS19
CarbonateHydroxide
AN167, AN184
5.0, 1.630.32
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
HydroxideHydroxide
AN187---
0.036,~ 0.004
Suppressed Cond. + Postcolumn ODA
317.0 Dionex IonPac AS9-HCDionex IonPac AS19
CarbonateHydroxide AN168
UV/vis
0.14
Suppressed Cond. + Postcolumn acidified KI
326.1 Dionex IonPac AS9-HCDionex 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
0 5 10 15 20 25 30–0.1
0.3
µS
Minutes
67 9 1023
4 5 8 11
1
–50
500
µS
0 5 10 15 20 25 30Minutes
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 0.013. Bromate 0.0054. Chloride 505. Nitrite 0.16. Chlorate 0.017. Bromide 0.018. Nitrate 109. Carbonate 50
10. Phosphate 0.111. Sulfate 50
24
Determination of Bromate in Drinking Water Using Reagent-Free Eluent Generation (Gradient)
Column: Dionex IonPac AS19 set, 4 250 mmEluent 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/minColumn Temp.:30 C Suppressor: Thermo Scientific™ Dionex™ ASRS
300 Anion Self-Regenerating Suppressor, 4 mm, external water modeInjection Vol.: 500 µL
Peaks: 1. Fluoride 1.0 mg/L 2. Formate –3. Chlorite 0.0054. Bromate 0.0055. Chloride 506 Nitrite 0.0057. Chlorate 0.0058. Bromide 0.0059. Nitrate 10
10. Carbonate 2511. Sulfate 5012. Phosphate 0.2
MDL = 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
121
5
78
34
2
Bromate MDL = 0.2 µg/L
25
Bromate in Simulated Drinking Water Using Eluent Generation, 4 µm Particle Column, and HPIC System
System: Dionex ICS-5000+ HPIC systemColumn: 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 minEluent Source: Dionex EGC 500 KOH CartridgeFlow Rate: 1.0 mL/minInj. Volume: 200 µLTemperature: 30 ˚CDetection: Suppressed Conductivity,
Dionex AERS 500 Suppressor, 4 mm, AutoSuppression, recycle mode
Sample: Simulated Drinking Water
Peaks: 1. Fluoride 1.0 mg/L2. Chlorite
0.005
3. Bromate
0.005
4. Chloride
50.0
5. Nitrite
0.0056. Chlorate
0.0057. Bromide
0.0058. Nitrate
10.0
9. Carbonate
25.010. Sulfate 50.011. 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 78
9
10
11
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
23
4
5
67 8
9
10
11
12
13 14
1516
0 8 16 24 32-10
80
µS
Minutes
1
2 3 4
5
67 8 9 10 11 12 13
14
15 16
System: Dionex ICS-5000+ HPIC SystemColumn: 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 minEluent Source: Dionex EGC 500 KOH CartridgeFlow Rate: 0.25 mL/minInj. Volume: 50 µLTemperature: 30 ˚CDetection: Suppressed Conductivity,
Dionex AERS 300 SuppressorAutoSuppression, recycle mode
Sample: Spiked with 1 ppm trichloroacetate
Peaks: 1. Fluoride0.736 mg/L
2. Acetate0.0333. Formate 0.0264. Chlorite 0.009
5. Chloride5.946. Unknown---7. Nitrite0.0098. Unknown ---9. Chlorate 0.110
10. Bromide0.004
11. Nitrate0.140
12. Trichloroacetate0.993
13. Carbonate ---14. Sulfate 2.7015. Oxalate 0.02916. Phosphate 0.059
27
Perchlorate
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
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
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
Perchlorate EPA Method Summary
Technique EPA Dionex
ColumnsApplication
MDL (Water) (ppb)
LCMRL(ppb)
IC Suppressed Conductivity 314.09058
Dionex IonPac AS16 or Dionex IonPac AS20
AU 148, AU 145AN 144 0.5 na
IC-Suppressed Conductivity Matrix Rinse-Elimination Primary and Confirmation
314.1 Dionex IonPac AS16 + Dionex IonPac AS20
AN 176AN 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 1780.06 0.19
IC-MS SIM 99 and 101 m/z
332.06860
Dionex IonPac AS16 or Dionex IonPac AS20
AN 151Applications
Guide0.010 0.050
IC-MS/MS SRM 99/83 and 101/85 m/z
332.06860
Dionex IonPac AS16 or Dionex IonPac AS20
PosterApplications
Guide0.005 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
331.06850 Dionex IonPac AS21 0.005 0.020
Notes: SIM = Selected Ion MonitoringSRM = Selective Reaction Monitoring
LCMRL = Lowest Concentration Method Reporting Limit
22481
32
1 µg/L Perchlorate in Deionized Water
Columns: Dionex IonPac AG16, Dionex IonPac AS16, 4 mmEluent: 65 mM KOH Eluent Source: Dionex EGC III KOH cartridgeTemperature: 30 C Flow Rate: 1.2 mL/minInj.Volume: 1000 µL Detection: Suppressed conductivity,
Dionex ASRS ULTRA II suppressor, external water mode
Peaks: 1. Perchlorate 1 µg/L
33
0.5 µg/L Perchlorate in Deionized Water
22481
Columns: Dionex IonPac AG16, Dionex IonPac AS16, 4 mmEluent: 65 mM KOH Eluent Source: Dionex EGC III KOH cartridgeTemperature: 30 C Flow Rate: 1.2 mL/minInj.Volume: 1000 µL Detection: Suppressed conductivity,
Dionex ASRS ULTRA II suppressor, external water mode
Peaks: 1. Perchlorate 0.5 µg/L (ppb)
34
5 µg/L Perchlorate in 200 mg/L each of Chloride, Sulfate, and Carbonate
22481
Columns: Dionex IonPac AG16, Dionex IonPac AS16, 4 mmEluent: 65 mM KOH Eluent Source: Dionex EGC III KOH cartridgeTemperature: 30 C Flow Rate: 1.2 mL/minInj. Volume: 1000 µL Detection: Suppressed conductivity,
Dionex ASRS ULTRA II suppressor, external water mode
Peaks: 1. Perchlorate 5 µg/L
35
Chromate(Hexavalent Chromium)
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
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)
Same218.6
Modified
4 mm Dionex IonPac NG1/Dionex
IonPac AS7 + 750 µL reaction coil
NH4SO4
NH4OHAU144 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 CD0.005
IC-ICP/MS with Digestion 3060
Chromate Method Summary
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 Diphenylcarbizide10% CH3OH1N 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
2Cr(VI)
mAU
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% CH3OH1N 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
Organic Contaminants
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
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 CartridgeDionex SolEx C18 CartridgeDionex SolEx C8-Clean (Phthalate-Free) CartridgeDionex SolEx C18-Clean (Phthalate-Free) CartridgeDionex SolEx C18-525 CartridgeDionex SolEx Unbonded Silica Cartridge
• Carbon-Based SPE CartridgesDionex SolEx Activated Carbon CartridgeDionex SolEx Graphatized Carbon Cartridge
• New Polymeric-Based CartridgesDionex SolEx HRPHS CartridgeDionex SolEx SAX CartridgeDionex SolEx SCX CartridgeDionex SolEx WAX CartridgeDionex SolEx WCX Cartridge
43
Dionex SolEx SPE Cartridge Product Line with Associated Chemistries and Recommended Applications
Cartridge Sorbent Media Example Applications
HRPHSDivinylbenzene (DVB) /Polyvinylpyrrolidone
Concentration: hydrophobic targets such as triclosan polyphenols, azo compounds
SAXDVB-Quaternary
AmmoniumConcentration: weak anions such as carboxylates
SCX DVB-Sulfonate Concentration: weak cations such as amines
WAX DVB-AmineConcentration: strong inorganic and organic anions,
sulfonates, and sulfates
WCX DVB-CarboxylateConcentration: strong inorganic and organic cations,
quaternary ammonium ions
Polymer-Based SPE CartridgesNEW!
Uniquely Grafted Phases to Isolate and Concentrate
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
Explosives (EPA Method 8330)
• Munitions disposed through combustion• Soil and groundwater contaminated• Target compounds are carcinogens, mutagens
AnalyticalColumn: Thermo Scientific™ Acclaim™
Explosives E2, 3 µm, 3.0 250 mm
Mobile Phase: 48/52 v/v MeOH/H2OTemperature: 25 CFlow Rate: 0.3 mL/minInj. Volume: 5 µLDetection: UV at 254 nmSamples: EPA 8330 Mix, 2 ppm each)Peaks: 1. HMX
2. RDX3. 1,3,5-trinitrobenzene4. 1,3-Dinitrobenzene5. Nitrobenenze6. 2,4,6-trinitrobenzene7. Tetryl8. 2,6-Dinitrotoluene9. 2,4-Dinitrotoluene
10. 2-Nitrotoluene11. 4-Nitrotoluene12. 3-Nitrotoluene13. 4-Amino-2,6-Dinitrotoluene14. 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
Ab
sorb
ance
[m
AU
]
Minutes
1
2
3
4
5
6
7 8
9
1011 12
13
14
Sample PrepInstrument: Thermo Scientific™ Dionex™
AutoTrace™ 280 (6 mL) cartridgeCartridge: 6 mL, 500 mg Resin HRPHSEluent: AcetonitrileFlow Rate: 10 mL/minSample: 100 mL, 2 ppb 14 Explosive Standard
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
45 6
Minutes
Sample PrepInstrument: Dionex AutoTrace 280 for 6 mL CartridgeCartridge: 6 mL, 200 mg of Resin HRPHSSample: 10 mL, 5 mg/L Harmone Standard Flow Rate: 5 mL/minElution: Acetonitrile
Analytical Column: Acclaim RSLC 120 C18, 2.1 × 150 mmMobile phase: A: Water
B: AcetonitrileGradient : 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/minInj. Volume: 2 µLColumn Temp.:20 C Detection: UV, 214 nm
Peaks: 1. Estriol2. Estradiol
3. Testosterone4.Ethynylestradiol5. Equilin6. Estrone7.
Androstenedione
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
Thank You!