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!