innovations in ion chromatography for the analysis of ... rm-mi - abballe... · innovations in ion...

Innovations in Ion Chromatography

for the analysis of difficult analytes

and disinfection by products

TBDThermo Fisher ScientificThermo Fisher Scientific

Outline

• Introduction

• Innovations in Ion Chromatography

• Reagent Free Ion Chromatography• Reagent Free Ion Chromatography

• Capillary Ion Chromatography

• Examples

• Back pressure tolerance for PEEK systems for fast analysis

• Routine anion and cation analysis

• 2-D for sensitivity

• Bromate, perchlorate, haloacetic acids

• IC-MS/MS

Proprietary & Confidential2 Dionex Confidential

• IC-MS/MS

• Haloacetic acids, endothal, glyphosate, AMPA, ethanolamines

• Conclusions

INNOVATIONS IN IC –


INNOVATIONS IN IC –REAGENT FREE ION CHROMATOGRAPHY (RFIC)

Evolution of Ion Chromatography

1975 1991 1998 2003 2010


IC Cube

Performance – Ease of Use – Reliability

Reagent Free IC for Environmental Analysis

• What has been proven:

• RFIC™ using hydroxide eluents is more sensitive.

• Hydroxide eluents are suppressed to water.

• Cation suppression more sensitive than non-suppressed!!

• Gradient separations using IonPac columns allow mono- to poly-valent

species separation in one run.

• RFIC provides ease-of-use

• Electrolytic eluent generation, suppression, and trap columns provide

ease-of-use.

• FAST!


• FAST!

• IC on Demand

• Ideal for hyphenated techniques

• Amenable to contaminants of emerging concern (CEC’s)

Hydroxide vs. Carbonate Eluents for Separation of Common Anions and DPBs in Mineral Water

Column: A) IonPac AS19B) IonPac AS23

Eluent: A. Hydroxide

B. Carbonate/bicarbonateDetection: Suppressed conductivity

A BPeaks 1. Fluoride µg/L

0.5

µS

1A 4

6

7

8 9 10 11

• Both eluents show excellent anion and

Peaks 1. Fluoride µg/L

2. Chlorite 8.8 11.33. Bromate 4.7 5.14. Chloride5. Nitrite 6. Chlorate 13.5 9.5

7. Bromide8. Nitrate9. Carbonate

10. Sulfate11. Orthophosphate

0.2

µS 23

0.7

µS

1

3

B 4

9

8

5

6

1110


• Both eluents show excellent anion and oxyhalide separation.

• Trace oxyhalides chlorite, bromate, and chlorate are well resolved.

• Hydroxide does not show the water dip

• Elution order of orthophosphate and sulfate are reversed

0 5 10 15 20 25 30

-0.1

2

3

5 6 7

Minutes

RFIC using Hydroxide is Sensitive!Hydroxide vs. Carbonate Eluents

AnalyteRange

(µg/L)Linearity (r2)

Retention Time

Precision

(%RSDb,c)

Peak Area

Precision

(%RSD)

MDL Standard

(µg/L)

MDL

Calculated

(µg/L)

IonPac AS19 – Hydroxide Eluent

Chlorite 2-50 0.9999 0.04 1.20 1.0 0.18

Bromate 1-25 0.9995 0.03 1.40 2.0 0.31

Chlorate 2-50 0.9999 0.01 0.54 1.0 0.28

IonPac AS23 – Carbonate/bicarbonate Eluent

Chlorite 10-50 0.9999 0.07 2.20 5.0 1.02


Bromate 5-25 0.9998 0.07 2.63 5.0 1.63

Chlorate 10-50 0.9998 0.11 2.48 9.0 2.05

a See Application Note 184 for conditionsb RSD = relative standard deviation, n = 7

c Quality control standard contained 10 ppb each of chlorite, chlorate, and bromide and 5 ppb bromate


INNOVATIONS IN IC – CAPILLARY IC

Parameter Analytical IC Capillary IC

Column diameter 4 mm 0.4 mm

The Dimension of Scale

Column diameter 4 mm 0.4 mm

Flow rate 1.0 mL/min 10 µL/min

Injection volume 25 µL 0.4 µL

Eluent consumption 43.2 L/month 0.432 L/month

EGC lifetime(@75 mmol/L)

28 days 18 months

Absolute detection limit 700 ppt 7 ppt


Absolute detection limit(with IC × IC)

700 ppt 7 ppt

The Most Important Values of Capillary IC

• “IC on Demand”

• Permanent availability of the system

• Higher laboratory productivity, because typical waiting times for equilibration are omitted

• Less calibration efforts• Less calibration efforts

• Isocratic and gradient elution due to RFIC

• Higher mass sensitivity

• High sensitivity with less sample volume

• 100-fold increase in absolute sensitivity in comparison to 4 mm systems

• IC x IC (2D IC) – detection limits in the ppt range with only 1 mLof sample


of sample

• Lower cost of ownership

• Lower eluent consumption, less waste

• 18 months lifetime of the EG cartridges

Reagent-Free IC (RFIC) Technology –A Prerequisite for Capillary IC

• Combination of three techniques

• Electrolytic eluent generation• Electrolytic eluent generation

• Electrolytic eluent purification

• Electrolytic eluent suppression

• All techniques depend on the electrolysis of water

Anode H2O 2 H+ + ½ O2 (g) + 2e–+OXIDATION


Anode H2O 2 H + ½ O2 (g) + 2e+

–REDUCTION

Cathode 2e– + 2H2O 2 OH– + H2 (g)

Advantages of Electrolytic Eluent Generationin Capillary IC Systems

• Feasible to construct eluent generators of very low dead volumes • Feasible to construct eluent generators of very low dead volumes

• Capable of providing high-fidelity gradient profiles at low µL/min flow rates through precise current and flow rate controls

• Practical and cost-effective to generate higher concentrations of eluents

• Ideal eluent delivery platform for both isocratic and gradient capillary ion chromatography


capillary ion chromatography

HIGHER BACK PRESSURE TOLERANCE OF


HIGHER BACK PRESSURE TOLERANCE OF CAPILLARY IC

Capillary IC with Higher Back Pressure Tolerance

• What is it?

• Continuous operation at 5000 psi (34.5 MPa) with an ICS-5000 capillary systemcapillary system

• Why is it important?

• Vendors and users are tending to systems tolerating a much higher back pressure to be able to use packing materials with smaller

particle diameter.

• Smaller particle diameter = higher chromatographic efficiency

• Higher chromatographic efficiency = faster separations without sacrificing resolution


sacrificing resolution

• (Smaller particle diameters , however, result in a much higher back

pressure)

The Challenge: Speed, Capacity, Resolution

Resolution High resolution sacrificing speed

High capacitysacrificing speed

Fast separationssacrificing resolution

or capacity


SpeedCapacity

Why Do We Need Faster Separations?

• Make laboratories more productive• Make laboratories more productive

• Save laboratories time and eluent

• Provide faster answers to analytical questions

• Improve LODs and LOQs in some cases

Faster separations are as accurate and precise as conventional methods!


as conventional methods!

16

Moving to Higher Sample Throughput in IC

• Two things were missing in ion chromatography:

• Ability to run fast chromatography

• Ability to perform high resolution ion chromatography

• The concepts for increasing sample throughput differ betweenLC and IC

• LC: UHPLC through the use of small particle size columns and the ability to run at higher pressures, higher temperature, and higher data collection

rates.


• IC: Use of conventional ion-exchange resins operated with higher linear velocities for simple samples or higher linear velocities on monolithic

supports.

• All currently available columns for Fast IC of inorganic anions and cations are only suitable for weakly contaminated samples!

Fast IC – Current Situation

and cations are only suitable for weakly contaminated samples!

• Identical selectivity in comparison to standard versions

• Shorter columns allow shorter analysis times due to higher flow rates

• Higher sample throughput

• Flow rates up to 3 mL/min (4 mm columns), 0.75 mL/min (2 mm columns) and 30 µL/min (0.4 mm columns)


columns) and 30 µL/min (0.4 mm columns)

• Standard anion/cation profiles in less than 5 min

• IonPac AS18-4µm fast column has the same selectivity asIonPac AS18

IonPac AS18-4µm Fast Anion Column

IonPac AS18

• Designed for common anions in a variety of sample matrices

• First commercially available 4 µm super-macroporous resin

• 4 µm particles allow higher flow rates with less peak dispersion

• High speed separation; as fast as IonPac AS18-Fast (150 mm)

• High efficiency peaks; as efficient as IonPac AS18 (250 mm)

• High resolution separations

• Supports high pressure IC


• Supports high pressure IC

• Can be operated up to 4000 psi

Comparison of IonPac AS18-4µm Fast and AS18-Fast Capillary Columns

Column: see chromatogramEluent: see chromatogram

2

µS1

4

6

3

2.0

AS18-Fast CapillaryEluent: 33 mmol/L KOH

Eluent: see chromatogramTemperature: 30 °CFlow rate: 30 µL/minInj. volume: 0.4 µLDetection: Suppressed conductivity,

AutoSuppression, recycle mode

Peaks: 1. Fluoride 0.2 mg/L2. Chloride 0.53. Nitrite 1.04. Sulfate 1.05. Bromide 1.0

Minutes

5.5

1

23

4

5 6

AS18-4µm Fast CapillaryEluent: 35 mmol/L KOH

5

1

7

6 5

3 421-0.2

0


5. Bromide 1.06. Nitrate 1.07. Orthophosphate 2.0

0 1 2 3 4 5-0.5

µS

Minutes

1 5 67

• Instead of shortening columns for faster separations, we increasecolumn length, but we sacrifice speed.

• In addition, it is possible to decrease particle diameter, but we

High Resolution IC

• In addition, it is possible to decrease particle diameter, but we sacrifice column back pressure.

Resolution

High capacity

High resolutionsacrificing speed


SpeedCapacity

High capacitysacrificing speed Faster separations

sacrificing resolution or capacity

High Resolution Cation Analysis on IonPac CS16at Different Flow Rates

7Column: IonPac CS16,

2 x 250 mm x 0.5 mm IDEluant: 30 mmol/L MSA (EG)Flow rate: A: 10 µL/min 30 µL/min 3600 psi30 µL/min 3600 psi

µS

BB

1 2 3

4

5

Flow rate: A: 10 µL/min B: 20 µL/min C: 30 µL/min

Inj. volume: 0.4 µLTemperature: 40 °C Detection: Suppressed conductivity

AutoSuppression,Recycle mode

Suppressor: CCES 300

Peaks: 1. Lithium 0.5 mg/L2. Sodium 2.0

6 CC

10 µL/min 1200 psi10 µL/min 1200 psi




Minutes

AAAA

0 40-1

1 2 3 2. Sodium 2.0 3. Ammonium2.5 4.

Potassium 5.05. Magnesium 2.56. Calcium 5.020

ANALYSIS OF DISINFECTION BY-PRODUCTS


ANALYSIS OF DISINFECTION BY-PRODUCTS AND DIFFICULT ANALYTES

Regulation of Bromate in MunicipalDrinking Water

1993

• World Health Organization (WHO) set a guideline of 25 µg/L bromate in drinking water

1998

• U.S. EPA established a 10 µg/L bromate maximum contaminant level • U.S. EPA established a 10 µg/L bromate maximum contaminant level (MCL) in drinking water and a maximum contaminant level goal (MCLG)

of zero under the Stage 1 disinfectants/ disinfection by-products (D/DBP) rule

• European Union reduced the regulatory value from 50 to 10 µg/L bromate

2003

• WHO set a provisional value of 10 µg/L bromate in drinking water

2004


2004

• U.S. Environmental Protection Agency, Stage II D/DBP rule leaves MCL at 10 µg/L

• The U.S. FDA adopted the U.S. EPA’s MCL for bromate in bottled waters

Trace Analysis of Bromate on IonPac AS19 with Reagent-Free IC

0.5

µS

3 8

17

65

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30

0.2

Minutes

12

4

0.0

2


Column: Ion Pac AS19 + guard (4 mm) Sample: 1. ChloriteFlow rate: 0.75 mL/min 2. Bromate 2 µg/LEluent: 20 mmol/L KOH (EG) 3. Chloride 100 mg/L

Detection: Suppressed conductivity / External Water Mode 4. ChlorateInj. volume: 100 µL 5. Bromide

6. Nitrate7. Carbonate8. Sulfate 100 mg/L

Sensitivity: Instrumental Setup for Bromate Analysis by IC×IC

Large Loop

Suppressor

1st Dimension

Large-loop injection

Partially resolve matrix Intermediate Step

Remove time segmentSuppressor

Cell 1Pump EG4 mm

ColumnInjection Valve

CRD

0.4 mm Column

UTAC-ULP1 Concentrator

Cell 2

CRD

Remove time segment

Trap and concentrate ions of interest

2nd Dimension


Switching Valve

EG PumpCell 2

Suppressor2nd Dimension

Resolve on smaller column

Sensitivity enhancement

Different selectivity optional

RFIC is Sensitive and Easy to Use for 2-D Applications!

• Used for high matrix samples

• More robust than post column Methods

• EPA 317 uses a toxic, unstable reagent

0.60

µS

First Dimension – IonPac AS19

• EPA 317 uses a toxic, unstable reagent

• EPA 326 is complicated, less robust

• RFIC - Just add water

• Full Chromeleon control

• EPA approved methods

• EPA 302.0 Bromate

• EPA 314.2 Perchlorate

0.30

0.64

BrO3

Concentrator

Second Dimension – IonPac 24


• EPA 314.2 Perchlorate

• EPA Haloacetic Acids (pending)

• Proven and validated for low ppb detection.

0 10 20 30 350.54

µS

BrO3

Minutes

Sensitivity Improvement strategy

• RFIC using hydroxide eluents suppressed to water, lower background

• RFIC in 2-D IC 4/2 mm results in 4x sensitivity enhancement

• 2-D IC in 4/0.4 mm format improves sensitivity 100x• 2-D IC in 4/0.4 mm format improves sensitivity 100x

Dimension Sensitivity Flow rate (mL/min)

First (4mm) 1 1

Second (2mm) 4 0.25

Proprietary & Confidential28 Dionex Confidential28

Second (2mm) 4 0.25

Second (0.4mm) 100 0.01

First Dimension

First DimensionColumn: IonPac AS24, 4 mm Flow rate: 1.0 mL/min

Suppressor: ASRS 300, 4 mmColumn temp.: 15 °CInj. volume: 1000 µL

13

45

27

6

8

3

Trace Analysis of HAA using a 2-D IC

12

Inj. volume: 1000 µL

Second Dimension

Column: IonPac AS26, 2 mmFlow rate: 0.25 mL/minSuppressor: ASRS 300, 2 mmColumn temp.: 15 °CConcentrator: IonPac UTAC-LP2

Peaks Concentration (µg/L)1.MCAA 1002.MBAA 1003.DCAA 100

Second Dimension

97 8

1

342

7

6

0 10 20 30 40 50 60-1


0 10 20 30 40 50 60-2

3.DCAA 100

4.BCAA 1005.DBAA 1006.TCAA 1007.BDCAA 1008.CDBAA 100

9.TBAA 100

Recovery >90% for 9 HAAs

4 52

9

7

8

High ionic strength water (specified in EPA methods): chloride, bicarbonate, sulfate 100 mg/L each; nitrate; orthophosphate 10 mg/L each

2-D IC configuration

Large Loop

Suppressor

Cell 1

PumpEG1st Dimension

Large Loop injection

Partially resolve analyte from matrix

Sensitivity: Instrumental Setup for IC×IC

Cell 14-mm

ColumnInjection Valve 1CRD

4-mm Column

Concentrator

Cell 2

CRD

analyte from matrixIntermediate Step

Transfer cut volume

Trap and focus ions of interest

2nd Dimension

Separate on smaller ID column

LoadInject


Valve 2

EGPump

Cell 2 SuppressorDifferent Selectivity

Signal Enhancement

Transfer to 2-DLoad Concentrator


Large Loop

Suppressor

Cell 1

PumpEG1st Dimension




Cell 14-mm


Concentrator

Cell 2

CRD


Transfer cut volume


2nd Dimension


LoadInject

2-mm Column


Valve 2

EGPump


Signal Enhancement



Large Loop

Suppressor

Cell 1

PumpEG1st Dimension




Cell 14-mm


Concentrator

Cell 2

CRD


Transfer cut volume


2nd Dimension


LoadInject

0.4-mm Column


Valve 2

EGPump


Signal Enhancement


Trace Perchlorate Using IC×IC with 2nd Column in Capillary Format

0.10

µS

1st dimension chromatogram0.1 µµµµS full scale

A. First-Dimension ConditionsColumn: IonPac AG16, AS16, 4 mm Flow rate: 1.0 mL/min

Eluent: 65 mM KOH (EG)Suppressor: SRS 300 1

0.0

10.0

µS

2nd dimension chromatogram10 µµµµS full scale

Suppressor: SRS 300 Inj. volume: 4000 µLTemperature: 30 °CB. Second-Dimension Conditions

Column: IonPac AS20, 0.4 mm

Flow rate: 10 µL/minEluent: 35 mM KOHSuppressor: ACES 300

Temperature: 30 °CConcentrator: Capillary concentrator,

5000 µL of 1st dimension suppressed effluent (19 to 24 min)

Peak: 1. Perchlorate 1.0 µg/L

0 60

1


0 600.0

µS

Minutes2

10 µµµµS full scalePeak: 1. Perchlorate 1.0 µg/L

Perchlorate Peak Area1st Dimension: 0.0115 µS*min2nd Dimension: 1.75 µS*min

CAP-IC gives 100-fold increase in sensitivity!

Trace Analysis of Bromate in Bottled Water by IC×IC

0.5

Bro

ma

te

A. 1st DimensionColumn: IonPac AG19, AS19, 4 mm

µS

Bro

ma

te

Column: IonPac AG19, AS19, 4 mm Flow rate: 1 mL/min

Eluent: 10-60 mmol/L KOH (EG)Suppressor: SRS 300 (4 mm) Inj. volume: 1000 µLTemperature: 30 °C

B. 2nd DimensionColumn: IonPac AS20 (0.4 mm)Flow rate: 10 µL/minEluent: 35 mmol/L KOH (EG)Suppressor: ACES 300

Temperature: 30 °CConcentrator: Capillary concentrator,


—— Sample A (54 ng/L)—— 100 ng/L bromate in deionized water—— 30 ng/L bromate in deionized water

—— Deionized water

17 20 -0.3

Minutes

1

Concentrator: Capillary concentrator,2500 µL of the suppressed effluate from the 1st dimension (7.5-10 min)

Trace Analysis of Perchlorate with IC×IC

A. First-Dimension ConditionsColumn: IonPac AG16, AS16, 4 mm Flow rate: 1.0 mL/min

Eluent: 65 mmol/L KOH (EG)

2.5

Pe

rch

lora

te

B. Second-Dimension ConditionsColumn: IonPac AS20, 0.4 mm

Flow rate: 10 µL/minEluent: 35 mmol/L KOH (EG)

µS


30 45-1.0

Minutes

—— Brand A bottled water (263 ng/L perchlorate)—— Brand B Bottled water (38.5 ng/L perchlorate)—— 30 ng/L perchlorate in DI water—— DI water


CAPILLARY IC-MS/MS

RFIC is Easily Coupled to an MS

• MS sensitivity can be improved by using ion-exchange-based separations

• More resolving power and better selectivity than reversed phase separations

• Good separation minimizes ion suppression due to co-elution with other analytes or matrix species

• Disinfection by-products• Disinfection by-products

• Bromate

• Haloacetic acids

• Organic contaminants

• Glyphosate

• Endothall

• Ethanolamines

• Fluoroacetate

Conductivity Conductivity DetectorDetector

Eluent Eluent GeneratorGenerator

ColumnColumnGuardGuard

SSuppressoruppressor

Pump Pump

WaterWater

OrganicOrganicSolventSolvent

Diverter Diverter ValveValve

WasteWaste


• Fluoroacetate

• Value

• Direct injection

• No derivatization!

• Excellent low level detection

WasteWaste

AuxAuxPumpPump

SolventSolvent

MS/MSMS/MS

United States Environmental Protection Agency TECHNICAL SUPPORT CENTER

OFFICE OF GROUND WATER AND DRINKING WATER

U. S. ENVIRONMENTAL PROTECTION AGENCY

CINCINNATI, OHIO 45268

Office of Research and Development: December 2009

Method 557.0DETERMINATION OF HALOCAETIC ACIDS, BROMATE, AND DALAPON IN DRINKING WATER BY ION CHROMATOGRAPHY ELECTROSPRAY IONIZATION TANDEM MASS SPECTROMETRY (IC/ESI-MS/MS)


CHROMATOGRAPHY ELECTROSPRAY IONIZATION TANDEM MASS SPECTROMETRY (IC/ESI-MS/MS)

A. D. Zaffiro and M. Zimmerman (Shaw Environmental, Inc.)B. V. Pepich (U.S. EPA, Region 10 Laboratory)Rosanne W Slingsby, R. F. Jack and Christopher A. Pohl (Dionex Corporation)D. J. Munch (U.S. EPA, Office of Ground Water and Drinking Water)

EPA 557: Determination of Bromate, Dalapon, and HAA9 by Direct Injection Using IC-MS/MS

• GC-ECD

• 3 h each sample Cl- SO4

CO3

NO

Diverted to waste

• RFIC-MS/MS

• Direct injection

• MRL ppb level

• No derivatization

NO3


• Glyphosate [N-(phosphonomethyl) glycine] is a nonselective herbicide. (RoundUp®)

• Endothall herbicide

Pesticides, Herbicides and Emerging Contaminants by RFIC-MS/MS

OHOH

O

O

O

EndothallOH

H2N P

O

OH

OH

NH

P

O

OH

O

HO

AMPAGlyphosate

• Ethanolamines are also produced directly (500ktons/year) and have uses as:

• Pesticides

• Emulsifying agents and detergents

• Bactericides

• Cosmetics

• Warfare agent

• Fluoroacetate

• Herbicide

Cl

N

Clbis (2-chloroethyl)methylamine (HN-2)

tris (2-chloroethyl)amine (HN-3)Cl

N

Cl

Cl

AMPA


Cl

N

Cl bis (2-chloroethyl)ethylamine (HN-1)

Cl

Separation of Glyphosate and AMPA from Common Anions

µS

AMPA

Glyphosate

Conductivity Data

Cl-NO3

CO3, SO4

Diverted to waste

Column: IonPac AG24, AS24Eluent: KOH (EG)Detection: Suppressed conductivity

and MS

Peaks: 1. AMPA 10 µg/L

-0.3 5.0 10.0 15.0 20.0 25.0 30.0 35.4

min

1110987654321

CO3, SO4

60,000

70,000

80,000

90,000

100,000

500

600

700

8003 - 03-06-09 #2 CD_1_Total

Chloride

Sulfate, Carbonate

Conductivity and MS/MS data


Peaks: 1. AMPA 10 µg/L2. Glyphosate 10 µg/L

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0 24.0 26.0 28.0 30.0 32.0 35.00

10,000

20,000

30,000

40,000

50,000

0

100

200

300

400

AMPA

1

Glyphosate

Nitrate

RFIC Separation of Cationic Ethanolamines

1000

50

100RT: 11.67

RT: 11.66

NL: 1.03E4

DEA: 106.1→88.1

NL: 2.02E4

Chromatographic ConditionsSystem: ICS-2000 RFIC IC SystemColumn: Ion Pac CS15 & CG15

Eluent: MSA (EG)

• Excellent chromatographic resolution for ethanolamines

• Avoids signal suppression

• Provides low detection limits0

50

1000

50

100

Rela

tive A

bundance

0

50

RT: 12.44

RT: 12.82

EDA-IS: 114.1→96.1

NL: 6.59E4

MDEA: 120.1→102.0

NL: 1.02E5

EDEA: 134.1→116.0


• Provides low detection limits

0 5 10 15 20Time (min)

0

50

1000

RT: 12.45

RT: 11.06

EDEA: 134.1→116.0

NL: 1.14E4

TEA:150.1→132.0

Matrix: Lake Tahoe Water

50

100

Re

lati

ve

Ab

un

da

nc

e

5.511.08E5 Endothall

50

100

Re

lati

ve

Ab

un

da

nc

e

5.429.23E4

Endothall

Matrix : Lake Mead Water (10x dilution)

RFIC Separation of Anionic Endothall

Chromatographic ConditionsSystem: ICS-2000 RFIC ICColumn: Ion Pac AS16 & AG16

Eluent: Hydroxide (EG)Detection: Suppressed conductivity,

MS

100

0

50

Re

lati

ve

Ab

un

da

nc

e

5.38Glutaric Acid – d6

6.84E4

SRM: 137 �� 74 m/z

3.06

30

40

50

60Conductivity

0

Re

lati

ve

Ab

un

da

nc

e

SRM: 185 �� 141 m/z

300

400

500550

µS

3.16

5.89Conductivity

0

50

100

Re

lati

ve

Ab

un

da

nc

e 5.366.69E4 Glutaric Acid – d6

SRM: 137 �� 74 m/z

0

Re

lati

ve

Ab

un

da

nc

e

SRM: 185 �� 141 m/z


0 1 2 3 4 5 6 7 8 9Time (min)

0

10

20

30

µS

6.31

3.87 5.512.55 5.24

0 1 2 3 4 5 6 7 8 9Time (min)

0

100

200

300µS

3.872.54 5.5

1

5 ppb Endothall spiked in Lake Tahoe (left) water sample and Lake Mead water sample (right, 10x dilution) 100% recoveries, 2-3% RSD peak area, MDL 0.566 ppb

Conclusions

• RFIC with suppressed conductivity detection offers highly • RFIC with suppressed conductivity detection offers highly reproducible isocratic and gradient separations of target analytes.

• High pressure Capillary IC facilitates higher resolution, which can be realized by longer columns.

• IC×IC can be used for improved sensitivity in complex matrices.

• Capillary RFIC with MS/MS is a highly sensitive analytical tool.


The New

ICS 4000


ICS-4000 Capillary HPIC

Dedicated High Pressure IC

The benefits of speedwithout compromising resolution;

24/7 uptime of Capillary IC24/7 uptime of Capillary ICand detection choices

in a compact, integrated system


46

ICS-4000 – Top User Values

• Always Ready with 24/7 Up-time• Better information with high resolution and speed• Low cost of ownership with low reagent use

• Ease-of-use with efficient, integrated design• Ease-of-use with efficient, integrated design• Application versatility with detector options

• Conductivity• Amperometric• The New Charge Detector

1.2

1

2

3

4

5

6

7


100

µS

Minutes

5-0.2

7 Anions - AS18 4 µm

What is Charge Detection?

• Response is proportional to ion charge, providing universal calibration

• Weakly dissociated analytes show higher response

• Improved linearity for weakly dissociated species:organic acids, amines, silicate, borateorganic acids, amines, silicate, borate

• Complements suppressed conductivity detection


Quantification of unknowns at low cost with universal, linear calibration

Capillary QD CellQD Cell

QD

CD

Separation of Inorganic Anions using the Dionex IonPac AS18-4µm Column at Different Flow Rates

Column: Dionex IonPac AG18-4µm/AS18-4µm, (0.4 x 150 mm)

Eluent Source: Dionex KOH Capillary Cartridge

Eluent: 30 mM

Col. Temp.: 30 °C

20

30 µL/min, 4141 psi

Col. Temp.: 30 °C

Inj. Volume: 0.4 µL

Detection: Suppressed Conductivity, Dionex ACES 300

Peaks: 1. Fluoride 0.2 mg/L2. Chloride 1

3. Nitrite 14. Sulfate 15. Bromide 16. Nitrate 17. Phosphate 2

µS



2

1

43

5 6


7. Phosphate 2

10-15

Minutes

5

57

QC IC PROGRAMMA 2012

Valutazione Esterna di Qualità in Cromatografia Ionica


QC IC PROGRAMMA 2012

Dionex Confidential

Thank you for your kind attention!


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