Capillary Ion Chromatography A New Platform to Reduce ... · Joachim Weiss, Ph.D. Thermo Fisher Scientific GmbH, Dreieich, Germany Capillary Ion Chromatography – A New Platform

Joachim Weiss, Ph.D.

Thermo Fisher Scientific GmbH, Dreieich, Germany

Capillary Ion Chromatography –

A New Platform to Reduce

Laboratory Operational Cost

and Increase Laboratory

Productivity

Proprietary & Confidential 2 Dionex Confidential Dionex Confidential

Outline

• Introduction to Capillary IC

• The dimension of scale

• Top values

• The new ICS-4000

• Charge detection

• Conclusions


INTRODUCTION TO CAPILLARY IC

Proprietary & Confidential 7 Dionex Confidential

Parameter Analytical IC Capillary IC

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

(with IC × IC)

700 ppt

7 ppt

The Dimension of Scale


The Dimension of Scale – The Concentration Factor

Overlay of chromatograms with 4 mm, 2 mm, and 0.4 mm columns –

all with optimum injection volume

Capillary IC with 0.4 µL injection volume

-2

16 1

Lithium Sodium

Ammonium

Potassium Magnesium Calcium

-2

16

Co

nd

uctivity [µ

S]

0 2 4 6 8 10 12 14

-2

16

Retention time [min]

Lithium Sodium

Ammonium


Lithium Sodium

Ammonium


Microbore IC with 10 µL injection volume

Standard bore IC with 40 µL injection volume


Overlay of chromatograms with 4 mm, 2 mm, and 0.4 mm columns –

all with equal injection volume (0.4 µL)

The Dimension of Scale – The Concentration Factor

-2

16 1

Lithium

Sodium

Ammonium


-2

16

0 2 4 6 8 10 12 14

-20

16

Capillary IC with 0.4 µL injection volume

Co

nd

uctivity [µ

S]


Microbore IC with 0.4 µL injection volume

Standard bore IC with 0.4 µL injection volume

Lithium

Sodium

Ammonium

Potassium

Magnesium Calcium

Lithium

Sodium

Ammonium

Potassium

Magnesium Calcium


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

• Combination of three techniques

• 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

REDUCTION Cathode 2e– + 2H2O

2 OH– + H2 (g)

Proprietary & Confidential 11

Advantages of Electrolytic Eluent Generation in Capillary IC Systems

• 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


Electrolytically Formed Gradients

• EG step gradient − accuracy up to 200 mmol/L in capillary mode

[Eluent] Current

Flow rate


The IC Cube − The Heart of a Cap IC System

Change of the IC Cube with all consumables – 6 connections!

Guard and analytical column

CRD 200

EG Degas

Injection valve

Suppressor

14 Proprietary & Confidential

The Thermo Scientific Dionex ICS-5000+ HPIC

Universal HPIC

• High-pressure capable with capillary

systems

• Continuous operation up to 5000 psi

when configured as a Reagent-Free™

(RFIC™) system

• Increased productivity with fast run

times

• Improved separations and higher

resolution with smaller particle diameter

columns

HPIC - High Resolution, Fast Analyses


Thermo Scientific Dionex ICS-5000+ – Positioning the IC Cube


Capillary IC – Reproducible Results

0 2 4 6 8 10 12 14 16 18 20 -4.0

-2.0

0.0

2.0

4.0

Co

nd

uc

tivit

y [

µS

]


Fluoride

Chlorite

Chloride

Nitrite

Chlorate

Bromide Nitrate

Sulfate

Fluoride Chlorite Chloride Nitrite Chlorate Bromide Nitrate Sulfate

Retention time

(% RSD)

0.048 0.045 0.037 0.030 0.023 0.024 0.021 0.026

Peak area

(% RSD)

0.287 0.363 0.367 0.328 0.349

0.359 0.354

0.287

IonPac AS19 – Isocratic

(10 µL/min)

Overlay of 50 consecutive analyses


Overlay of 30 consecutive runs

% RSD retention times:

0.09% for arsenate to 0.18% for fluoride

Column: IonPac AS19

(250 mm × 0.4 mm i. d.)

Eluent: KOH (EG)

Gradient: 10 mmol/L (0 to 10 min),

10-52 mmol/L (10 to 42 min),

52-70 mmol/L (42 to 45 min)

Flow rate: 10 µL/min

Temperature: 30°C

Detection: Suppressed conductivity

ACES 300, AutoSuppression,

Recycle mode

0 50 0

16

µS

Minutes

Flu

orid

e

Ace

tate

Form

ate

C

hlo

rite

B

rom

ate

C

hlo

rid

e

Nitrite

Chlo

rate

B

rom

ide

Nitra

te

Su

lfa

te

Ma

lon

ate

S

ele

nate

O

xa

late

Iod

ide

T

hio

su

lfate

C

hro

ma

te

Ph

osp

ha

te

Fum

ara

te

Ars

en

ate

Th

iocya

nate

Pe

rchlo

rate

Separation of 22 Anions on a Capillary IonPac AS19 Column


• 15 columns are available at the moment

• All IonPac columns are in 0.4 mm or 0.5 mm format

• AS18-4µm and CS12A-5μm in 150 mm length format

• Remainder of columns are in 250 mm length format

• All columns are using current resin media

• Future columns may utilize new capabilities in capillary format

• Columns to be placed into a cartridge holder

Capillary Ion-Exchange Separator Columns


Current IonPac Capillary Column Portfolio

IonPac AS11-HC-4µm

IonPac AS15

IonPac AS18

IonPac AS18-Fast-4µm

IonPac AS19

IonPac AS20

IonPac AS25

IonPac AS26

IonSwift MAX-100

IonSwift MAX-200

IonPac CS12A

IonPac CS12A-5µm

IonPac CS16

IonPac CS17

IonPac CS19-4µm

Speed, Resolution, Capacity

Anions and oxyhalides

Organic acids and haloacetic acids

Perchlorate

Sulfur species

Cations

Amines

U.S.EPA, ASTM , ISO, AWWA, NIOSH, OSHA, EN, AFNOR


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

• 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 mL

of sample

• Lower cost of ownership

• Lower eluent consumption, less waste

• 18 months lifetime of the EG cartridges


Advantages of “IC on Demand” Mode

• Simplifies and speeds up

• Eliminate time-consuming and error prone steps such as manual eluent

preparation, system start-up, and equilibration time.

• Increased system stability

• Lower noise and more stable detector response.

• Just run check standards

• Enhanced stability saves time as fewer calibration sequences are

required and the system can be quickly verified for system performance

by just running a check standard.

• Suitable for multi-users

• Allows “walk up” capability to the system; just download method and

inject the sample.

• Lower maintenance

• Reduced preventive maintenance and down time.


Typical Workflow of a Capillary IC System

Run

Check

Standard

Capillary IC Speeds Up & Simplifies

IC Workflow!

“IC on Demand” – Walk-up IC Workflow

Run

Samples Results


System Performance – Peak-to-Peak Noise

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

0 20 40 60 80

nS

Days

Peak-to-peak noise of Capillary IC using Dionex IonPac CS16 over 80 days.

Conditions: 30 mmol/L MSA at 10 µL/min; suppressed conductivity


System Performance – Retention Time Stability

Average anion peak retention time reproducibility of Capillary IC using

Dionex IonPac AS19 over 90 days.

Conditions: 20 mmol/L KOH at 10 µL/min; suppressed conductivity

-0,05%

0,00%

0,05%

0,10%

0,15%

0,20%

0 20 40 60 80 100

# Days


Linear Ranges for Anion and Cation Analyses

Linear Range

(µg/L)

Coefficient of

Linearity (r2)

Fluoride 1.5 – 150 1.000

Chlorite 5 – 500 0.9997

Bromate 10 – 1000 0.9997

Chloride 3 – 300 0.9998

Nitrite 7.5 – 750 1.000

Chlorate 12.5 – 1250 0.9997

Bromide 12.5 – 1250 0.9998

Nitrate 12.5 – 1250 0.9998

Sulfate 15 – 1500 0.9999

Linear ranges for capillary systems

using the Dionex IonPac AS19

Linear

Range

(µg/L)

Coefficient of

Linearity (r2)

Lithium 0.5 – 50 0.9996

Sodium 2 – 200 0.9996

Ammonium+ 2.5 – 250 0.9997

Potassium 5 – 500 0.9997

Magnesium 2.5 – 250 0.9993

Calcium 5 – 500 0.9994

+Quadratic fit

Linear ranges for capillary systems

using the Dionex IonPac CS16


ICS-4000 CAPILLARY HPIC


ICS-4000 Capillary HPIC

Dedicated High-Pressure IC

The benefits of speed without

compromising resolution;

24/7 uptime of Capillary IC and detection

choices in a compact, integrated system


ICS-4000 – Feature Overview

• Single channel, integrated and compact

• Capillary HPIC for 24/7 uptime

• Reagent-Free IC for performance and simplicity

• Integrated IC Cube

(uses same consumables as ICS-5000+)

• Active thermal control

• Detection options

• Conductivity

• Electrochemical

• Charge Detection for weakly dissociated ions

• Touchpad for stand-alone control

• Chromeleon 7.x and 6.8 support


Integrated Design Benefits

• Front access for easy user

maintenance

• Integrated, orderly tubing layout

reduces the number of connections,

improves ease-of-use.

• IC Cube provides convenient plumbing

of components, reducing dead

volumes, improving peak efficiencies,

and improving ease-of-use.

• Configure with CD, or CD and new QD,

or ED for versatility.

• Option for reversible door


RFIC – Always Ready (accessible if required)

• Tilt-up hood keeps ECG and

CR-TC located out-of-site and

out-of-mind, yet readily

accessible for maintenance or

18 month replacement

• Display tilts forward to allow

local control while hood is

open

• Eluent shut-off valve provides

positive shut-off of source for

easy pump servicing

• Leak management and

detection


Versatile Detector Options – CD and QD

• The ICS-4000 can be configured with

either a CD or an ED

• Detectors are user installable

• The new Charge Detector (QD) can

be configured with the CD to provide

a complimentary detection mode for

weakly-dissociated species

• The QD requires eluent suppression

• CD-4000 and CD-5000 are not

interchangeable

• CD flow cells are the same except for

internal waste lines QD Cell QD CD


What is a Charge Detector ?

• Responds to ionic species by drawing a current at a fixed potential

• Uses a membrane device similar to a CR-TC (app. lifetime 24 months)

• Response is proportional to charge, universal calibration

• Weakly dissociated (suppressed) analytes will show higher response

• Response vs. Concentration will be linear for weakly dissociated species

• Organic acids, amines, silicate, borate

• Complements suppressed conductivity detection

33

Cation Exchange

Membrane

Anion Exchange

Membrane H20 H20

- + DC

H2O 2H+ + ½ O2 + 2e

– 2H2O + 2e

– 2OH– + H2

H+ OH-

OH-

OH-

OH-

H+

H+

H+ H+ OH-

H+ OH-

H+ OH-

H+ OH-

H+ OH-

H+ OH-

H+ OH-

H+ OH-

H+ Cl- H+ Cl- H+ Cl-

Electrodialytic Water Purifier and the Charge Detector Concept

H+ OH-

H+ OH-

H+ OH-

H+ OH-


0 20 40 60Time, min

28

28.4

28.8

29.2

29.6

30

Cu

rre

nt,

A

HClO4

CH3SO3HHNO3

KCl

NaClNaNO3

20 µmol/L; Voltage: 1.5 V

Specific Conductance

HNO3 : 421 S/cm

CH3SO3H : 380 S/cm

HClO4 : 418 S/cm

NaNO3 : 121 S/cm

Charge Detector Response (Flow Injection)

Similar response for different ions with the same charge


Data Management

Conductivity Detector

High-Pressure Non-Metallic Pump

Eluent Generator (OH– or H+)

Waste

Sample Inject (Autosampler) Recycle Mode

H20

CR-TC

Electrolytic Eluent

Suppressor

Separation Column Charge Detector

Ion Chromatography System Setup with QD


Charge Detector Characteristics

• Background is due to dissociation of water

• Baseline noise stems from dissociation of water

• The applied voltage impacts the signal as well as the noise

• Removal efficiency depends on the applied voltage as well as

residence time

• Response high for all ions

• Super faradaic behavior

• Hypothesis: Dissociation of water is enhanced due to the relatively lower

resistance during the transition of an analyte peak

• Weak acids and bases show a relatively higher response

• S/N is slightly worse than conductivity

Dasgupta et. al., Anal. Chem. 82 (2010) 951-958


Conductivity and charge detection: capillary format (IonPac AS19, 250 mm × 0.4 mm i. d.)

0.0

2.0

4.0

6.0

8.0

11.01 - 03012011 charge detector #102 15+3 anion 5x dilution CD_1_TotalµS

1

Az

-0.1 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 40.8

0.665

0.700

0.750

0.800

0.8502 - 03012011 charge detector #102 15+3 anion 5x dilution CD_2_TotalµS

min

2

1

2

3

4

5 6 7

8 9

10

11

12

13

14

15

16 17

18 19

1. Fluoride

2. Acetate

3. Formate

4. Bromate

5. Chloride

6. Nitrite

7. Chlorate

8. Bromide

9. Nitrate

10. Carbonate

11. Sulfate

12. Malonate

13. Oxalate

14. Thiosulfate

15. Chromate

16. Orthophosphate

17. Arsenate

18. Thiocyanate

19. Perchlorate

QD Results – Anion Standard

Weakly dissociated ions show larger peaks in QD

38

Response vs. Concentration (Conductivity vs. Charge)

y = -0,001x2 + 0,2795x + 0,0306 R² = 0,9999

0

5

10

15

20

0 20 40 60 80 100 120

y = 0,0536x - 0,0376 R² = 0,9998

-1

0

1

2

3

4

5

6

0 50 100 150

Chloride Chloride

y = 0,06x - 0,0427 R² = 0,9997

-2

0

2

4

6

8

0 50 100 150

y = 0,4995x - 0,0061 R² = 1

0

10

20

30

40

50

60

0 20 40 60 80 100 120

Formate (pKa 3.75) Formate (pKa 3.75)

Silicate (pKa 9.8) Silicate (pKa 9.8)

y = -4E-06x 2 + 0.0006x + 5E-05

R 2 = 0.9999

0

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0.016

0 10 20 30 40

Series1

Poly. (Series1)

More linear behavior for weakly dissociated ions – easier quantification

CD QD

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

0.0007

0.0008

0.0009

0.001

0 10 20 30 40

Series1

Poly. (Series1)


Versatile Detector Options – ED

• The ICS-4000 can be configured with either a CD or an ED

• Detectors are user installable

• ED-4000 and ED-5000 are not interchangeable

• Cell and electrodes are the same


The IC Portfolio

ICS-4000 Capillary HPIC compliments the ICS-5000+ HPIC as well as the

existing array of Dionex IC system solutions

• The ICS-5000+ provides versatility and performance, including dual-system

support, hybrid configurations, and capillary HPIC support

• The ICS-4000 provides dedicated ease-of-use and performance, coupled with

the cost effectiveness of capillary HPIC

RFICRFIC

ICSICS--40004000

ICSICS--900900

Starter Line

IC System

Smallest FootprintDrinking Water Analysis

ICSICS--16001600ICSICS--11001100

Standard Integrated

RFIC™ System

Routine

Drinking & Waste

Water Analysis

ICSICS--21002100

Superior Integrated

RFIC™ System

Award Winning

Great Performance

High Purity Water and

Beverage Analysis

Basic Integrated

RFIC™ System

Routine IC

Drinking & Waste

Water Analysis

Premier High-End

HPIC & RFIC™ System

Award Winning

Flexible

Dual Channel

Ion Analysis

Carbohydrate & Amino Acid

Analysis

ICSICS--50005000

Integrated Dedicated

Capillary IC System

Capillary HPIC

RFIC-EG Technology

Carbohydrate Analysis

Drinking & Waste Water

Analysis

RFICRFICRFICRFIC

ICSICS--40004000ICSICS--40004000

ICSICS--900900ICSICS--900900

Starter Line

IC System

Smallest FootprintDrinking Water Analysis

ICSICS--16001600ICSICS--16001600ICSICS--16001600ICSICS--11001100ICSICS--11001100ICSICS--11001100

Standard Integrated

RFIC™ System

Routine

Drinking & Waste

Water Analysis

ICSICS--21002100ICSICS--21002100ICSICS--21002100

Superior Integrated

RFIC™ System

Award Winning

Great Performance

High Purity Water and

Beverage Analysis

Basic Integrated

RFIC™ System

Routine IC

Drinking & Waste

Water Analysis

Premier High-End

HPIC & RFIC™ System

Award Winning

Flexible

Dual Channel

Ion Analysis

Carbohydrate & Amino Acid

Analysis

ICSICS--50005000ICSICS--50005000

Integrated Dedicated

Capillary IC System

Capillary HPIC

RFIC-EG Technology

Carbohydrate Analysis

Drinking & Waste Water

Analysis


Conclusions

• Capillary RFIC with suppressed conductivity detection offers

highly reproducible isocratic and gradient separations of target

analytes.

• The ICS-5000+ provides versatility and performance, including

dual-system support, hybrid configurations, and capillary HPIC

support.

• The ICS-4000 provides dedicated ease-of-use and performance,

coupled with the cost effectiveness of capillary HPIC.

• Weakly dissociated (suppressed) analytes will show higher

response with charge detection.

• Charge detection complements suppressed conductivity

detection.


Thank you for your kind attention!

Documents

Capillary Ion Chromatography A New Platform to Reduce ... · Joachim Weiss, Ph.D. Thermo Fisher Scientific GmbH, Dreieich, Germany Capillary Ion Chromatography – A New Platform