automated sample preparation for ion chromatography · sample preparation): automation to prepare...
Post on 16-Oct-2020
6 Views
Preview:
TRANSCRIPT
Automated Sample Preparation for
Ion Chromatography
Joachim Weiss, Ph.D.
Thermo Fisher Scientific GmbH, Dreieich, Germany
Proprietary & Confidential2 Dionex Confidential
• Retention times too short
• Poor peak efficiency
• Poor resolution
• Poor reproducibility
• Irregular baseline
• Interference with analyte signal
• Quantitative dynamic range too narrow
• Electrochemical detector electrode fouling
Reasons for Sample Preparation
Proprietary & Confidential3 Dionex ConfidentialDionex ConfidentialDionex Confidential
Off-line and In-line Sample Preparation Tools
IonChromatography
Off-Line Sample Preparation
On-Line Sample Preparation
OnGuard
ASE
AutoTrace
AutoDilution
Concentration
RFIC-ESP
Electrolytic Water Purifier
CR-TC
AutoNeutralization
Matrix Elimination
AutoPrep
Filtration
Filtration
Filter Caps
InLine Filters
CRD 200/300
Combustion Bomb
Combustion IC
InGuard™
Proprietary & Confidential4 Dionex ConfidentialDionex ConfidentialDionex Confidential
New Publications
• Application notes, Application Briefs
• AB 106 − Trace analysis on ICS-2100
• AN 220 − Inorganic ions in water insoluble pharmaceuticals
• AN 244 − Phosphate using “heart cut” technique, 10-valve and concentrator
• TN 81 − AutoDilution, partial loop injection
• TN 83 − AutoDilution, vial-to-vial dilution
• TN 84 − AutoDilution, large loop/ small loop (updated)
• LC/GC application book page − Chloride removal using InGuard Ag and Na
• InGuard™ manual
Proprietary & Confidential5 Dionex ConfidentialDionex ConfidentialDionex Confidential
AUTODILUTION
Proprietary & Confidential6 Dionex Confidential
Thermo Scientific Dionex AutoDilution
• Suitable for IC and HPLC
• No additonal hardware required – low cost
• Based on the Chromeleon AutoDilution license
• Easy to install – no service engineer necessary
• Wizard for choosing re-injection conditions
• Easy to set up
• Determination is based on peak area, peak height, amount
(any Chromeleon variable)
• Dilution/injection volume is defined in a new Program File
• New sequence is only created for re-injected samples
• Different tasks with conditional programs can be defined
• Customized solutions for different budgets
• Partial loop re-injection (AS-AP)
• True dilution in a new sample vial (ASAP)
• Small/large injection loop (AS-DV or Dionex ICS with 10-port valve)
Proprietary & Confidential7 Dionex Confidential
AutoDilution: Large Loop / Small LoopConditional Injection
0.0
4.0
0 20
Sulfate Calibration Function
Are
a
(µS
*min
)
Concentration (mg/L)
Highest Calibration Standard
Analytical Result
0 12
0.0
2.5Wastewater
AS18, 4 mm,
33 mmol/L KOH
µS
Minutes
Fluoride
Chlo
ride
Nitrate
Sulfate
Phosphate
Analytical result is outside the calibrated range
Sample will be re-injected
Proprietary & Confidential8 Dionex Confidential
0.0
1.4
0
Sulfate Calibration Function
Are
a
(µS
*min
)Concentration (mg/L)
7
Highest Standard
Analyical result
0 12
0.0
2.5Wastewater re-injected, small loop
AS18, 4 mm, 33 mmol/L KOH
[µS]
Minutes
Chloride
Nitrate
Sulfate
The analytical result now lies well within the calibrated range
AutoDilution: Large Loop / Small LoopConditional Injection
Proprietary & Confidential9 Dionex Confidential
Chromeleon adds lines for the sample re-injections to the same
or a different sequence:
AutoDilution: Large Loop / Small LoopConditional Injection
Proprietary & Confidential10 Dionex Confidential
PRE-CONCENTRATION AND IN-LINE CALIBRATION
Proprietary & Confidential11 Dionex Confidential
IonPac UTAC-LP2, UTAC-ULP2 and UTAC-XLP2 Concentrator Columns
• Improved back pressure resilience, no pulse damper required
• Compatible with polyacrylic acid application in the power
generating industry
• Ultra-clean (no bleed of sulfate) concentrator columns providing
reliable quantification
• Available in 3 formats
• UTAC-LP2 (4 x 35 mm)
• UTAC-ULP2 (5 x 23 mm)
• UTAC-XLP2 (6 x 16 mm)
• Replacement for UTAC 1 columns
Proprietary & Confidential12 Dionex Confidential
IonPac AC-ER Concentrator Column
• Very low dead volume concentrator based on the UTAC 2 resin
• Each injection only adds 75 μL of sample matrix into the eluant regardless
of the sample volume
• 266 injections can be performed before the eluant needs to be replaced,
regardless of the actual amount of sample loaded onto the concentrator
• Enables matrix elimination
• Solvents can be directly injected onto the AC-ER and then flushed off
before injection into the RFIC-ER system
• Enables a host of new applications with RFIC-ER systems
• Analysis of bromate to 5 ppb in drinking water
• Analysis of common anions in ethanol
Expands application capabilities of RFIC-ER
Proprietary & Confidential13 Dionex Confidential
RFIC-ESP™
• RFIC-ESP™ (Reagent Free Ion Chromatography – Electrolytic
Sample Preparation): Automation to prepare samples on-line with an
electrolytic water purifier
• Electrolytic water purifier
• Enables use of ICS-2100 for
automated trace analysis
• Column effluent is passed through
the water purifier and is used to
transfer samples and standards from
loops to a concentrator column
Proprietary & Confidential14 Dionex Confidential
Why RFIC-ESP™
• Only one pump needed (lower cost)
• Simplifies trace analysis
• Very low backgrounds
• Very low detection limits (<5 ppt) with less pre-concentration
volume
• Automated sample calibration and concentration
• Fewer errors, improved reliability, lower labor costs
Proprietary & Confidential15 Dionex Confidential
Electrolytic Water Polisher
2 H2O + 2e-
2OH-+ H2H2O 2H
++ ½ O2 + 2e
-
CathodeAnode
Anion
Exchange
Membrane
Cation
Exchange
Membrane
OH-H+
H+OH-H2O
H2O H2O
Na+ Cl-Cl-Na+
UPW
Proprietary & Confidential16 Dionex Confidential
RFIC-ESP: How Does the Water Polisher Work?
• Continuous electrolytic purification of aqueous input
• Point-of-use operation for automated preparation of standards
and samples
• Single-digit parts-per-trillion or better quality output water
• Cleaner input water to IC results in better MDL’s and system
performance
• No contamination of samples during pre-concentration
• Blank levels 10x lower than reported values
Proprietary & Confidential17 Dionex Confidential
Water Quality after Polisher Treatment
0 5 10 15 20 26
–0.2
1.0
µS
F-
Minutes
20 mL pre-concentration of UPW from polisher
Less than 5 ppt fluoride, acetate and formate (from fluoropolymer tubing)
Very low and consistent chloride, nitrate, and sulfate blank!
Proprietary & Confidential18 Dionex Confidential
RFIC-ESP™ Configuration
ASRS
EluentGenerator
LP Concentrator
Guard Column CD Cell
Eluent
Suppressed Eluent
Pure Water
Electrolytic
Polisher
Standard or Sample
(10 µL)
Large volume
Autosampler
310
58
Electrolytic
Polisher
Proprietary & Confidential19 Dionex Confidential
Standard Calibration Procedure
• Use incremental volume of fixed loop to increase
standard concentration (X1, X2…..X10)
• Calibrate IC dilution factor from known standards
(e.g., 1:1000 of 1000 µg/L)
• Use response from fixed loop (1000X) to
determine the required pre-concentration volume
• Use the resulted pre-concentration volume to
validate and qualify the calibration procedure
Proprietary & Confidential20 Dionex Confidential
Calibration with RFIC-ESP™ (Cal 1x)
ASRS
EluentGenerator
Guard Column CD-Cell
EluentSuppressed
Eluent
Pure Water
Standard
Electrolytic Water Polisher
Proprietary & Confidential21 Dionex Confidential
Calibration with RFIC-ESP™ (Cal 5x)
ASRS
EluentGenerator
Guard Column CD Cell
EluentSuppressed
Eluent
Pure Water
Standard
Repeat Load/Inject 5 times
Use same
flushing volume
Electrolytic Water Polisher
Proprietary & Confidential22 Dionex Confidential
RFIC-ESP™ – Automated Calibration
Proprietary & Confidential23 Dionex Confidential
RFIC-ESP™ : Anions at ng/L Levels in UPW
Peak Name Amount (ng/L)
F 24.033
Cl 22.307
NO2 42.532
0 5 10 15 20 26
0
1
µS
Minutes
F Cl NO2
Proprietary & Confidential24 Dionex Confidential
RFIC-ESP™ : Cations at ng/L Levels in UPW
Peak Name Amount (ng/L)
Li 11.511
Na 28.403
NH4 13.499
K 15.197
Mg 7.729
Ca 11.238
0 5 10 15 20 26
0
0.5
µS
Minutes
Li Na NH4 KMg Ca
Proprietary & Confidential25 Dionex Confidential
RFIC-ESP™ – Detection Limits
Estimated Detection Limits (3xSD)
Fluoride 0.6-0.9 ppt
Chloride 1.0-2.4 ppt
Nitrite 2.3-3.2 ppt
Bromide 3.3-5.8 ppt
Sulfate 2.3-3.2 ppt
Nitrate 2.7-4.4 ppt
Orthophosphate 3.0-3.8 ppt
Proprietary & Confidential26 Dionex Confidential
RFIC-ESP™ – Summary
• RFIC-ESP offers a simple method to perform ng/L analyses
• Online standard addition can be used for automated system
calibration
• Target markets: power generating and semiconductor industries
• Ease of installation and operation
• Simple matrix removal techniques can easily be incorporated
into the concept
Proprietary & Confidential27 Dionex Confidential
MATRIX ELIMINATION
Proprietary & Confidential28 Dionex ConfidentialDionex Confidential
Matrix Elimination − Commonly Used for Sample Clean-up in Ion Chromatography
• Mechanism
• Solid phase does not retain the analytes; matrix interferences
are bound to the phase while the analyte flows through
• Instances where analyte is collected and matrix washed away
• Applications
• Impurity removal
• Desalting
• pH adjustment
• Chemistry
• Ion exchange
• Precipitation
• Neutralization, pH adjustment
Proprietary & Confidential29 Dionex Confidential
“2-D” Phosphate Analysis − Fun with Valves
11
0
8
6
5
2
7
3
Analytical
Column
Guard
Column
Suppressor
Detector
9
4
L
C
LS
W
P
Auto-
Sampler
PUMPWaste
Waste
Courtesy of Rolf Maurer, Thermo Fisher Scientific Switzerland
“Waste” stream is directed via 10-port valve to concentrator,
then re-injected
Proprietary & Confidential30 Dionex Confidential
“2-D” Phosphate Analysis − Fun with Valves(AN 244)
0
0
10
µS
Phosphate Phosphate
Minutes 23
0 23
0
1
µS
Minutes
Phosphate
Phosphate
Valve switch to concentrator
Valve switch to waste
0 23
0
1
µS
Minutes
Phosphate
Phosphate
Valve switch to concentrator
Valve switch to waste 0
1
µS
Auxiliary valve enables “heart cut”, improving LOD
Courtesy of Rolf Maurer, Thermo Fisher Scientific Switzerland
Proprietary & Confidential31 Dionex Confidential
ONGUARD CARTRIDGES
Proprietary & Confidential32 Dionex Confidential
OnGuard™ Sample Pre-treatment Phase Chemistries
Phase Functionality Retention
Mechanism
Application
A Anion exchange resin
Bicarbonate form
Ion exchange Remove anions, increase pH
Ag Sulfonated resin
Silver form
Ion exchange/ Precipitation Remove halides
Ba Sulfonated resin
Barium form
Ion exchange/ Precipitation Remove sulfate
H Sulfonated resin
Acid form
Ion exchange Remove cations, reduce pH
M Iminodiacetate
Ammonium form
Chelation Remove transition metals
Na Sulfonated resin
Sodium form
Ion exchange Remove cations, no pH change
P Polyvinylpyrrolidone H-Bonding/ Complexation Remove phenols, azo dyes, humic acids
RP Polydivinylbenzene Adsorption Remove neutral hydrophobics
Proprietary & Confidential33 Dionex Confidential
OnGuard™ Application Examples
• Iodate in sodium hydroxide OnGuard H: Neutralization
• Cations in sulfuric acid OnGuard A: Neutralization
• Organic acids (maleate, fumarate,
acetate, and lactate) in cider and vinegar OnGuard P: Remove organics
• Anions in respiratory drugs OnGuard H: Remove basic drugs
• Anions in a quaternary amine solution OnGuard Na: Remove alkyl
ammonium
ions
• Iodide in urine OnGuard RP: Remove organics
• Bromate in hypochlorite solution OnGuard Ag: Remove chloride
• Carbohydrates in instant coffee OnGuard P: Remove phenolics
Proprietary & Confidential34 Dionex Confidential
INGUARD CARTRIDGES
Proprietary & Confidential35 Dionex Confidential
InGuard™ Cartridges
• New cartridges designed for automated matrix elimination procedures
• Several versions available for various applications:
Cartridge Functional group(s) Binding mode Example applications
Ag Ag+ form sulfonate Ion Exchange Removal of halides
Na Na+ form sulfonate Ion Exchange Removal of cations
H H+ form sulfonate Ion Exchange Removal of cations,
pH adjustment
HRP Hydrophilic
divinylbenzene
Adsorption, π-π
bonding
Removal of hydrophobic species,
azo- and cyano-containing species
Na/HRP Na+ form sulfonate,
Hydrophilic
Ion exchange
(Na)
and Adsorption
Remove Ca2+ (Na) and lipids (HRP)
from dairy products
Proprietary & Confidential36 Dionex Confidential
InGuard™ Cartridges
• Cartridges are of high capacity
• In-line approach − sample volume per cycle equals injection volume
• Small amount loaded onto cartridge increases effective capacity to
many samples per cartridge
• Reduced sample processing time, labor and cost
50% Na / 50% HRPNa/HRP
2 g resinHRP
5 to 5.5 mequivNa
5 to 5.5 mequivH
5 to 5.5 mequivAg
Cartridge CapacityCartridge Type
Proprietary & Confidential37 Dionex Confidential
InGuard™ Cartridges
• Cartridges are all PEEK, 9 mm by 24 mm form factor
• Designed for low back pressure − less than 50 psi at 2 mL/min
• Enables sample loading with an autosampler
• Two or more cartridges can be operated in series- for example, Ag and Na
L
CL
S
W
P
Waste
SuppressorAnalytical
Column
Guard
Column
Detector
Auto-
Sampler
InGuard
Cartridge
Concentrator
Column
Pump
Proprietary & Confidential38 Dionex Confidential
InGuard™ Cartridges
Cartridge capacity example − 1% sodium chloride sample
• 1% NaCl contains 170 mequiv per liter of sodium
• 100 µL injection contains 0.017 mequiv of sodium
• Cartridge capacity is 5 mequiv, so…
• Each InGuard Ag cartridge has a nominal capacity of 292 samples
1% NaCl = 10 g/L NaCl
10 g/L NaCl is 10 g / 58.45 g/mol = 0.171 mol
1% NaCl is 0.171 mol/L
100 µL injected is 0.0001 L
0.0001 L* 0.171 mol/L = 0.0000171 mol, 1.71*10-5 mol.
NaCl is 1 equivalent Na / mol,
so each sample is 1.71*10-5 equivalent of Na per injection
5*10-2 equivalents per cartridge / 1.71*10-5 equivalents per sample
= 292 samples / cartridge
Proprietary & Confidential39 Dionex Confidential
InGuard™ Cartridges
Application example:
Anion analysis in 1.6% NaCl, treat with InGuard Ag followed by InGuard Na
1
Minutes0 40
0
7
µS
1
2
3 45
1.6% NaCl w/o InGuard
1.6% NaCl blank without InGuard
1.6% NaCl with InGuard Ag and Na
Water blank with InGuard
Std of 2 mg/L nitrite, sulfate, and nitrate in 1.6% NaCl using InGuard
Peaks: mg/L (in standard)
1 Chloride
2 Nitrite 2
3 Carbonate
4 Nitrate 2
5 Sulfate 2
Column: IonPac AS15 + guard, 4 mm
Eluent: 23 mmol/L KOH (EG)
Flow rate: 1 mL/min
Sample prep: InGuard Ag and Na cartridges
Inj. volume: 100 µL
Detection: Suppressed conductivity
Proprietary & Confidential40 Dionex Confidential
InGuard™ Cartridges
Application example:
1.6% NaCl, plumbing schematic
4
6
12
3
5
PumpWaste
Suppressor
Analytical
Column
Guard
Column
Detector
L
C
LS
W
P
Loading
Pump
Auto-
Sampler
Waste
InGuard
Ag
Trap
Column
Concentrator
Column
InGuard
Na
Proprietary & Confidential41 Dionex Confidential
RFIC-ESP Configuration for Matrix Elimination
^
ASRS
EluentGenerator
LP Concentrator
Guard Column CD Cell
Eluent
Suppressed Eluent
Pure Water
Electrolytic
Polisher
Autosampler
310
58
Waste or
EWP (2)
InGuard
Proprietary & Confidential42 Dionex Confidential
Caustic Wastewater (Bayer Liquor Plant)
Sample
Concentrator
Guard
Separator
EWP
CD
3
5
7
9
1
P Waste
RP Cartridge
Eluent(RFIC EG)
1]
2]
3]
[4
[5
[6
L
L
C S
W
S
RS
Matrix: Aluminium hydroxide
Calcium and magnesium
Transition metals
Organics
Proprietary & Confidential43 Dionex Confidential
Plating Bath Wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
0.0
2.5
5.0
7.5
10.0
µS
Minutes
Chl
orid
e
Ort
hoph
osph
ite
Sul
fate
Ort
hoph
osph
ate
Column: AS18 + guard, 4 mm
Eluent: KOH gradient (EG)
Detection: Suppressed conductivity,
External water mode
Flow rate: 1 mL/min
Inj. volume: 10 µL
Sample: Nickel plating bath
1:1000 dilution and filter
Analytes: 0.28% chloride
1.47% orthophosphite
13.3% sulfate
0.04% orthophosphate
Concentrator
Separator
Sample
GuardEWP
CD
3
5
7
9
1
P Waste
RP Cartridge
Eluent(RFIC EG)
1]
2]
3]
[4
[5
[6
L
L
C S
W
SRS
Proprietary & Confidential44 Dionex Confidential
Carbonate Removal
Sample
Concentrator
Guard
Separator
EWP
CD
3
5
7
9
1
P Waste
RP Cartridge
Eluent(RFIC EG)
1]
2]
3]
[4
[5
[6
L
L
C S
W
SRS
CRD 0 1 2 3 4 5 6 7 8 9 10 11 12 13
2.5
5.0
9.0AS18 Control
µS
Minutes
0 1 2 3 4 5 6 7 8 9 10 11 12 13
2.5
5.0
9.0AS18 Recycle Tap water
µS
Minutes
Carbonate
Proprietary & Confidential45 Dionex Confidential
Adsorption Removal
0 5 10 15 20
0.0
0.2
0.4
0.6
0.8
1.0
µS
Minutes
Concentration: 14.00 mM
50.00
Sample
Concentrator
Guard
Separator
EWP
CD
3
5
7
9
1
P Waste
RP Cartridge
Eluent(RFIC EG)
1]
2]
3]
[4
[5
[6
L
L
C S
W
SRS
Column: IonPac AS15 + guard, 4mm
Eluent: 15 mmol/L KOH (EG) for
0-20 min, 60 mmol/L for
20-40 min
Detection: Suppressed conductivity,
External water mode
Flow rate: 1mL/min
Inj. volume: 25 µL
Sample: Pasteurized milk
1:10 dilution and filter
Analytes: 0.2 mg/L nitrite (spiked)
2.5 mg/L nitrate
Proprietary & Confidential46 Dionex Confidential
InGuard™ Cartridges
• Ordering Information (box of 4 cartridges each):
• Ag+ P/N 074038
• H+ P/N 074037
• Na+ P/N 074036
• HRP P/N 074034
• Na+/ HRP P/N 074035
Proprietary & Confidential47 Dionex Confidential
FILTRATION
Proprietary & Confidential48 Dionex Confidential
In-line Filtration with Cartridges and Valves
• Multiple configurations available
• Filter in sample line before injection valve
• In-line on high pressure side
• Dual filters and 10-port valve with back flush pump
• High capacity, high volume filter stack of 35 µm,7 m, 0.45 µm filters
• Low capacity, low volume filter frit, 0.5 m
• Advantages
• Entire sample is filtered − no sample loss
• Small sample volume loaded onto filter maximizes capacity
• Filter back flush minimizes carryover and extends filter lifetime
Proprietary & Confidential49 Dionex Confidential
In-line Filtration: Low Pressure or High Pressure
Suppressor
AnalyticalColumn
GuardColumn
Detector
Auto-
Sampler
L
C
LS
W
P
Pump
Waste
AXP
Waste
1
10
98
6
54
2
7
3
1
10
98
6
54
2
7
3
AXP
Suppressor
AnalyticalColumn
GuardColumn
Detector
Waste
LC
LS
W
P
Pump
Auto-
Sampler
Waste
Filter on the high-pressure side Filter on the low-pressure side
Proprietary & Confidential50 Dionex ConfidentialDionex ConfidentialDionex Confidential
Auxiliary Valves: ICS-2100 and ICS-5000+
Proprietary & Confidential51 Dionex ConfidentialDionex ConfidentialDionex Confidential
Plumbing, Dual In-line Filter with Back Flush
1
10
9
8
6
54
2
7
3
L
C
LS
W
P
AXP
Pump
Auto-
Sampler
Suppressor
Analytical
Column
Guard
Column
Detector
Waste
Waste
Proprietary & Confidential52 Dionex ConfidentialDionex ConfidentialDionex Confidential
AUTOMATED SAMPLE PREPARATION KITS
Proprietary & Confidential53 Dionex ConfidentialDionex ConfidentialDionex Confidential
Automated Sample Preparation Kits
• In-line filter cartridge and 0.5 µm frits P/N 074505
• Replacement 0.5 µm frits P/N 074506
• In-line filter (dual) with back flush P/N 074507
• Hydrophobic organics removal, NG1 P/N 074508
• Hydrophobic organics removal, NG1 (2 mm) P/N 074509
• Humic acids removal, InGuard HRP P/N 074510
• Halides removal, InGuard Ag and Na P/N 074511
• Metals and organics removal, InGuard Na/HRP P/N 074512
Proprietary & Confidential54 Dionex ConfidentialDionex ConfidentialDionex Confidential
Automated Sample Preparation Kits – Example
• Humic acid removal, InGuard HRP w/ concentrator column, P/N 074510
• InGuard HRP (box of 4 cartridges)
• UTAC-ULP1 concentrator column
• ATC-HC trap column (purify loading water)
• Bolt, double cone ferrule (5)
• Double cone ferrules (pack of 10)
• 0.01 inch PEEK tubing (black), 5 feet
• Basic instructions and plumbing diagrams
• Necessary, not included in kit:
• Sample loading
• AXP pump, bottle and cable OR
• EWP for sample loading
• 10-port valve
Proprietary & Confidential55 Dionex ConfidentialDionex ConfidentialDionex Confidential
Summary
• Many new applications notes, briefs and more to come!
• New InGuard inline matrix elimination cartridges
• New concentrator columns
• New automated sample preparation kits
56 Proprietary & Confidential
Thank you for your kind attention!
top related