ic_sampl_prep_26062003_e.ppt 1
IC ICIC IC
IC
Metrohm inline sample preparationMetrohm inline sample preparationTechniques for analytical successTechniques for analytical success
Metrohm Ion Chromatography
Bart Cleeren, Metrohm België
ic_sampl_prep_26062003_e.ppt 2
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
ic_sampl_prep_26062003_e.ppt 3
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
ic_sampl_prep_26062003_e.ppt 4
IC ICIC IC
IC
Metrohm Ion Chromatography
UltrafiltrationUltrafiltration
Inline sample preparationInline sample preparation
Ultrafiltration cell
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
S Sample
P2 Peristaltic pump
A position fill
C
P1
E D
2
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IC ICIC IC
IC
Metrohm Ion Chromatography
Ultrafiltration CellUltrafiltration Cell
Inline sample preparationInline sample preparation
No particles on the acceptor side
Big particles are flushed away
and do not clog the membrane
High flow on the sample side
Low flow on the acceptor side
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IC ICIC IC
IC
Metrohm Ion Chromatography
UltrafiltrationUltrafiltration
Inline sample preparationInline sample preparation
# 1 Sample filtration
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
S Sample
P2 Peristaltic pump
A position fill
C
P1
E D
2
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IC ICIC IC
IC
Metrohm Ion Chromatography
UltrafiltrationUltrafiltration
Inline sample preparationInline sample preparation
# 2 Sample injection
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
S Sample
P2 Peristaltic pump
A position inject
C
P1
E D
2
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IC ICIC IC
IC
Metrohm Ion Chromatography
Ultrafiltration: vegetable juiceUltrafiltration: vegetable juice
Inline sample preparationInline sample preparation
A Supp 4 – 250
1 Organics n.q.
2 Organics n.q.
3 Cl– 4141
4 NO3– 102
5 HPO42– 577
6 SO42– 842
7 Oxalate n.q.
ppt
NaHCO3/Na2CO3; 1.7/1.8 mmol/L; dilution 1:100; 0.15 µm rec. cellul.
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
ic_sampl_prep_26062003_e.ppt 10
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Dialysis cell, acceptor solution
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
P3 Peristaltic pump (2 Ch.)
Dialysis cell
A Acceptor solution
DialysisDialysis
C
P1
E D
2
A E
P1P2
P3
A D
CX
X
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 2 Stopped flow dialysis
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
Injection Valve «B»
Dialysis cell
A Acceptor solution
DialysisDialysis
C
P1
E D
2
A
P3
P2
A
P1
C
DEX
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IC ICIC IC
IC
Metrohm Ion Chromatography
Dialysis cellDialysis cell
Inline sample preparationInline sample preparation
Continuous flow dialysis
Exclusion diameter 0.2 µm
Ions can pass
Oil droplets, fat micelles, particles are excluded
Strong concentration gradient
No equilibrium concentration
Cellulose acetate membrane
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IC ICIC IC
IC
Metrohm Ion Chromatography
Dialysis cellDialysis cell
Inline sample preparationInline sample preparation
Stopped flow dialysis
Dialysis time 2 ... 8 min
Sample volume 10 mL
No loss of concentration on the sample side
Equilibrium concentration
Dialysis rate > 99 %
No filtration, no pre concentration
Unique technique, that had significantly improves the field of application for IC
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IC ICIC IC
IC
Metrohm Ion Chromatography
Dialysis: milkDialysis: milk
Inline sample preparationInline sample preparation
Metrosep Dual 1 – 70
1 Chloride 938
2 Nitrate n.q.
3 Phosphate n.q
4 Sufate 103
ppm
NaHCO3/Na2CO3; 2.4/2.0 mmol/L; dilution 1:5; 0.2 µm cellul. acetat
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IC ICIC IC
IC
Metrohm Ion Chromatography
Dialysis: cutting oil emulsionDialysis: cutting oil emulsion
Inline sample preparationInline sample preparation
Metrosep Dual 2
1 Chloride 74.7
2 Nitrite 20.5.
3 Nitrate 23.9
4 n. det. -
5 Phosphate 25.2
6 Sulfate 192.7
7 n. det. -
NaHCO3/Na2CO3; 2.0/1.3 mmol/L; dilution 1:5; 0.2 µm cellul. acetat
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 1 Sample preconcentration
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
C
P1
D
P3 2
S
Inline pre concentrationInline pre concentration
E
C
P1P 2
D
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 2 Sample analysis
E Mobile phase: eluent
P 1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P 2 Peristaltic pump
C
P1
E D
P3 2
S
Inline preconcentrationInline preconcentration
E
C
D
P1P 2
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline preconcentration: ultra pure waterInline preconcentration: ultra pure water
Inline sample preparationInline sample preparation
Metrosep A Supp 5 – 150
1 Acetate 2.3
2 Formate 22.0
3 Chloride 13.0
4 Carbonate n.q.
5 Nitrate 4.5
6 Phosphate 16.0
7 Sulfate 8.5
8 Oxalate 12.0
ppt
NaHCO3/Na2CO3; 1.0/3.2 mmol/L; 20 mL preconc,
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline preconcentration: ultra pure waterInline preconcentration: ultra pure water
Inline sample preparationInline sample preparation
Metrosep Dual 2
1 Fluoride 45 – 150
2 Chloride 100 – 210
3 Bromide 0 – 100
4 Nitrate 10 – 112
5 Sulfate 40 – 145
ppt
NaHCO3/Na2CO3; 2.0/3.2 mmol/L; 10 mL preconc, spiked 100 ppt
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
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IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Transfer solution «T»
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
Injection Valve «B»
P3 Peristaltic pump
T Transfer solution
A position fill, B position fill
C
P1
E D
2
T
Matrix eliminationMatrix elimination
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IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 1 Preconcentrator column inline
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
Injection Valve «B»
P3 Peristaltic pump
T Transfer solution
A position fill, B position fill
C
P1
E D
2
T
Matrix eliminationMatrix elimination
ic_sampl_prep_26062003_e.ppt 24
IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 2 Sample transfer, matrix elim.
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
Injection Valve «B»
P3 Peristaltic pump
T Transfer solution
A position fill, B position inject
C
P1
E D
2
T
Matrix eliminationMatrix elimination
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IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 3 Sample inject
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2 Peristaltic pump
Injection Valve «B»
P3 Peristaltic pump
T Transfer solution
A position inject, B position inject
C
P1
E D
2
T
Matrix eliminationMatrix elimination
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IC ICIC IC
IC
Metrohm Ion Chromatography
Matrix elimination: organic solventsMatrix elimination: organic solvents
Inline sample preparationInline sample preparation
50 µL iPrOH
B with matrix elimination
A without matrix elimination
ppt
F–Ac–
443 Cl–
30 NO3– 28 SO4
2–
425 Cl–
24 NO3– 17 SO4
2–
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IC ICIC IC
IC
Metrohm Ion Chromatography
Matrix elimination: 35 % HMatrix elimination: 35 % H22OO22
Inline sample preparationInline sample preparation
left:
without m.e.
Loop 20 µL
right:
with m.e.
Loop 20 µL
transfer vol . 2 mL
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IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
ic_sampl_prep_26062003_e.ppt 29
IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
833.0030 IC Sample Prep. Unit
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2, 3 Peristaltic pumps
Injection Valve «B»
T Transfer solution
833 IC Sample Prep
A position inject, B position fill
C
P1
E D
2
T
Matrix neutralizationMatrix neutralization
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IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 1 Preconcentrator column inline
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2, 3 Peristaltic pumps
Injection Valve «B»
T Transfer solution
833 IC Sample Prep
A position fill, B position fill
C
P1
E D
2
T
Matrix neutralizationMatrix neutralization
ic_sampl_prep_26062003_e.ppt 31
IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 2 Sample transfer/neutralization
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2, 3 Peristaltic pumps
Injection Valve «B»
T Transfer solution
833 IC Sample Prep
A position fill, B position inject
C
P1
E D
2
T
Matrix neutralizationMatrix neutralization
ic_sampl_prep_26062003_e.ppt 32
IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 4 Sample inject
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2, 3 Peristaltic pumps
Injection Valve «B»
T Transfer solution
833 IC Sample Prep
A position inject, B position inject
C
P1
E D
2
T
Matrix neutralizationMatrix neutralization
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IC ICIC IC
IC
0.74 F–
3.6 Cl–
0.97 NO3–
0.98 HPO42–
1.1 SO42–
Metrohm Ion Chromatography
Matrix neutralization: caustic sodaMatrix neutralization: caustic soda
Inline sample preparationInline sample preparation
30 % NaOH, 20 µL loop
B with matrix elimination
A without matrix elimination
ppm
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IC ICIC IC
IC
Metrohm Ion Chromatography
Matrix neutralization: caustic sodaMatrix neutralization: caustic soda
Inline sample preparationInline sample preparation
Metrosep Dual 2
1 Chloride 25.08
2 Carbonate n.q.
3 Chlorate 4.76
4 Sulfate 10.43
ppm
NaHCO3/Na2CO3; 1.7/1.8 mmol/L; 50 % NaOH, 20 µL loop
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IC ICIC IC
IC
1
Metrohm Ion Chromatography
Matrix neutralization: ammoniaMatrix neutralization: ammonia
Inline sample preparationInline sample preparation
Metrosep A Supp 4 – 250
1 Formate n.q.
2 Chloride 0.03
3 Nitrite n.q.
4 Bromide 0.95
5 Nitrat 0.04
6 Carbonate n.q.
7 Sulfate 0.13
ppm
NaHCO3/Na2CO3; 1.7/1.8 mmol/L; 26 % NH3, 20 µL loop
23
4
5 67
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IC ICIC IC
IC
P3
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
OH cartridge
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P2, 3 Peristaltic pumps
Injection Valve «B»
T Transfer solution
Cartridge
A position fill, B position fill
C
P1
E D
2
T
Matrix neutralizationMatrix neutralization
Ctr
ic_sampl_prep_26062003_e.ppt 37
IC ICIC IC
IC
Metrohm Ion Chromatography
Matrix neutralization: HClMatrix neutralization: HCl
Inline sample preparationInline sample preparation
10 µL
HCl direct injection
ppm
Metrosep C2 – 250
ic_sampl_prep_26062003_e.ppt 38
IC ICIC IC
IC
Metrohm Ion Chromatography
Matrix neutralization: HClMatrix neutralization: HCl
Inline sample preparationInline sample preparation
Metrosep C2 – 250
1 Nickel n.q.
2 Sodium 5.4
3 Ammonium 1.3
4 Potassium 0.8
5 Magnesium 1.5
6 Calcium 0.8
ppm
Tartaric-/dipicolinic acid; 4.0/0.75 mmol/L; 7 mol HCl, 10 µL loop
1
2
3
4 5 6
ic_sampl_prep_26062003_e.ppt 39
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Ultra filtrationStop flow dialysisPre concentration techniqueMatrix eliminationMatrix neutralizationIn- line calibration
ic_sampl_prep_26062003_e.ppt 40
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
Standard S, flow path
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P1,2,3 Peristaltic pumps
Injection Valve «B»
S Standard
A position inject, B position fill
Inline calibrationInline calibration
C
P1
E D
P3 2
S
ic_sampl_prep_26062003_e.ppt 41
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 1 Measurement of standard
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P1,2,3 Peristaltic pumps
Injection Valve «B»
S Standard
A position inject, B position fill
C
P1
E D
P3 2
S
Inline calibrationInline calibration
ic_sampl_prep_26062003_e.ppt 42
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 2 Preconcentrator inline
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P1,2,3 Peristaltic pumps
Injection Valve «B»
S Standard
A position fill, B position fill
C
P1
E D
P3 2
S
Inline calibrationInline calibration
ic_sampl_prep_26062003_e.ppt 43
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 3 Transfer of standard
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P1,2,3 Peristaltic pumps
Injection Valve «B»
S Standard
A position fill, B position inject
C
P1
E D
P3 2
S
Inline calibrationInline calibration
ic_sampl_prep_26062003_e.ppt 44
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 4 Inject of standard
E Mobile phase: eluent
P1 High pressure pump
Injection valve «A»
C Analytical column
»MSM» Suppressor
D Conductivity detector
P1,2,3 Peristaltic pumps
Injection Valve «B»
S Standard
A position inject, B position inject
C
P1
E D
P3 2
S
Inline calibrationInline calibration
ic_sampl_prep_26062003_e.ppt 45
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparation
# 1: Transfer of 2 mL ultrapure water to the preconcentrator
Blank value
# 2: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back once
Calibration level 1
# 3: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back twice
Calibration level 2
# 4: Transfer of 2 mL ultrapure water to the preconcentrator. Valve B is thrown from fill to inject and back three times
Calibration level 3, etc
Inline calibrationInline calibration
ic_sampl_prep_26062003_e.ppt 46
IC ICIC IC
IC
Metrohm Ion Chromatography
Inline sample preparationInline sample preparationInline calibrationInline calibration
100 ppt 100 ... 400 ppt
ic_sampl_prep_26062003_e.ppt 47
IC ICIC IC
IC
inline sample preparation ?inline sample preparation ?Metrohm can do thatMetrohm can do that
Metrohm Ion Chromatography