ics-5000 capillary ion chromatograph€¦ · ion chromatography (part i) ... iodide 0.67 3....
TRANSCRIPT
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ICS-5000ICS 5000Capillary Ion Chromatograph
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Types of Surface Contamination
Organic Impurities
Particles
Organic Impurities
Adsorbed Molecules MetalsIons
S fSurface
14924
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Standard Electronics Industry Methods Specifying Ion Chromatography (Part I)
● SEMI—Recommended Guidelines for Pure Waterfor Semiconductor Processingfor Semiconductor Processing
● ASTM—Guidelines for Electronics Grade Water● SEMI—Standard Test Method for Measurement of
Ionic Contamination on Semiconductor Lead Frames● SEMI—Standard Test Method for Trace Contaminants
in Molding Compoundsin Molding Compounds
12277
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Standard Electronics Industry Methods Specifying Ion Chromatography (Part II)
● SEMI—Alternative to Wet Chemistry for the Analysis of Mixed Acid Etchantsof Mixed Acid Etchants
● U.S. Military—Adhesives, Polymeric, Specifications for Use in Microcircuits
● IPC—Standard for Measurement of Residues on Circuit Boards● IDEMA—Measurement of Extractable/Leachable
Anion Contamination Levels on Drive Components Anion Contamination Levels on Drive Components by Ion Chromatography
● IDEMA—Special Cations Analysis
12278
Main Menu
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ICS-5000 - Dimension of Scale
Overlay of chromatograms from 2 mm and 0.4 mm with appropriate injection volumesj
Capillary (0.4 mm column) IC with 0.4 µL Injection Volume116
LithiumSodium
Potassium
MagnesiumCalcium
Conductivity
0
AmmoniaConductivity[µS]
16Lithium
Sodium
Ammonia
PotassiumMagnesium Calcium
Standard (4 mm column) IC with 40 µL Injection Volume
Conductivity
0 2 4 6 8 10 12 14R t ti Ti [ i ]
0
Conductivity[µS]
Retention Time [min]
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Advantages of Capillary Ion Chromatography
● Capable of continuous operation with minimal intervention ● Ease of use, higher sample throughput, and improved calibration● Improved separation efficiency or speed● Improved trace analysis (10 µL injection = large loop injection)● Improved trace analysis (10 µL injection = large-loop injection)● Improved compatibility with MS and “small sample size”
applications● Possibilities of offering new selectivity for difficult applications
using new columns packed with more costly and difficult-to-make stationary phases stationary phases
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Typical Operating Parameters for Conventional and Capillary RFIC™ Systemsp y y
Conventional RFIC Capillary RFIC
Column ID 4 mm 0.4 mm
Flow Rate 1.0 mL/min 10 µL/min
Injection Loop 25 µL 0.4 µL
Suppressor Dead Volume 60 µL 0.6 µL
EG C rrent (50 mM KOH) 80 4 mA 0 804 mA EG Current (50 mM KOH) 80.4 mA 0.804 mA
EG Current (200 mM KOH) 321.6 mA 3.216 mA
K+ Consumption/Year 26 3 Moles (50 mM KOH) 0 263 Moles (50 mM KOH) K+ Consumption/Year 26.3 Moles (50 mM KOH) 0.263 Moles (50 mM KOH)
H2O Consumption/Year 525 L 5.25 L
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Separation of 9 Anions on a Capillary AS19 Column
)
Column: AS19 column(0.4 mm x 30 cm)
Eluent Source: Capillary EGC KOH cartridge 8.0
de (
1346
6) (1
4115
)72
)e
(165
88)
e (1
5542
)
(147
25)
(159
19)
rate
(150
46)
Sulfa
te (1
2730
) Eluent Source: Capillary EGC-KOH cartridge Eluent: 20 mM KOH Flow Rate: 10 µL/minTemperature: 30 °C
µS
Fluor
idCh
lorite
Br
omate
(14
37Ch
loride
Nitrit
Chlor
ate (
Brom
ide
Nit r S Temperature: 30 C
Suppressor: Electrolytic capillary anion suppressor
Overlay of 30 consecutive runs% retention time RSD: 0.06% for chloride to 0.22% fluoride
µ
0 0 20 00.0
Minutes0.0 20.0Minutes
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Separation of 22 Anions on a Capillary AS19 Column
Column: Capillary AS19 column (0.4 mm x 250 mm)
16.0
lfate
Overlay of 30 consecutive runs% retention time RSD: 0.09% for arsenate to 0.18% for fluoride
Eluent Source: EGC-KOH cartridge Eluent: 10 mM KOH (0 to 10 min), 10 to 52 mM
KOH (10 to 42 min), 52 to 70 mM (42 to 45 min), 10 mM (45 to 50 min)
Sul
Selen
ate
Arse
nate
Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary anion suppressor
µS
e orite
hlorid
e
ate Oxa
late
mate
Phos
phate
umar
at
Fluor
ide
Aceta
teFo
rmat Ch
lBr
omate
Ch
Nitrit
e Chlor
ateBr
omide
Nitra
Malon
ate
dide
ulfate
Chro
m P Fu e
Thioc
yana
te
rchlor
ate0.0 50.0
0.0Minutes
IodTh
iosu Pe
0.0 50.0Minutes
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Anions in Coke on a Capillary AS19 Column
Column: 0.4 x 250 mm AS19 and 0.4 x 50 mm AG19
60.0
Eluent: KOH (RFIC-EG)Gradient: 7 min 15 mM isocratic,
in 18 min to 60 mM gradientCol. Temp.: 30 °C
40.0
[µS
]
-Chl
orid
e
hosp
hate
trate
Col. Temp.: 30 CFlow Rate: 10 µL/minInj. Volume: 0.4 µLDetection: Suppressed ConductivitySample: Coke 1:10
20.0
ondu
ctiv
ity
4 -
itrat
e
-Sul
fate
11 -
Mal
ate
14 -
P h
17 -
Cit
Sample: Coke 1:10
10 0
C
7 -N 9
- 1
0.0 10.0 20.0 30.0-10.0
Retention Time [min]
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Cation Standard on a Prototype Capillary CS16 Column
20.0 µS
m m um
Column: 0.4 x 250 mm CS16 and 0.4 x 50 mm CG16
15.0
y [µ
S]
thiu
m
Sod
ium
um 4 -
Pot
assi
um
5 - M
agne
siu
6 - C
alci
u
Eluent: MSA (RFIC-EG)Gradient: 6 mM in 30 min to 66 mM Col. Temp.: 40 °CFlow Rate: 0.010 mL/min
5 0
10.0
Con
duct
ivity
1 - L
it
2 -
3 - A
mm
oni u 4 5 Flow Rate: 0.010 mL/min
Inj. Volume: 0.4 µLDetection: Suppressed ConductivitySample: 6 Cation Standard 1:50
2 0
5.0
min
C
0.0 10.0 20.0 30.0-2.0 min
Retention Time [min]
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Fast Separation of Six Cations on a Capillary CS12A-5 Column
20 1 23
5
4
6
Column: CS12A-5 column (0.4 mm x 15 cm)Eluent Source: Capillary EGC-MSA cartridge Eluent: 20 mM MSA
18 µL/min Flow Rate: 12 to 18 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary cation suppressor
µS
14 µL/min
16 µL/minPeak Retention Time Concentration
at 18 µL/min (mg/L) (minutes)
1 Lithium 1 037 0 5 14 µL/min
12 µL/min
1 23 5
46
1. Lithium 1.037 0.5 2. Sodium 1.250 2.03. Ammonium 1.443 2.54. Potassium 1.813 5.0 5. Magnesium 4.507 2.56. Calcium 5.790 5.0
0.0 2.0 4.0 6.0 8.0 10.0 12.00
Minutes
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Rapid Determination of Cations - Treated Waste Water
Column: CS12A-5 column (0.4 mm x 15 cm)Eluent Source: Capillary EGC-MSA cartridge Eluent: 28 mM MSA 1
Flow Rate: 18 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary cation suppressor
O l f 20 ti Sample: Treated Waste Water (1:10 dilution)
Peak Concentration (mg/L)
Overlay of 20 consecutive runsRetention time RDS (n=20): 0.053% (calcium) to 0.28% (sodium)Peak area RSD (n=20): 0.5% (sodium) to 0.9% (magnesium)
1. Sodium 19.62. Potassium 0.83. Magnesium 3.54. Calcium 3.1
23
42
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Trace Analysis Using Capillary Ion Chromatography
● Large-volume direct injection or pre-concentrationLarge volume direct injection or pre concentration
● A 10 µL injection onto a 0.4 mm ID column is equivalent to a 1000 µL injection onto a 4 mm I.D. column.
● Loading a 250 L sample onto a capillary concentrator can be accomplished with an AS autosampler in shorter time than loading a 25 mL sample onto a con entional concentrator ith an AS HV conventional concentrator with an AS-HV.
● Suitable for samples with low levels of matrix ions
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Trace Analysis, Microbore IC
4 00
Reactor water sample, 75 ng/L Chloride
FluorideChloride 2 mm AS14 column
3.00
4.00 2 mm AS14 column0.38 mL/ min
2.00
µS
1.00
0.00
10 2015Retention time, minutes
2 mL Sample, Direct Injection
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Inorganic Anions at Trace Concentrations with 10 µL Injection
Column: Prototype AS20 column (0.4 x 250 mm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 35 mM KOH Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary suppressorDetection: Suppressed conductivityInjection Volume: 10 µL
0.22511
Injection Volume: 10 µL Peaks: 1. Thiosulfate 0.33 µg/L
2. Iodide 0.673. Thiocyanate 0.674. Perchlorate 1.0
µS4. Perchlorate 1.0
22 33 44
0 160.210
Minutes
1515
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Trace Bromate in Drinking Water Large Loop (10 µL) Injections
2.0
Column: Capillary AS19 column (0.4 x 250 mm)2.0
Brom
ate
Eluent Source: Capillary EGC-KOH cartridge Eluent: 10 mM KOH (0 to 10 min), 10 to 52 mM
KOH (10 to 42 min), 52 to 70 mM (42 to 45 min) 10 mM (45 to 50 min)
µS
(42 to 45 min), 10 mM (45 to 50 min) Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Electrolytic capillary anion suppressor
Sunnyvale drinking waterSunnyvale drinking water + 2 ppb bromate
0.0 40.00.50
Minutes
Sunnyvale drinking water + 2 ppb bromate Sunnyvale drinking water + 4 ppb bromate
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Separation of Inorganic Anions at Trace Concentrations10 µL Injection
0.47
Column: AS19 column (0.4 mm x 25 cm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 20 mM KOH 1Flow Rate: 10 µL/minTemperature: 30 °CSuppressor: Capillary anion suppressor
1
3 7
µS
Detection: Suppressed conductivity Injection Volume: 10 µL
P k C t ti ( /L)
2 4 56
Peak Concentration (µg/L)1. Fluoride 0.2 2. Chloride 0.33. Nitrite 1.04. Bromide 1.05 Nit t 1 0
—— Standards in deionized water—— Deionized water
Minutes0.0 20.00.36
5. Nitrate 1.06. Carbonate 7. Sulfate 1.0
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Trace Analysis Using Capillary Ion Chromatography
● Two-dimensional ion chromatography using a capillary column in the second dimension
● Perform large-loop injection and separation of matrix ions using a 4 mm ID column in the 1st dimension
F th i f i t t i t t l ft i i th 1 t● Focuses the ions of interest in a concentrator column after suppression in the 1stdimension
● Perform separation using a 0.4 mm ID column of different selectivity in the 2nd dimensiondimension
● Provide sensitivity enhancement that is proportional to the flow rate ratio (e.g. a factor of 100)
● Suitable for samples with high levels of matrix ions
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ICS-5000 2D RFIC™ System Using a Capillary Column in the Second Dimension
Auto-
Waste
L
WWaste
Sampler Detector
CRD 200
L
W
CL
S
P
Pump
Suppressor
CL
S
P
Capillary Concentrator Column
0.4 mm Guard & Sample Loop
4 mm Guard & Analytical ColumnSuppressor
Capillary Pump
Analytical Column
DetectorDetector
Standard Bore: 4 mm, 1 mL/min Capillary: 0.4 mm, 10 L/min
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Determination of Trace Perchlorate Using a 2D RFIC™ System with a Second-Dimension Capillary Column
1st dimension chromatogram
A. First-Dimension ConditionsColumn: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min
1.0
chromatogram1.0 S full scale Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300
Inj. Volume: 4000 µLTemperature: 30 °CB. Second-Dimension Conditions
µS
1
10.0
2 d di i
B. Second Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOHSuppressor: Capillary Anion SuppressorTemperature: 30 °C
0.00.0 60.0
1
µS
2nd dimension chromatogram10 S full scale
Temperature: 30 CConcentrator: Capillary concentrator,
5000 µL of 1st dimension suppressed effluent (19 to 24 minutes)
Peak: 1 Perchlorate 1 0 g/L
1
0.0 60.00.0 Minutes2
Peak: 1. Perchlorate 1.0 g/L
Perchlorate Peak Area1st Dimension: 0.0115 µS*min2nd Dimension: 1.75 µS*minµ
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Determination of Trace Perchlorate Using a 2D RFIC™ System with a Second-Dimension Capillary Column
A. First-Dimension ConditionsColumn: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min El t 65 M KOH (EG)
1.00
rate
Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300 Inj. Volume: 4000 µLTemperature: 30 °CB. Second-Dimension Conditions
Perch
lor
B. Second Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOH (EG)Suppressor: Capillary Anion SuppressorT t 30 °C
µS
Temperature: 30 °CConcentrator: Capillary concentrator,
5000 µL of 1st dimension suppressed effluent (19 to 24 minutes)
Deionized Water 30 ng/L perchlorate in deionized water
29.0 44.00.00
Minutes
30 ng/L perchlorate in 1000 mg/L chloride,sulfate and bicarbonate
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Determination of Perchlorate in Bottled Water Samples Using an ICS-5000 2D RFIC™ Systemg y
A. First-Dimension ConditionsColumn: IonPac® AG16 AS16 4 mm 2.5 hl
orat
e
Column: IonPac® AG16, AS16, 4 mm Flow Rate: 1.0 mL/min Eluent: 65 mM KOH (EG)Suppressor: 4 mm SRS 300 Inj. Volume: 4000 µL
Perc
h
Temperature: 30 °CB. Second-Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/minEluent: 35 mM KOH (EG)
µSEluent: 35 mM KOH (EG)Suppressor: Capillary Anion SuppressorTemperature: 30 °CConcentrator: Capillary concentrator,
5000 µL of 1st dimension —— Brand A bottled water (263 ng/L perchlorate)B d B B ttl d t (38 5 /L hl t ) suppressed effluent (19 to 24 minutes)13
30 0 45 0-1.0
Minutes
—— Brand B Bottled water (38.5 ng/L perchlorate)—— 30 ng/L perchlorate in DI water—— DI water
30.0 45.0Minutes
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Determination of Trace Bromate in a Bottled Water Sample Using an ICS-5000 2D Capillary RFIC System g p y y
0.5
e
A. First-Dimension ConditionsColumn: IonPac® AG19, AS19, 4 mm Fl R 1 0 L/ i
Brom
ate Flow Rate: 1.0 mL/min
Eluent: 10 to 60 mM KOH (EGC-KOH )Suppressor: 4 mm SRS 300 Inj. Volume: 1000 µLTemperature: 30 °C
µS
Temperature: 30 C
B. Second-Dimension ConditionsColumn: Prototype AS20 (0.4 mm x 25 cm)Flow Rate: 10 µL/min
O ( GC O )
—— Dionized water
Eluent: 35 mM KOH (EGC-KOH)Suppressor: Capillary Anion SuppressorTemperature: 30 °CConcentrator: Capillary concentrator,
2500 µL of 1st dimension —— Brand A bottled water (54 ng/L)—— 100 ng/L bromate in deionized water—— 30 ng/L bromate in deionized water
17.0 20.0 -0.3
Minutes
1
2500 µL of 1st dimension suppressed effluent (7.5 to 10 minutes)
Minutes
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Operating Conditions of a Capillary IC System with MS/MS Detection
● Capillary IC System:● Column: Prototype AS20 (0.4 mm x 250 mm)● Eluent Source: Capillary EGC-KOH cartridge ● Flow Rate: 10 to 20 µL/min● Temperature: 30 °CTemperature: 30 C● Suppressor: Electrolytic capillary anion suppressor
operated in the external water mode (20 µL/min) ● ABI SCIEX API 2000TM MS/MS System:
P t dditi f t it il t 15 L/ i i d d 0 15 b ● Post-suppressor addition of acetonitrile at 15 µL/min via a grounded 0.15 mm bore mixing Tee
● Negative ESI with optimized probe position ● Optimized multiple reaction monitoring (MRM) channels for target analytes.
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Determination of Inorganic and Organic Anions Using a Capillary IC and API 2000™ MS/MS System
Column: Prototype AS20 (0.4 mm x 250 mm)Eluent Source: Capillary EGC-KOH cartridge Eluent: 4-55 mM KOH Flow Rate: 15 µL/minTemperature: 30 °C
520006
11 Temperature: 30 CSuppressor: Electrolytic capillary anion suppressor Detection: API2000 MS/MS with post suppressor
addition of acetonitrile at 15 µL/min; Negative ESI
Injection vol.: 10 µLj µMRM (m/z)
Peaks: 1. Acetate 10 g/L 59/592. Formate 10 45/453. Chlorite 10 67/514. Bromate 10 126.7/110.8ns
ity, c
ps
8 5. Bromoacetate 10 137/78.86. Dichloroacetate 10 127/82.97. Dibromoacetate 10 214.7/170.78. Chlorate 10 83/66.99. Bromide 10 79/79
Inten
1
34 5
79
8
10. Nitrate 10 62/4611.Trichloroacetate 10 161/116.812.Tribromoacetate 10 250.8/78.813.Perchlorate 1.0 99/83
Minutes0.02000
2 10 12 13
28.0Minutes 28.0
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Separation of Six Monosaccharides
Column: CarboPac PA 20 (0.4 mm x 150 mm)
T 30 °C
40
Temp.: 30 °CEluent: 10 mM KOH Flow Rate: 10 µl/minInj. Vol. : 0.4 LDetection: PAD (Carbohydrate Quadruple
30
2Detection: PAD (Carbohydrate Quadruple
Waveform)Electrode: ED Au
Sample: Standards (10 µM)
nC 20
4
3
1
Peaks: 1. Fucose (Fuc)2. Galactoseamine (GalN) 3. Glucoseamine (GalN)
10 64
5
4. Galactose (Gal)5. Glucose (Glc)6. Mannose (Man)
Minutes0 2 4 6 8 10 12
0
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ICS-5000 Technology – Ease of Use
Guard and Separation ColumnCRD 200
Side view of ACESSide view of ACESSuppressor
Suppressor Injection ValveEG Degas
j
-
ICS-5000 System Top Values
● Just Add Water once a Quarter –Add Samples any TimeAdd Samples any Time
● Just Increase Sensitivity –Ultimate Sensitivity (IC x IC)
● Just Save Money● Just Save Money –Low Cost of Ownership
The Next Big Thing in IC is Small
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Summary
● Capillary RFIC™ systems with suppressed conductivity detection offer highly reproducible isocratic and gradient separations of target analytes p g p g y
● Capillary RFIC™ systems provide improved capability for trace analysis
● Capillary RFIC™ systems can be used to achieve fast separation (Fast IC) ● Capillary RFIC™ systems can be used to achieve fast separation (Fast IC) and determination of common anions and cations
● Capillary RFIC systems with MS/MS and electrochemical detection are highly iti l ti l t lsensitive analytical tools
● Capillary RFIC systems leads to improved ion chromatographic methods for determination of ionic analytes in CMP consumables, chemicals, DI water and y , ,on post-CMP surfaces
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Anion Sample
Peak Name Amount (ppt)
1.00
(ppt)F 24.033Cl 22.307
NO2 42 532NO2 42.532
µS
F Cl NO2
–0.200 5 10 15 20 26
Minutes23414
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Anion Sample
Overlay of 20 Runs 0.206
FF
ClNO2
SO4µS NO2 Br NO3 PO4
–0.0744.1 10 15 20 23.7
Minutes23415
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Cation Sample
Peak Name Amount (ppt)
0.500
(ppt)Li 11.511Na 28.403
NH4 13 499NH4 13.499K 15.197
Mg 7.729Ca 11 238
µSCa 11.238
Li Na NH4 KMg Ca
–0.1000 5 10 15 20 26Minutes
23420
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Overlay—Cation Sample
Overlay of 20 Runs0.312
Peaks: 2. Li 6.7673. Na 9.2334. NH4 11.7805. MEA 12.440y0.3126. DEA 13.9537. — 14.5678. K 16.7579. TEA 17.477
10 17 853
µS
10. — 17.85311. Mg 21.72012. Ca 24.000
2
µS
3
1112
47 8 9
106
–0 029
5 96
6.1 10 15 20 24.70.029
Minutes23421
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Cation Blank
1.00
µS
Na NH4 Mg Ca
–0.20
Minutes0 5 10 15 20 26
0.20
23423