This document discusses speciation analysis using ion chromatography coupled with inductively coupled plasma-mass spectrometry (IC-ICP-MS). It provides an overview of the technique, including separation of species using ion chromatography, detection of elements using ICP-MS, and integration of the two systems. Examples are given of speciation analysis of chromium, arsenic, and sulfur to determine different chemical forms in environmental and drinking water samples. The technique allows sensitive detection of multiple elements and their species simultaneously for applications such as monitoring regulatory compliance and studying environmental processes.

1. 1
The world leader in serving science
Complete Inorganic Elemental
Speciation Solutions for Environmental
Applications
Mr. Kristan Bahten
Thermo Scientific, Sunnyvale, CA, USA
Dr. Shona McSheehy
Thermo Scientific, Bremen, Germany

2. 2
Metals in the Environment
Natural
sources
Industrial
sources
Geochemical
cycling
Uptake in
food chain Wastes

3. 3
Metals in the Environment
Hg
As
Cr
Pb Sn

4. 4
Metals in the Environment and Speciation
HO-As-OH
|
OH
O
||
H3C-As-CH3
|
OH
Environmental Fate
Mobility Toxicity
Bioavailability
Reactivity
[Cr(H2O)6]3+
H3C-Hg+
Hg0
Cr2O7
2-

5. 5
Who Needs Speciation?
Industry Needs
Environment
• Environmental concerns
• Mobility and reactivity
Food Safety
• Toxicity
• Nutritional value
Occupational Exposure and
Consumer Goods
• Toxicity
• Mobility
Pharmaceutical
• Toxicity
• Activity
Petrochemical
• Contamination
• Remediation

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Legislation – the Principal Driving Factor
Industry Legislation
Environment
• TBT in natural waters
• Waste water monitoring
• Hexavalent chromium in drinking waters
• Geochemical processes
Food Safety
• MeHg+ in fish
• Bromate in drinking waters
Occupational Exposure and
Consumer Goods
• Hexavalent chromium in: toys, workplace air
Pharmaceutical
• Characterisation of food
supplements
• USP
Petrochemical
• Sulfur, mercury remediation
• Contamination of processes/catalysts

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Why Use ICP-MS for Environmental Analysis?
• It can measure almost the whole
periodic table in just about everything
• Information derived:
• Elemental concentrations
• High precision isotope ratios
• Species concentrations
• Particle number and composition
• High matrix tolerance
• Interference removal
• High sensitivity
• > 9 orders dynamic range
Thermo Scientific™ iCAP™ ICP-MS

8. 8
What is ICP-MS?
Inductively Coupled Plasma - Mass Spectrometry

9. 9
What is ICP-MS?
1. Sample
introduction
Inductively Coupled Plasma - Mass Spectrometry

10. 10
What is ICP-MS?
2. Elements in
sample ionized
in Inductively
Coupled
Plasma
Inductively Coupled Plasma - Mass Spectrometry

11. 11
What is ICP-MS?
3. Sampling
interface
Inductively Coupled Plasma - Mass Spectrometry

12. 12
What is ICP-MS?
4. Interference
removal - CRC
Inductively Coupled Plasma - Mass Spectrometry

13. 13
What is ICP-MS?
5. Quadrupole
Mass Spectrometer
Inductively Coupled Plasma - Mass Spectrometry

14. 14
What is ICP-MS?
6. Detector
Inductively Coupled Plasma - Mass Spectrometry

15. 15
How Can We Perform Speciation Analysis?
Separation Detection
Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ System
iCAP Q ICP-MS System
Thermo Scientific™ TRACE 1310 Gas Chromatography

16. 16
Principle Steps of Speciation Analysis
Extraction DetectionSeparation
Sample containing
various compounds
Preservation of
original species
distribution
Loss of species
during sample
preparation
Transformation of
species
Different separation
mechanisms
Ion chromatography:
Analyte retention is
achieved by interaction
of charges with
stationary phase
ICP-MS detects the
element enclosed in a
species
Accurate and reliable
quantification of
different compounds
containing the same
element

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SEM Image of 4 µm Supermacroporous Bead
What are the Advantages of Ion Chromatography?
• Metal-free PEEK systems
• Powerful separation chemistries
• Reagent-Free™ Ion
Chromatography (RFIC™)
• Extensive IC product line for full
flexibility
• Smaller particles provide better
performance
• Fast run times with higher flow
rates using 150 mm columns
• High resolution with standard
flow rates using 250 mm columns
New High Efficiency Thermo
Scientific™ Dionex™ IonPac™ 4 µm
HPIC™ Columns
Benefits:

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Dionex Ion Chromatography System Portfolio
Thermo Scientific
Thermo Scientific
Dionex ICS-1100
Basic Integrated
Ion Chromatography
System
Thermo Scientific
Thermo Scientific
Dionex ICS-900
Starter Line Ion
Chromatography
System
Thermo Scientific
Thermo Scientific
Dionex ICS-1600
Standard
Integrated Ion
Chromatography
System
Thermo Scientific™
Thermo Scientific
Dionex ICS-2100
Reagent-Free Ion
Chromatography
(RFIC) System
Dionex ICS-5000+ HPIC
Ion Chromatography
System
Thermo Scientific
Thermo Scientific
Dionex ICS-4000
Capillary HPIC Ion
Chromatography
System
RFIC

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Speciation with IC-ICP-MS
• Fully integrated software:
• Thermo Scientific™ Qtegra™ Intelligent
Scientific Data Solution ISDS with
Thermo Scientific™ Dionex™
Chromeleon™ Chromatography Data
System (CDS) plug-in drivers to control
IC or HPLC
• No need for external hardware trigger
• Fully integrated chromatographic data
processing software
• Automated peak integration, species
quantification and internal standard
correction
• Thermo Scientific Dionex IC
systems are entirely metal-free
(PEEK)
• Simple hardware connection
IC-ICP-MS is the ideal choice for trace elemental speciation

20. 20
Data
System
• Very simple hardware
connection:
• Simple interchange between
standard ICP-MS analysis
and IC-ICP-MS
• No need to turn off plasma
• A single software interface for
both the IC and ICP-MS:
• Chromeleon CDS software
interface built into workflow
• Fully integrated analysis and
automated shutdown
• No trigger cable needed
• One sample driving both
devices
Inert tubing
0.125 mm i.d.
A Complete Integrated IC-ICP-MS System

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EPA Method 200.8 Determination of Metals and Trace
Elements in Water and Wastes by ICP-MS
• EPA 200.8 used for the
determination of twenty-two
dissolved elements in ground,
surface and drinking waters
• Method applicable to wide
variety of samples
• Thousands of analyses
required/week in a typical
routine laboratory
Isotope
LCS
Certified Found Recovery
(µg/kg)$
(µg/L) (%)
9
Be 0.005* 0.005 100.0
27
Al 49.5 51.6 104.2
51
V 0.317 0.333 104.9
52
Cr 0.208 0.222 106.7
55
Mn 4.33 4.45 102.8
56
Fe 91.2 88.1 96.6
60
Ni 0.476 0.462 97.1
63
Cu 17.4 18.4 105.5
66
Zn 0.845 0.925 109.5
75
As 0.413 0.420 101.8
111
Cd 0.006 0.006 104.3
135
Ba 14 14.4 103.0
208
Pb 0.081 0.081 100.0
238
U 0.093 0.092 98.9
(ug/g) (mg/L) (%)
23
Na 5.38 5.58 103.7
25
Mg 2.54 2.65 107.5
39
K 0.839 0.892 106.3
43
Ca 10.5 10.1 96.2

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Matrix Tolerance and the iCAP Q ICP-MS Interface
• Unique design with:
• Optimized thermal properties
• Adjustable matrix tolerance

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EPA Method 200.8 Determination of Metals and Trace
Elements in Water and Wastes by ICP-MS
Internal standard recovery within EPA protocol defined limits of 60 -
125 % of initial internal standard over complete 15 hour analysis

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Chromium in Drinking Water
• Current requirements in drinking water:
Legislation MCL (µg/L)
EPA National Primary Drinking
Water Regulations
100 µg Cr/L
European Commission Directive
1998/83/EC
50 µg Cr/L
California Legislation PHG (µg/L)
California EPA (OEHHA ) 1999 2.5 µg Cr/L
0.2 µg Cr(VI)/L
California EPA (OEHHA ) 2009 0.06 µg Cr(VI)/L
California EPA (OEHHA ) Dec
2010 revision
0.02 µg Cr(VI)/L

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Considerations for HPLC-ICP-MS Parameters
• The determination of Cr by ICP-MS is complicated by
polyatomic interferences:
• 40Ar12C+ on 52Cr
• 37Cl16O+ on 53Cr
• IC and sample preparation parameters need to be chosen
carefully due to the complex redox chemistry of Cr
Chemical forms of Cr as a function of pH and potential
HCrO4
- CrO4
2-
H2CrO4
[Cr(H2O)6]3+
Cr3+
Cr(OH)3(s) Cr(OH)4
-
Cr(OH)2+
Cr(OH)2
+
Cr(OH)3
°
Cr(VI)
Cr(III)
pH
0,7
964
6,5
Eh
Cr2O7
2-

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QCell - Interference Removal by Collision/Reaction Cell
• Collision/Reaction Cell
• A multipole/flatapole enclosed in a
chamber
• Controlled flow of gas into the cell
• Interaction of ions with the gas
mainly by collisions
• If reactive gas used, reactions
occur
• All cells are reaction cells
M+ and
XnYn’
+
M+ only
out
• RF field produced by Flatapole
• Advantages:
• Automatic low mass cut-off
• High transmission
• Non consumable

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QCell - Interference Removal by Collision/Reaction Cell
• Low mass cut-off:
• Prevents recombination of
precursors in cell  reduced BECs
Anal. LMCO Interferences Precursors
51V 35 35Cl16O, 37Cl14N,
34S16OH
H, N, O, S,
Cl
56Fe 39 40Ar16O, 40Ca16O O, Ar, Ca
63Cu 45 40Ar23Na,
12C16O35Cl, 31P32S
C, N, O, Na,
P, S, Cl, Ar
75As 47 40Ar35Cl, 40Ca35Cl,
40Ar34SH, 37Cl2H
H, S, Cl, Ca,
Ar
2.5% HNO3 / 1.5% HCl
75As BEC: 8.5ppt,
LoD: 0.4ppt

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QCell - Interference Removal by Collision/Reaction Cell
• Low mass cut-off:
• Prevents recombination of
precursors in cell  reduced BECs
Anal. LMCO Interferences Precursors
51V 35 35Cl16O, 37Cl14N,
34S16OH
H, N, O, S,
Cl
56Fe 39 40Ar16O, 40Ca16O O, Ar, Ca
63Cu 45 40Ar23Na,
12C16O35Cl, 31P32S
C, N, O, Na,
P, S, Cl, Ar
75As 47 40Ar35Cl, 40Ca35Cl,
40Ar34SH, 37Cl2H
H, S, Cl, Ca,
Ar
2.5% HNO3 / 1.5% HCl
75As BEC: 8.5ppt,
LoD: 0.4ppt

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Dionex ICS-900 IC System with iCAP Q ICP-MS
• Single channel
• Isocratic elution
• AN 43098:Speciation analysis of
Cr(III) and Cr(VI) in drinking
waters

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Chromium Speciation in Drinking Water
Column Dionex IonPac AS7 (50 x 2 mm)
Mobile Phase 0.4 M HNO3
Flow(mL/min) 0.4
Injection vol (µL) 20

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IC-ICP-MS for the Speciation of Cr(III) and Cr(VI)
• Both chromium isotopes, 52, 53Cr,
can be monitored
• Cr(III) and Cr(VI) are completely
baseline separated
• Limits of detection:
• 0.20 ng L-1 [Cr(VI)]
• 0.38 ng L-1 [Cr(III)]
• Isocratic chromatography
performed in less than 3 minutes

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Speciation of Cr in Drinking Water
Analysis of locally sourced tap water (Bremen):
Only Cr(VI) was detected, concentration 42.5 ng L-1
Injection without further sample treatment

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Chromium Speciation Analysis of Drinking Water
• A sensitive and fast method based on ion chromatography
for the speciation of Cr has been developed
• No need for the addition of EDTA or other charge pairing agents
necessary, no additional sample preparation, no additional spectral
interferences in the mass spectra
• The IC eluent, dilute HNO3, is relatively cheap, easily sourced and
allows detection of Cr species in the single digit ppt range
• Reduced column dimensions allow reduction of the mobile phase flow
rate to 0.4 mL min-1

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Dionex ICS-2100 IC System with iCAP Q ICP-MS
• Single channel – isocratic
elution with mobile phase of
choice
• Integrated RFIC – gradient
elution with
• KOH – anion-exchange
• MSA – cation-exchange
• Arsenic, Iodine, Chromium,
Iron speciation

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Arsenic and Sulfur Speciation in Natural Waters
• Arsenic is ubiquitous in the
environment
• Speciation is essential for
understanding the mobility and
toxicity of arsenic
• Thioarsenates have been identified
in neutral to high pH and sulfidic
conditions
D. Wallschläger, C. J. Stadey, Anal. Chem. 79 (2007), 3873-80

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Arsenic and Sulfur Speciation in Natural Waters
• Detection of S is hampered by
spectral interferences
• 16O2+, 16O18O+ etc.
• Use of CCT mode with O2 to
convert As and S in AsO+ (m/z
91) and SO+ (m/z 48), resp.
Parameter Value
Column Dionex IonPac AS18
(2x250mm)
Mobile phase KOH, automatically
generated using RFIC
Gradient
Conditions
0-5 min: 12-44mM KOH
8-10 min 44-52 mM KOH
12-15 min 52-100mM KOH
Injected vol. 20 µL
32S+ + 16O2 → 32S16O+ + 16O

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Arsenic and Sulfur Speciation in Natural Waters
• Different As and S containing anions separated and individually detected
• Simultaneously, also metal based species as MoO4
2- can be detected
Instrumental
Performance:
LOD [SO4
2-]:
4.8 ng g-1
BEC: 2.5 ng g-1
LOD [As(III)]:
0.02 ng g-1
BEC: 0.08 ng g-1
48SO+ 91AsO+ 114MoO+
Standards

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Arsenic and Sulfur Speciation in Natural Waters
• Unknown As/S-species found in natural water samples
• Stoichiometry determined using peak area
48SO+ 91AsO+ 114MoO+
Natural Water

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Arsenic and Sulfur Speciation in Natural Waters
• A multi-elemental speciation method has been developed for
the simultaneous characterization of sulfur and arsenic
containing species:
• A simple autotune procedure configures the instrument for optimal
detection of sulfur and arsenic using reaction with O2 in Qcell
• RFIC with a KOH gradient significantly simplifies set-up and ensures
separation of eight sulfur/arsenic containing species in under 15 mins
• Narrow bore column (2 mm i.d.) allows reduction of the mobile phase
flow rate to 0.4 mL min-1
• Oxyanions containing other species can also be measured
simultaneously

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IC-ICP-MS: A Powerful Tool for Elemental Speciation
• IC-ICP-MS is a fully integrated technique
• One software, no triggering, simple hardware connection
• The completely metal free ICS product line eradicates
possibility of contamination
• Large range of IC systems and columns
• IC tailored for your application
• Flexibility and support for developing applications
• For many elemental speciation applications IC is the
preferred chromatographic choice for ICP-MS:
• Mobile phases are simpler/cleaner for lower interferences, lower
background and lower limits of detection
• Narrower bore columns (2 mm ID) for higher efficiency separation and
lower mobile phase consumption

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iCAP Q ICP-MS for Environmental Analysis
• Proprietary interface designed for matrix
tolerance
• Increases productivity by minimizing QC
failure and increasing analysis periods
between maintenance
• Collision Reaction Cell technology with
• Low mass cut-off for accurate analysis at
low concentrations
• Single mode He-KED for simplicity and
high throughput
• Flexibility of CCT mode for challenging
applications

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iCAP Q ICP-MS for Environmental Analysis
• Minimal bench space requirements
• 66 cm wide
• Easy to use and maintain
• Quick connect sample introduction system
• Pop out interface for easy access
• Intuitive Qtegra software platform
• Common to iCAP ICP-OES
• Integrated Get Ready, Workflows and QC
• Fully integrated IC-ICP-MS package with
full set of chromatographic data evaluation
features

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Thank You!
WS71159_E 06/14S