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A Thermo Electron Corporation új XSeriesII ICP-MS készülékének és
környezetvédelmi alkalmazásainak bemutatása
Száraz SándorUnicam Magyarország Kft.1144 Budapest, Kőszeg u. 29.
XSeriesII ICP-MS
Brief introduction to ICP-MS
Characteristics of ICP-MS
• Wide element coverage
• Low limits of detection
• Elemental and isotopic information
• Wide dynamic range
• Wide variety of samples
ICP-MS Process
• 4 Basic Stages1. Sample Introduction and Ion
Generation
2. Ion Focusing
3. Separation of Analyte Ions in Quadrupole Mass Filter
4. Ion Detection
Ar PlasmaCellQuadDetector
SampleGas
1.
M+ Species Generated
in the Plasma
2.
Ion Focusing / Optional
Collision Cell
M+M+
4.
Ion Detection by electron multiplier
3.
Ion Analysis Separation by
m/z ratio
M+
ICP-MS - Sample Introduction
As the solution passes throughthe Ar plasma, 4 main processeswill occur
• Samples are normally analyzed as solutions
• Sample is introduced into an argon plasma as a fine aerosol, via a peristaltic pump, nebulizer and spray chamber
• Within the plasma (< 6000K) the solvent is evaporated and the sample species are decomposed into their constituent atoms and ionised
- Ionisation process is extremely efficient in the plasma, and contributes to the high sensitivity of ICP-MS
ICP-MS - Sample Introduction
• Normally via concentric nebulizer ~1ml/min uptake
• Typical sample volume - 20 elements using 3 x 2 secs. integrations - 4 - 5ml sample required
• Optional low flow nebulizer for μl. sample analysis
• Optional laser ablation for direct solids analysis
ICP-MS - Sample Introduction
• Maximize M+- Minimize MO+
- Minimize M++
• Sample Uptake- Nebulizer dependent
• Plasma Gases- Cool
- Auxiliary
- Nebulizer dependent
• Torch Position
- x, y, z control
Hotter
M++M+MO+
Cooler
Ion Sampling and Focusing
• Ions formed in the plasma are extracted through a sample and skimmer cone arrangement
• Ion Lenses focus & optimize ion transmission to quadrupole analyser
• Sample treatment is important to minimize deposition on cones:-
- Dissolve and dilute to ~ 0.2% w/v
- up to ~ 5% nitric acid preferred
- up to ~ 5% hydrochloric acid
- ~ 1% hydrofluoric acid (using an Inert Sample Introduction Kit), phosphoric acid or sulfuric acid Increasing vacuum
Sample Cone
Skimmer ConeIon
LensDA
Extraction Lens
Slide Valve
Ion Focusing Mechanism
• Optimizes ion transmission to quadrupole analyser
• Conventional ion focusing devices - Complex lens configuration and often
incorporate a photon stop
- Backgrounds typically 10-20 cps
• XSeriesII: New high efficiency ion guide- Simple design with reduced number
of lenses
- Incorporate an innovative chicane deflector and off-axis quadrupole
- Backgrounds of <0.5 cps
- Upgradeable to collision cell technology (CCT)
Ion Analysis – Quadrupole MS
• Quadrupole consists of 4 rods mounted equidistant to each other around the circumference of a circle
• Separates Ions according to their mass to charge (m/z) ratio
• Principles of operation- Alternating RF / DC potentials are applied to the quadrupole rod pairs
- Ions move in a spiral motion down the quadrupole axis
- Majority of masses are put into an unstable trajectory and are rejected
- However under a given condition, ions of a specific m/z will pass through the analyser and reach the detector
Ion Detection
• Ion detection is made with an electron multiplier
• Measures the number of Ions arriving at the detector - proportional to the concentration of that isotope in the original solution
• Detector operates in pulse counting (ion counting) and analogue (ion current) modes
• With automatic cross calibration measures major, minor and trace analytes in a single acquisition
-2Kv-2Kv
Data Acquisition Modes
• Scanning- Qualitative analysis and Quantitative analysis
- SemiQuantitative analysis: Post run data retrieval on un-calibrated elements
• Peak Jumping- Selected isotopes
- Optimized dwell times
- Improved detection limits
• Time Resolved Analysis- Transient signal analysis
- Applicable to laser ablation ICP-MS and chromatographic studies
ICP-MS Full Mass Spectrum
• Simple spectra (primary M+ ions)
- Facilitates simple interpretation
• Very high signal to background- Low detection limit capabilities
V ICP-AES Spectra - Vanadium 10mg/LV ICP-MS Spectra - Vanadium 10mg/L
Calibration Techniques
• Semi Quantitative- Analyte sensitivity can be determined from the instrument
response built from the response to other known analytes.
- Relative Sensitivity Factors (RSF) apply corrections for ionization and sample processing effects, these can be pre-determined for a given matrix to improve accuracy
• Full Quantitative- Multi element external calibration standards
- Standard additions calibration
- Isotope ratio determination (for isotope dilution measurement)
Semi-Quantitative Analysis
• External standards not required for each analyte
• Calibration via RSFs from Response Curve
Semi Quantitative Calibration Plot
• Full elemental and isotopic information
• Major to trace concentration determined
• No prior knowledge of sample required
Fully Quantitative Analysis
• External calibration standards measured prior to unknown samples
• Element or isotope responses are plotted against concentration
• Concentration of unknown samples calculated from the calibration graph
External Calibration
• Known sample is spiked with known concentrations of analytes
• Standard addition calibration plot provides accurate low level concentration data from the x-axis intercept
• Eliminates need for matrix matched calibration standards
Standard Additions
3.8 6.0 8.1 10.3Time (min)
AsC +AsB
As(III)
DMA
MMA
As(V)
Time Resolved Analysis
• Enables time resolved data to be acquired both qualitatively and quantitatively from transient signals
• Wide applicability including Laser Ablation ICP-MS and chromatographic studies
XSeriesII ICP-MS
Routine Environmental Applications
Environmental Applications – Sample types
• Wide variety of environmental sample types
Drinking water Ground water Waste water / effluent Leachates Soil / contaminated land digests Sediment digests Plant / animal tissue digests
• Generally high sample numbers (>100 per day in many laboratories)
Enviromental applications:Myths and misconceptions in ICP-MS
• Considered in the flame AA, furnace AA and ICP-OES communities that:
Not possible to measure high ppm concentrations (>100ppm) by ICP-MS
Interferences are a significant problem
Instrumentation is complex and difficult to use
Very high cost
Memory effects vs wide dynamic range: Monitored Sample Uptake and Wash
•Intelligent sample monitoring to ensure stability prior to data acquisition.
•Monitored washout eliminates sample carry over.
XSeriesII - Xt Interface
• Optimized response for Environmental Analysis
• Maximum productivity through long-term matrix tolerance and excellent signal stability
• Minimum recalibrations between samples
• Extended dynamic range- Enables Linear determination of
Na,Mg,K,Ca to 200 mg/L
- >> 1000mg/L when used in conjunction with high resolution measurement
Reaching high ppm concentrations:Variable resolution – what does it mean in practice?
• Allows the user to extend the dynamic range even further
The dynamic range limitation then becomes the 0.2% total dissolved solids upper level imposed by the interface cones
• Can be adjusted down to peak widths lower than 0.3 amu
• Can be adjusted on-the-fly to allow standard and ‘high’ resolution measurements to be made analyte by analyte
RF
DC
MM+
1
M-1
Na, Ca, calibration – Xt interface, standard resolution
Na: blank to 300 ppm
Standard XSeriesII configuration (no CCT), using In as the internal standard
Sensitivity = 0.9 Mcps/ppmBEC = 107 ppb
Cr: blank to 100 ppb
Sensitivity = 1.3 Mcps/ppmBEC = 0.2 ppb
Peak width (at 10% peak height) = 0.75 amu
Reaching even higher ppm concentrations:Na calibration – Xt interface, increased resolution
Na: blank to 2000 ppm
Standard XSeriesII configuration (no CCT), using Ga as the internal standard
Sensitivity = 0.5 Mcps/ppmBEC = 38 ppb
Peak width (at 10% peak height) = 0.2 amu
2000 ppm
Long Term Drift of X Series with Xt Interface (Borehole Water Matrix)
0.90
0.95
1.00
1.05
1.10
0 2 4 6 8 10 12 14 16 18
Time /hours
Rel
ativ
e re
spon
se
7Li 115In 238U
Li = 21 µg l-1 RSD = 1.6 %
In = 10 µg l-1 RSD = 1.1 %
U = 4 µg l-1 RSD = 1.5 %
Comparison with ICP-OES
Calcium
0
50
100
150
200
250
300
0 50 100 150 200 250 300
ICP-MS mg l-1
ICP
-AE
S m
g l-1
Potassium
0
20
40
60
80
100
0 20 40 60 80 100ICP-MS mg l-1
ICP
-AE
S m
g l-1
R2 = 0.984 R2 = 0.997
n = 188
Conclusions for XSeriesII standard with environmental work
•Hardware and software advancements of the XSeriesII ICP-MS allow rapid, accurate analyses of environmental samples with turnkey operation.
•Great improvement in sample throughput.
•Linear range extended and matrix tolerance improved with Xt interface.
•Protocol compliance even without CCT.
XSeriesII ICP-MS
Performance Options for
Environmental Research Applications
Peltier Controller option – do we need it?
• Rapid, precise temperature control of spray chamber for optimum performance
- constant aerosol formation independent of the laboratory temperature control
• Typical operation at 2oC
- reduced solvent loading into the plasma
- lower oxides and other interferences
- improved MDLs
• Can be used with the standard quartz or inert spray chamber
• Rapid changeover between aqueous and organic matrices using the organics kit
Variable temperature Peltier (thermo-electric) block
CCTED – When do we need it?
• Research Applications
• Ultimate Detection Limits - well below regulatory levels
• Analysis of some complex or pristine environmental matrices such as seawater or snow / ice.
- Common interferences can not be eliminated using conventional quadrupole ICP-MS technology
- Interference correction equations
- Matrix removal
• CCTED enables direct analysis without the need for matrix removal leading to improved DLs and enhanced productivity
Element m/z Interfences
K 39 ArH
Ca 40 Ar
V 51 ClO, ArC
Cr 52 ArC, ClOH
Mn 55 ClO
Fe 56 ArO, CaO
Co 59 ArNa, CaOH
Cu 63 ArNa
Zn 66 ArMg
As 75 ArCl
Se 80 ArAr
Introduction to the use of CCT with environmental analysis:Principles of Collision Cell Technology
Isotope Interferant Isotope Interferant 6,7Li Background 52Cr ArC, ClOH 23Na Background 55Mn ClO, KO 28Si N2, CO 56Fe ArO, CaO 31P NOH 59Co ArNa, CaOH 32S O2
63Cu ArNa 39,40K ArH, Ar 66Zn ArMg 40Ca Ar 75As ArCl, CaO2 48Ti SO 80Se Ar2, FeH2O 51V ClO, ArC 81Br Ar2H
Iron
Argon
Oxygen
Helium
Introduction to the use of CCT with environmental analysis
• Some analytes have few interference problems and perform best with the cell unpressurised, i.e. standard ICP-MS mode, e.g. Pb
• The ideal multi-element analysis would result in several analyses under different conditions, e.g.
Standard mode
H2 mode
NH3 mode
• A more efficient method is to switch modes “in-sample”
is this viable in terms of speed, stability and accuracy?
Uses for CCT - Analytes, Interferents & Gases
Mass / amu Analyte Interferent Gas24 Mg CC H2 / He28 Si N2 H2 / He
32 S O2 Xe / He1
39 K ArH H2 or NH3 / He40 Ca Ar H2 or NH3 / He51 V ClO NH3 / He52 Cr ArC H2 / He54 Fe ArN H2 / He56 Fe ArO H2 or NH3 / He63 Cu ArNa H2 / He66 Zn ArMg H2 / He72 Ge ArAr H2 / He75 As ArCl H2 / He77 Se ArCl H2 / He78 Se ArAr H2 / He80 Se ArAr H2 / He82 Se ArHArH H2 / He
Spectra for UPW Water (35-65 amu)
CCTCCT ModeModeCCTCCT ModeMode
StandardStandard ModeModeStandardStandard ModeMode
CCT for environmental applications: Instrument
• XSeriesII ICP-MS with CCTED and Xt interface
• CCT connected to two gases:
8% H2 in He 1% NH3 in He
• 2 computer controlled MFCs allow gases to be changed “in-sample”
Wide range of typical environmental analytes were measured:
- 30 analytes, 55 isotopes
Many analytes have associated interference problems….
CCT for environmental applications: Experimental - considerations
Mass / amu Analyte Interferent Gas24 Mg CC H2 / He28 Si N2 H2 / He
32 S O2 Xe / He1
39 K ArH H2 or NH3 / He40 Ca Ar H2 or NH3 / He51 V ClO NH3 / He52 Cr ArC H2 / He54 Fe ArN H2 / He56 Fe ArO H2 or NH3 / He63 Cu ArNa H2 / He66 Zn ArMg H2 / He72 Ge ArAr H2 / He75 As ArCl H2 / He77 Se ArCl H2 / He78 Se ArAr H2 / He80 Se ArAr H2 / He82 Se ArHArH H2 / He
Uptake
25s
CCT for environmental applications:Experimental - Timing
An
aly
tes
Settle
Delay
30s
Settle
Delay
30s
Standard
Mode
3x18s reps
Wash
25s
Total Time Per Sample (3 repeats) = 3 minutes, 45 seconds
Tim
e
Pro
file
VCr
NH3/He
3x1.6s reps
LiBeNaRbSrRbMoAgCdSnCsBaTlPbU
MgAlK
CaCrFeMnNiCuZnGaAsSe
H2/He
3x18s reps
7Li 0.01 55Mn 0.01 77Se 0.1 114Cd 0.0039Be 0.003 56Fe 0.06 78Se 0.03 118Sn 0.01
23Na 2 58Ni 0.02 80Se 0.03 120Sn 0.00924Mg 0.1 59Co 0.005 82Se 0.1 133Cs <0.00125Mg 0.3 60Ni 0.03 85Rb 0.004 138Ba 0.00727Al 0.2 63Cu 0.02 87Rb 0.008 140Ce <0.00140Ca 3 64Zn 0.05 88Sr 0.005 203Tl 0.00244Ca 1 65Cu 0.02 95Mo 0.007 205Tl 0.00151V 0.01 66Zn 0.05 98Mo 0.005 206Pb 0.0152Cr 0.2 69Ga 0.02 107Ag 0.009 207Pb 0.0153Cr 0.05 71Ga 0.005 109Ag 0.009 208Pb 0.00954Fe 1 75As 0.01 111Cd 0.002 238U <0.001
H2/He ModeNH3/He ModeStandard Mode
CCT for environmental applications: Results - detection limits (g/L)
Based on 3 on 12x10 replicates of blank, each from a new calibration
Stability of NIST 1640x10 - 10 Hours, 12 Different Calibrations
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10
Time (Hours)
Co
nce
ntr
atio
n (
ug
/L)
51V NH3 Mode (1.5%)
80Se H2 Mode (1.7%)
111Cd Std Mode (0.3%)
CCT for environmental applications: Results – stability of real sample in different modes
Sample diluted 1+9 and spiked to
2% HCl
CCT for environmental applications:Conclusions
• The XSeriesII allows rapid settings changes, allowing two different cell gases and normal ICP-MS mode to be used in a single sample analysis
3¾ minutes per sample, 55 isotopes, 3 measurements/isotope,
• Excellent stability is retained in each mode RSDs of typically <1% over a 12 hour duration for a signal of
~50,000cps
• Mode switching allows the optimum conditions for each analyte to be utilised, resulting in ultimate performance:
DLs in the ppt or sub-ppt range for almost all elements
• The technique results in freedom from many interferences
Accuracy of within ±5% for the vast majority of analytes, even after spiking to 700ppm chloride
Xs Interface option – do we need it?
• Xs- extraction provides enhanced sensitivity whilst retaining the extremely low background characteristics of the XSeriesII
• For research and ultra trace applications
- Actinides
- Isotope ratios
- Small spot laser applications
• Interchangeable with the Xi interface
- User interchangeable ~ 2 minutes
• Typical sensitivity >200Mcps/ppm for mid –high mass elements (In – U)
X Series Environmental Methods ICP-MS Productivity Pack
• Supplied to customers on instrument delivery:
PlasmaLab Productivity Method Template
Detailed instructions on instrument set-up, solution
preparation and sample analysis
A Productivity Method Template that can be modified to a
laboratory’s own working method
All calibration and quality control solutions required to run
each protocol
A printed file containing the Productivity Method Template
Environmental Protocols
• US EPA has developed a series of methods for the
analysis of drinking water, waste water and other
environmental samples: -
OW 200.8 drinking water 1991
OSW 6020 waters, wastes, soils, etc 1994
OSW 6020A waters, wastes, soils, etc 1998
CLP ILM05.2D waters, wastes, soils, etc 2001
These are challenging, QC intensive, multiple analyte, multiple concentration
methods with tough specifications for accuracy, precision and DLs
Environmental Protocols - Typical Requirements
• Methods are ‘Prescriptive’ with specific rules on various analytical practices that must be followed e.g.
• Specified Elements: Up to 23 elements, 7-orders of magnitude range (ppt to high ppm)
• QC Checks – post calibration: Separate source calibration verification Interference check - High Matrix Interference check - High Matrix + Spike
• QC Checks – every 10 samples: Continuing calibration verification Reference material Detection limit check standard
• Sample QCs - every 20 samples: Duplicate Serial Dilution and Spike Recovery
XSeriesII - Interference Correction Equations
X Series interference correction equations derived for use with EPA protocols
XSeriesII MDLs vs. ILM05.3 CRQLs- EPA ILM 05.3 Environmental water and waste water
0.001
0.01
0.1
1
10
100
1000
10000
Con
cent
ratio
n ug
/L (
ppb)
Analyte
9Be
23Na
25Mg
27Al
39K44C
a51V52C
r55M
n56F
e59C
o60N
i65C
u66Z
n75A
s77S
e78S
e82S
e107A
g114C121S
b137B
a205T
l208P
b
Comparison of XSeriesII MDLs and CLP CRQLs
XSeriesII MDL0.5*CRQL
0.001
0.01
0.1
1
10
100
1000
10000
Con
cent
ratio
n ug
/L (
ppb)
Analyte
9Be
23Na
25Mg
27Al
39K44C
a51V52C
r55M
n56F
e59C
o60N
i65C
u66Z
n75A
s77S
e78S
e82S
e107A
g114C121S
b137B
a205T
l208P
b
Comparison of XSeriesII MDLs and CLP CRQLs
9Be
23Na
25Mg
27Al
39K44C
a51V52C
r55M
n56F
e59C
o60N
i65C
u66Z
n75A
s77S
e78S
e82S
e107A
g114C121S
b137B
a205T
l208P
b
Comparison of XSeriesII MDLs and CLP CRQLs
XSeriesII MDL0.5*CRQL
PlasmaLab Productivity Method
Template on CD
Detailed instructions on instrument
set-up, solution preparation and
sample analysis
Productivity Method Template can be
modified to a laboratory’s own SOP
All calibration and quality control
solutions required to run each protocol
A printed file containing full
instructions of the operating
procedure
XSeriesII Environmental Productivity Pack
Environmental Productivity Pack - Contents
Supplied to customers on instrument delivery:
XSeriesII ICP-MS – Environmental Analysis Summary
• Routine MDLs - XSeriesII ICP-MS easily provides protocol compliant
detection limits QC checks: XSeriesII consistently produces accurate results on
QCs and samples Interference checks : XSeriesII design offers excellent freedom
from interference and stable correction where necessary Fastest sample throughput with protocol compliance
• Productivity Pack uniquely offers: Proven, reliable off-the-shelf EPA methods for the - XSeriesII ICP-
MS Unbeatable rapidity of start-up after installation
• Research Peltier cooled spray chamber for improved long term stability and
MDLs CCTED for interference removal / improved accuracy and detection
limits in complex matrices Xs interface for special applications requiring the ultimate
signal/background LC / GC packages for speciation studies
XSeriesII ICP-MS
Speciation analysis
Why Speciation Analysis?
• Elemental speciation data can reveal valuable information in addition to total element concentrations: -
bioavailability, mobility, metabolic processes, bio transformations and toxicity implications
• Elemental speciation is receiving increasing interest in both academic & commercial laboratory environments
Applications often use HPLC-ICP-MS and GC-ICP-MS techniques
Growing number of publications for elemental speciation analyses
Elemental speciation increasingly recognised in EPA protocols
Inorganic As3+ arsenite (AsO3)3-
Inorganic As5+ arsenate (AsO4)3-
Monomethylarsonate (MMA)
Dimethylarsinate (DMA)
Arsenobetaine ((CH3)3As+CH2COOH)-
Arsenocholine ((CH3)3As+
(CH2)2OH)
Increasing Increasing ToxicityToxicity
e.g. Arsenic Toxicity
Topical Species in Environmental, Life Science and Food Samples
• Arsenic – (As5+, As3+, DMA, MMA, AB) urine, biological tissues, foods, waters
• Chromium – (CrVI and CrIII) biological fluids, waters
• Selenium – (SeIV, SeVI, SeMet, SeEth, SeMC) urine, biological tissues, foods & supplements,
• Mercury – (Hg2+, MeHg) biological tissues, foods, waters
• Tin – (MBT, DBT, TBT) biological tissues, foods, waters
Flexible HPLC-ICP-MS product packages
• XSeriesII ICP-MS with Finnigan Surveyor HPLC
• XSeriesII ICP-MS with SpectraSYSTEM HPLC
• ‘HPLC Coupling Packs’ for X Series ICP-MS
Simple analytical and electrical connections to ‘any’ HPLC
External Trigger Board for 2-way communications between the LC and the ICP-MS
X Series ICP-MS for HPLC applications
• Simple to interchange between standard ICP-MS & HPLC sample introduction
• XSeriesII ICP-MS organics kit for reverse/normal phase HPLC
• Burgener AriMist nebulizer for mobile phases with high TDS & 50–2000 μL/min flow rates
• Sensitive multi-element capability
• Field upgradeable XSeriesII ICP-MS
Flexible GC-ICP-MS product packages
• XSeriesII ICP-MS with Finnigan Focus GC
• XSeriesII ICP-MS with Finnigan Trace GC
• ‘GC Coupling Packs’ for XSeriesII ICP-MS
Simple analytical and electrical connection to ‘any’ GC
XSeriesII ICP-MS for GC applications
• Unique DUAL MODE sample introduction Gas or solution analyses
without reconfiguring the interface
Three legged GC-ICP-MS torch
Flexible tuning & performance testing with aqueous solution
On-line addition of aqueous internal standards
Robust plasma conditions for GC-ICP-MS analysis
Speciation with LC-ICP-MS: Arseno sugars in kelp
• SpectraSYSTEM HPLC mobile phase: 5 mM TBAH at pH 6.0 (0.7 ml/min) HPLC column: Discovery C18 (150mm x 2.1mm i.d) 0.2 g kelp extracted in 5ml MeOH/water (50:50 v/v) Injection volume: 1 micro-litre Dimethylarsinoylriboside standards (deionised water) Fast separation, baseline separation
of all peaks in just over 2 mins.
• LC-ICP-MS Coupling Pack
• XSeriesII ICP-MS Xt interface PlasmaScreen Plus Peltier Cooled Spray Chamber
Arsenosugar II
Arsenosugar III
Arsenosugar I
Arsenosugar IV
Speciation with GC-ICP-MS Organo-Sn speciation in Sediments
• Finnigan Focus GC GC column: 30 m Restek MXT-1 Mobile phase: He at 25 ml/min Make-up gas: Ar 350 ml/min Injection volume: 1 μL Oven program: 70-250ºC (50ºC/min plus 1 minute hold)
• GC-ICP-MS Coupling Kit
• XSeriesII ICP-MS Xt interface PlasmaScreen Plus Timeslice internal standard: (5 ng/ml Sb)
PlasmaLab for chromatographic applications
• Transient TRA data acquisition
• External Triggers for controlling ‘any’ HPLC or GC accessory
• Intelligent bi-directional communication for failsafe, high throughput analysis
• Unique ‘Timeslice’ & ‘Transient’ internal standard modes for improved data quality
• In-house peak integration for quantitative analysis
The New XSeriesII ICP-MS
More Practicality, More Productivity, More Performance for every application
