Post on 13-Dec-2015
X Series ICP-MS Training Course
• Introduction to ICP-MS theory and X Series ICP-MS
• PlasmaLab• Analytical Method
Development• Dealing with
interferences
Application areas
Metals / Industrial
Analysis of major, minor and trace elements
Purity of fine metals
Solution Analysis via nebulisation
Solids Analysis via Laser Ablation
Reagents required:
40% v/v/ Primar Nitric acid and deionised water
No sample preparation required. Bulk or feature analysis can be performed on metals.
Nuclear
Fuel quality certification
Environmental and bioassay monitoring of low level actinides
Precise and accurate isotope ratio measurementSignal to noise ratio needs
to be maximized for ppq & sub ppq LOD’s. Use of high efficiency nebulisers.
For waste minimization use of low flow nebulisers, e.g. PFA-50
Semiconductor
Determination of low levels of impurities in ultra-pure process reagents
Impurity analysis of wafers
Transition metals suffer from Argon oxide and Argon nitride interferences, which are greatly reduced with the PlasmaScreen Plus and CCT options.
Use ultra-clean glassware, cones etc.
Recommended Accessories: USN and PFA-50, if low sample volume
Biological & Clinical
Speciation of metals
Elemental uptake and excretion studies
Stable isotope tracer studies
Analysis of salvia, serum, blood and urine
CCT technique recommended to overcome interferences on key elements such as Cr, Fe, As, Se in heavy biological matrices
Geological
Rocks, sediments and soils
Direct solid analysis using Laser Ablation on:
Individual minerals, thin section, isotope ratios, zonation studies, depth profiling.
Oxide interferences within REE
e.g. BaO on 151Eu and 153Eu, NdO on 150Tb, 160Gd and 162Dy.
Residual HClO4 or saline matrices will interfere with Cr,V and As(ClO & ArCl interferences).
Environmental
Analysis of drinking and waste water
Seawater and marine life (shellfish, corals etc.)
Analysis of industrial effluents
Soil/sediment studiesTransition metals suffer from Argon oxide and Argon nitride interferences, which are greatly reduced with the CCT option.
Reagents required
40% v/v Primar Nitric acid and deionised water
Sample dried into a digest ‘bomb’, if required.
Minimising contamination
• Laboratory environment• Water quality• Ultrapure reagents
Handling of ultrapure reagents
• Selection of material for containers & cleaning procedures
• Sample and standard preparation
Tracing sources of contamination
The Step-by-Step Approach
• Instrument blank
• Water blank
• Dilute acid blank
• Analysis blank
Causes of interferences
Interferences – mass spectroscopic
Interferences – non mass spectroscopic
ELEMENTI ISOTOPI in ICP-MS
Isotopi : Atomi dello stesso elemento con differenti masse (stesso numero di protoni & elettroni ma diverso numero di neutroni)
50 4.34552 83.78953 9.50154 2.365
Mass : 55,9116
Mass : 52,0554
Isobaric Interference
Mass 54
Isotope for FeIsotope for Cr
Mass Abundance 54 5.80056 91.72057 2.2058 0.280
Isotopes for Iron
Isotopes for Chromium
Cr
Fe
INTERFERENZE
Le interferenze Molecolari e Isobariche vengono classificate come interferenze spettroscopiche
- Interferenze Molecolari (poliatomiche): sono Ossidi ed Idruri, Specie poliatomiche
Gli ossidi possono essere minimizzati attraverso il tuning, gli idruri mediante sistemi per l’abbattimento delle interferenze (CCT)
-Interferenze Isobariche: questo tipo di interferenze sono dovute alla sovrapposizione di diversi isotopi
Interferences
SpectrometerLenses(CCT)
Ar +, N +, O +, N 2+, O 2
+, Ar 2+, etc.
ArO + ,ClO + ,ArNa + etc.
Ar Ar + (0.1%)
Ar
diss .“metal”,H 20, HNO 3,HCI, etc.
dry “metal” or
metal-oxide, decomposing
anions
MetalAtoms
MetalIons (M +)
Conventional “Front-End” approaches toreduce interferences
“Analyzer approach” to reduce or resolve interferences
Mo > M + + e -
“Ionization potential”
ESEMPI DI INTERFERENZE SPETTROSCOPICHE
Interferenze poliatomiche Interferenzeda Ossidi, Idrossidi,
Idruri e doppie cariche
• Polyatomic peak overlaps Causes/sources : solvent
– Anions in sample– Cations in sample– Ar gas– Entrained air
• Signal suppression • Ionisation suppression or enhancement
Causes/sources : Overloading plasma– Overloading nebuliser– Cone orifice issues– Unintended plasma cooling effects
• Elemental peak (isobaric) overlaps Generally precludes the use of some
isotopes if overlap exists
Interferences
Analyte portion of total measured signal
Illustration of overlapping peaks
Total measured signal = analyte + polyatomic
Correction equations
Monoisotopic As in a Cl matrix
76 77 78 79 80 81 8275
Se(82)
ArAr40,40
ArAr38,40
ArAr36,40
ArCl40,37
Se77
ArCl40,35
As75
Therefore we can calculatethe contribution of ArCl at 77
Correction equations
76 77 78 79 80 81 8275
Se(82)
ArAr40,40
ArAr38,40
ArAr36,40
ArCl40,37
Se77
ArCl40,35
As75
Se(77) = Se(82) x AbSe(77)
AbSe(82)
ArCl(77) = Int(77) - Se(77)
ArCl(75) = ArCl(77) x Ab(ArCl(77)) Ab(ArCl(75))
As(75) = Int(75) - ArCl(75)
Monoisotopic As in a Cl matrix
Calculate 77Se contribution at mass 77 from 82Se
Calculate 77ArCl contribution at mass 77 from 77Se
Calculate ArCl contribution at mass 75 from 77ArCl
Calculate 75As contribution from 75ArCl
Instrument performance options
But the X Series ICP-MS, does supply a few ‘hardware’ remedies for these problems…..
• PlasmaScreenPlus - a)‘cool’ screen operation - analysis of Li, Na, K, Ca, Feb) ‘hot’ screen operation – enhances sensitivity while maintaining low background
• CCT - removal of polyatomics
• Xi – improves matrix tolerance and reduces polyatomics
Instrument performance options
Isotope Interferant Technique 6,7 Li Background CP 23Na Background CP 24Mg C 2 CCT 28Si N2 CCT 31P NOH CCT
56Fe ArO CP,CCT 39,40 K ArH, Ar CP,CCT 40Ca Ar CP,CCT 75As ArCl CCT 51V ClO CCT
52Cr ArC CCT 60Ni CaO Xi80Se Ar 2 CCT
PlasmaScreen Plus
• PlasmaScreenTM Torch
- Grounded metal screen inserted between torch and load coil
- Reliable automatic switching between ‘hot’ and ‘cool’ plasma conditions
• Cool screen conditions (~600 Watts)
- Minimizes argon-based interferences i.e. 38Ar1H+, 40Ar16O+, 40Ar2
+
- Minimizes high backgrounds associated with easily ionizable elements i.e. Li, Na
- ng/L LODs for Li, Na, Ca, K, Fe, Cr
• Hot screen operation
- Enhanced sensitivity
- Low background maintained
- Improved detection limits
COOL PLASMA
Caratteristiche
• RF a bassa potenza: 500-650w con nebulizzatore a flusso alto
• Temperatura del Plasma prossima a 2500-3000K
Vantaggi
• Permette di determinare in ICP-MS elementi come Ca, Mg, Fe, Na, K, Cr, V
Limitazioni
• Plasma non robusto: è necessario analizzare campioni nella medesima matrice
• Impossilità di analizzare elementi con alto potenziale di eccitazione/ionizazione ( As, Hg, Se)
CCT
HEXAPOLE RODS
SKIMMER CONE
EXTRACTION LENSSAMPLE CONE
• Operating the ion guide with a suitable collision/reaction gas (in CCT mode) Selective attenuation of polyatomic
interference ions
– 40Ar35Cl, 40Ar12C, 40Ar22+, 40Ar2H, 38Ar1H+,
40Ar16O+, 40Ar2+
• Innovative, user selectable CCT
• Plasma operated at normal power- Transmission of the analyte ions
remains largely unaffected
• Ability to switch to CCT mode within sample
CCT - ArAr
59Co+
ArAr+H2
He
He
59Co+
ArAr(neutral) + H2+
CCT – analysis of iron
10ppb Fe - CCT
Blank - CCT
• Based on a multipole ion guide contained in a cell into which the collision cell gases flow; cell is located between the interface and the quadrupole analyser
• Hexapole or octopole ion guides are used
Collision cell
Split-flow high-compression turbo pump
Cell Gas
1
Cell Gas
2
MFC 1MFC 2
Detector
COLLISION CELL
Rotary Pump
Plasma
Slide Valve
Quadrupole
• Based on a multipole ion guide contained in a cell into which the collision cell gases flow; cell is located between the interface and the quadrupole analyser
• Hexapole or octopole ion guides are used
Collision cell
Split-flow high-compression turbo pump
Cell Gas
1
Cell Gas
2
MFC 1MFC 2
Detector
COLLISION CELL
Rotary Pump
Plasma
Slide Valve
Quadrupole
Principi della tecnologia a cella di collisione
• Il fascio ionico viene iniettato in una cella pressurizzata
- Tradizionalmente vengono impiegate miscele He, H2 or a He/H2
• Gli ioni poliatomici collidono con il gas della celle e vengono dissociati nei loro componenti atomici, ioni etc.
- 38Ar1H+/39K, 40Ar+/40Ca, 40Ar12C+/52Cr, 40Ar23Na+/63Cu, 40Ar16O+/56Fe, 40Ar35Cl+/75As, 40Ar2+/80Se
• La trasmissione degli ioni analiti attraverso la cella non viene praticamante influenzata
• Le condizioni di plasma ad alta temperartura vengono mantenute
Ferro
ArgonOssigenoIdrogeno
ArO+ ArH2
H2O+
H2
H2
Fe+ Fe+
CCTED – Meccanismi possibili
• Meccanismi possibili Dissociazione collisionale?
–e.g. ArAr+ + He = Ar + Ar+ + He
Reazione chimica?–e.g. ArAr+ + H2 = ArH + ArH+
Trasferimento di carica?–e.g. ArAr+ + H = ArAr + H+
Ritardo collisioneale e successiva flitrazione in termini di energia delle specie?
–e.g. ArAr+* + He = ArAr+ + He*
Solving the problem of cell generated interferences
• Subsequent collisions of cell-generated ions cause them to lose kinetic energy
• These ions (and also plasma derived polyatomic ions), with their larger
collision cross section, lose more energy than the smaller analyte ions
• Can prevent these lower energy interfering ions from being detected by
using an energy barrier between the cell and the quadrupole analyser –
this is called (kinetic) energy discrimination (ED or KED)
+++
+
+
+
+
++
+
How is energy discrimination set up?
• Changing collision cell and quadrupole bias voltages provides a simple way to set up the required energy barrier
Polyatomic ions from plasma or cell reaction products have insufficient energy to pass through the energy discrimination barrier
Po
ten
tial
Position
Without ED
With ED
Potential Barrier
Collision CellLensesQuadrupole
-2V-9V
-18V-14V
Analyte Ion
Isobaric Polyatomic ion
Key
The power of energy discrimination (1)
• In environmental and clinical samples, containing Cl and Ca, 75As is interfered by 40Ar35Cl+ and to a lesser extent, 40Ca35Cl+
• Collision cells are effective for removing these interferences, however, if ED is not used, a large signal is still observed on 75As
• This signal does not match the 3:1 m/z 75 to m/z 77 ratio expected if the interference is Cl - related, so it must be another species
• If Ca is not present, the interference is not observed, so it must be related to Ca
Mass 75 = 17,000 cps
(Mass 77 = 2,000cps)
Scan of 100ppm Ca, collision cell without ED
The power of energy discrimination (2)
• The interference is believed to be CaOH(H2O)+ or CaO(H3O)+, formed from collision, then reaction, between CaOH+ and H2O in the cell
• As the Ca-species forms in the cell it’s energy is immediately reduced relative to the As+ analyte ion; further collisions as it passes through the cell reduce the energy further
• Applying a few volts of ED results in elimination of the species
• As+ is still transmitted to the quadrupole and can be determined to low ppt levels
Mass 75 = 6 cps
Scan of 100ppm Ca, collision cell with 2V ED
The power of energy discrimination (2)
1ppb 75As = 300 cps
Scan of 100ppm Ca + 1ppb As, collision cell with 2V ED
• The interference is believed to be CaOH(H2O)+ or CaO(H3O)+, formed from collision, then reaction, between CaOH+ and H2O in the cell
• As the Ca-species forms in the cell it’s energy is immediately reduced relative to the As+ analyte ion; further collisions as it passes through the cell reduce the energy further
• Applying a few volts of ED results in elimination of the species
• As+ is still transmitted to the quadrupole and can be determined to low ppt levels
1% HNO3 Blank
1ppb Fe
1ppb Fe
1% HNO3 Blank
Quadrupole – Standard Mode
Quadrupole – CCT Mode (H2/He)
Reduction of 40Ar16O+ and Ar2+ using the collision
cell
Quadrupole – Standard Mode
Quadrupole – CCT Mode (H2/He)
10ppb Se1% HNO3 Blank
10ppb Se
Collision cell ICP-MS Fe / Se calibration performance
80Se (40Ar2+ attenuated)
0.99994
4.0
14.2
3607
56Fe
1.0 Detection limit (3σ, n = 5) (ppt)
4.3 BEC (ppt)
0.99997Correlation coefficient
1648 Sensitivity (cps/ppb)
80SeParameter
56Fe (40Ar16O+ attenuated)
Sample matrix = 2% HNO3, 8% H2 in He collision gas used
Why use oxygen as a collision / reaction gas?
• Some interferences cannot be efficiently removed using 'standard' cell gases (e.g. He, H2, NH3)
• Some interfered analytes react (along with their
interferences), with certain cell gases (e.g. NH3)
– Lose analyte sensitivity; degrade detection limit
• Kinetic energy discrimination (KED) or bandpass
application sometimes not sufficiently effective
– Interference suppression results in too much sensitivity loss
– BEC's and detection limits not low enough for the analytical
requirement
XSeriesII – New Proof Data - 1
Fast Cd and Pb in whole blood analysis
• Blood reference materials measured; diluted 1:50 for analysis
• Standard addition calibration on one sample used to quantify other samples Unique ability for Thermo! Ideal approach for biomedical samples!
• Autosampler probe-to-wash-early function used to maximise throughput Unique for Thermo!
• Sample throughput = 51 per hour, or more than 400 per 8 hour day!
430 - 650499 ± 126 - 3933.3 ± 0.5Bio Rad 3
230 - 340
353 - 443
Reference 208Pb (ppb)
10.4 - 15.6
5.4 - 7.2
Reference 111Cd (ppb)
254 ± 212.5 ± 0.4Bio Rad 2
412 ± 136.2 ± 0.5Seronorm blood 2
Measured
208Pb (ppb)Measured
111Cd (ppb)Sample identity
111Cd
208Pb
XSeriesII – New Proof Data - 2
• Urine reference material diluted 1:20 with 1% (v/v) HNO3 for analysis; spike recovery (0.50 ppb Cd) performed on sample doped with Mo (5 ppm)
• Standard addition calibration on the sample used to quantify other
samples
• Samples run in standard and collision cell mode with O2 in the cell
O2 promotes MoO+ to higher Mo oxides; Cd does not react
Cd in urine in the presence of Mo (removing the MoO interference)
96Mo16O+
95Mo16O+
Mo interference
0.02
0.04
Detection limit3σ (ppb)
5.26
7.98
Conc. (ppb)
Standard mode Collision cell mode (O2)
Spiked Cd value (ppb)Isotope
0.05
0.03
Detection limit 3σ (ppb)
0.490.50113Cd
0.500.50111Cd
Conc. (ppb)
O2 in the cell completely removes the MoO interference!
Without O2 the interference is large
Detection of Pt in 10 ppm Hf solutions
• The problems: HfO+ and HfOH+ interferences on all Pt
isotopes (m/z 190 to 198)
m/z 190 and 198 interferences low
abundance but 190Pt very low abundance
(0.01%) and 198Pt also low (7.2%)
Must suppress HfO+ / HfOH+ interferences
on most abundant remaining Pt isotopes
(194Pt, 195Pt and 196Pt)
• The proposed solution: Use O2 as the collision gas, to promote
formation of higher Hf oxides / hydroxides
Pt less reactive with O2
HfO+, HfOH+ interferences, 10ppm Hf
179Hf16O+ = 3 Mcps
Pt isotopes, 12ppb Pt195Pt+ = 250 Kcps
Pt in 10 ppm Hf, standard mode and O2 data
9
5
7
Detection limit 3σ (ppb)
467*
154*
281*
BEC (ppb)*
Standard mode Standard BEC / collision cell BEC
Collision cell mode (O2)#Hf interference
Isotope
0.054
0.006
0.003
Detection limit 3σ (ppb)
122890.04180Hf16O+196Pt
171110.01179Hf16O+195Pt
165290.02178Hf16O+194Pt
BEC (ppb)
* estimated using the 198Pt (linear) calibration sensitivity # O2 flow rate = 2.7 mL/min, non-KED
195Pt standard mode 195Pt collision cell mode (O2)
Detection of Hg in 10 ppm W solutions
• The problems: WO+ and WOH+ interferences on all Hg
isotopes (m/z 196 to 204)
m/z 196 and 204 interferences low abundance, but 196Hg very low abundance (0.14%) and 204Hg also low (6.8%)
Also have 204Pb interference on 204Hg
Must suppress WO+ / WOH+ interferences on most abundant remaining Hg isotopes (198Hg, 199Hg, 200Hg, 201Hg and 202Hg)
• The proposed solution: Use O2 as the collision gas, to promote
formation of higher W oxides / hydroxides
Hg less reactive with O2
WO+, WOH+ interferences, 10ppm W
184W16O+ = 2.4 Mcps
Hg isotopes, 20ppb Hg200Hg+ = 140 Kcps
Hg in 10 ppm W, standard mode and O2 data
16700.020.24.2334*184W16O+200Hg
8130.030.31.0244*183W16O+199Hg
4.2
0.4
13
Detection limit 3σ (ppb)
247*
12
640*
BEC (ppb)*
Standard mode Standard BEC / collision cell BEC
Collision cell mode (O2)#
W interference
Isotope
0.02
0.05
0.02
Detection limit 3σ (ppb)
12350.2186W16O+202Hg
400.3184W16O1H+201Hg
32000.2182W16O+198Hg
BEC (ppb)
* estimated using the 201Hg (linear) calibration sensitivity # O2 flow rate = 3.4 mL/min, non-KED
200Hg standard mode 200Hg collision cell mode (O2)
Detection of Cu and Zn in 10 ppm Ti solutions
• The problems: TiO+ (and TiOH+) interferences on all Cu and
Zn isotopes (m/z 63 to 70)
m/z 68 and 70 interferences low abundance
but 70Zn also low (0.6%)
68Zn most useful in absence of collision cell
Must suppress TiO+ / TiOH+ interferences on
Cu and most abundant Zn isotopes
• The proposed solutions: Use O2 as the collision gas to try to promote
formation of higher Ti oxides / hydroxides
Compare with kinetic energy discrimination
(KED) approach, using H2/He collision gas
TiO+ interferences, 10ppm Ti
Cu / Zn isotopes, 10ppb Cu / Zn
47Ti16O+ = 13 Kcps 48Ti16O+ = 130 Kcps49Ti16O+ = 11 Kcps
63Cu+ = 85 Kcps64Zn+ = 68 Kcps65Cu+ = 42 Kcps
Cu, Zn in 10 ppm Ti, standard mode and O2 data
64Zn standard mode 64Zn collision cell mode (O2)
10.150.170.030.250Ti18O+68Zn
90.050.340.042.950Ti16O+66Zn
0.38
0.06
0.20
Detection limit 3σ (ppb)
20.3
3.1
2.1
BEC (ppb)
Standard mode Standard BEC / collision cell BEC
Collision cell mode (O2)#Ti interference
Isotope
0.23
0.11
0.05
Detection limit 3σ (ppb)
151.3548Ti16O+64Zn
170.1849Ti16O+65Cu
130.1647Ti16O+63Cu
BEC (ppb)
# O2 flow rate = 7.0 mL/min, non-KED
Cu, Zn in 10 ppm Ti, standard mode and H2/He KED data
64Zn standard mode 64Zn collision cell mode H2/He KED
10.130.250.030.250Ti18O+68Zn
120.020.250.042.950Ti16O+66Zn
0.38
0.06
0.20
Detection limit 3σ (ppb)
20.3
3.1
2.1
BEC (ppb)
Standard mode Standard BEC / collision cell
BEC
Collision cell (KED) modeTi interference
Isotope
0.05
0.07
0.02
Detection limit 3σ (ppb)
620.3348Ti16O+64Zn
220.1449Ti16O+65Cu
150.1447Ti16O+63Cu
BEC (ppb)
Data obtained using a 8% H2/He gas flow of 5.5 ml/min and a KED barrier of 3.5V
• 4 Standard Reference Waters were analyzed as ‘unknown’ samples over a 10-hour period
• Wide range of typical environmental analytes were measured - 30 analytes, 55 isotopes
• Several analytes had associated interference problems….
CCTED – Evaluation of Performance
Uptake
25s
Experimental - analytical profileA
naly
tes
Settle
Delay
30s
Settle
Delay
30s
Standard
Mode
3x18s reps
Wash
25s
Total Time Per Sample = 3 minutes, 45 seconds
Tim
e
Pro
file
V
Cr
NH3/He
3x1.6s reps
Li
Be
Na
Rb
Sr
Rb
Mo
Ag
Cd
Sn
Cs
Ba
Tl
Pb
U
Mg
Al
K
Ca
Cr
Fe
Mn
Ni
Cu
Zn
Ga
As
Se
H2/He
3x18s reps
Experimental - procedure
• Calibration: Blank 1ppb multi-element solution 10ppb multi-element solution
• 4 reference water samples analysed as QC checks 12 times over a period of 10 hours against 12 different calibrations
NIST 1640 diluted 1+9 and spiked to 2% HCl CNRC SLRS-2 spiked to 2% HCl CNRC SLRS-3 spiked to 2% HCl CNRC SLRS-4 diluted 1+1 and spiked to 2% HCl
• Detection limits calculated by running 10-replicate blank samples 12 times against 12 different calibrations
Results: stability in different measurement modes -10ppb standard
Long-Term Stability - 12 Hours
0.9
0.95
1
1.05
1.1
0 2 4 6 8 10 12
Time / Hours
No
rma
lise
d S
ign
al I
nte
ns
ity
206Pb NH3 Mode (0.6%)
207Pb H2 Mode (0.6%)
208Pb Std Mode (0.6%)
10ppb Solution
No internal
standard
correction
Each isotope measured in a different mode, switching from NH3 to H2 to Std mode in-sample
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%)
Results: stability of real sample in different modes
Sample diluted 1+9 and spiked to 2% HCl
7Li 0.01 55Mn 0.01 77Se 0.1 114Cd 0.0039Be 0.003 56Fe 0.06 78Se 0.03 118Sn 0.0123Na 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
Results – Method detection limits (g/L)
Based on 3s on 12x10replicates of blank, each from a new calibration
1640x10 7Li 9Be 24Mg 51V 52Cr 55Mn 59Co 60Ni 65CuMeasured 4.96±0.03 3.40±0.02 579±4 1.30±0.02 3.58±0.05 11.89±0.09 2.02±0.02 2.67±0.02 8.39±0.07Reference 5.07 3.49 582 1.3 3.86 12.19 2.03 2.74 8.52
Recovery % 98 97 100 100 93 98 99 97 99
1640x10 66Zn 75As 80Se 85Rb 88Sr 107Ag 111Cd 138Ba 208PbMeasured 5.11±0.05 2.61±0.02 2.12±0.04 0.192±0.004 12.0±0.1 0.75±0.03 2.21±0.02 14.2±0.1 2.65±0.03Reference 5.32 2.66 2.2 0.200 12.4 0.762 2.28 14.8 2.79
Recovery % 96 98 97 96 97 98 97 96 95
Results – accuracy of reference samples
SLRS-2 27Al 40Ca 51V 55Mn 56Fe 60NiMeasured 87±3 5500±300 0.248±0.007 10.1±0.2 127±2 1.01±0.03Reference 84 5700 0.25 10.1 129 1.03
Recovery % 104 97 99 100 98 98
SLRS-2 65Cu 66Zn 75As 88Sr 138Ba 238UMeasured 2.96±0.05 3.42±0.06 0.78±0.03 28.1±0.4 13.5±0.1 0.0464±0.0005Reference 2.76 3.33 0.77 27 13.80 0.049
Recovery % 107 103 101 103 98 95
NH3/He ModeH2/He ModeStd Mode
All concentrations in g/L
n=12
Results – accuracy of reference samples
Accuracy of Analysis Summary Plot
y = 0.9664x
R2 = 1
0.001
0.01
0.1
1
10
100
1000
10000
0.001 0.01 0.1 1 10 100 1000 10000
Reference Values (ug/L)
Measu
red
Valu
es (
ug
/L)
Analysis of Seawater Reference Materials
• Direct analysis of seawater is challenging: Extreme matrix Severe interferences Ultra trace analyte concentrations
• Analysed against a matched external calibration
• H2/He KED CCT mode used for ALL analytes
• Rapid method (~3 min/sample)
• No gas switching required
• No instrument settings switching required
• Easy set-up
XSeriesII – New Proof Data (ppt)
Analyte Measured Known Rec% 100ppt Spike Rec% 51V 146.2 120 122 9452Cr 13.43 11 122 9855Mn 93.72 91.9 102 10256Fe 60.88 20.7 294 9859Co 1.923 1.1 175 10060Ni 25.09 25.3 99 10365Cu 33.03 29.7 111 9366Zn 9.898 10.2 97 11075As 162.2 127 128 9778Se 1.927 1.8 108 84
111Cd 1.686 2.3 73 107114Cd 2.55 2.3 111 99208Pb 1.291 0.8 161 99
NASS-5 1:10
XSeriesII – New Proof Data (ppt)
Analyte Measured Known Rec% 100ppt Spike Rec%51V 139.5 118 118 10652Cr 14.36 14.4 100 9455Mn 282.1 278 101 10256Fe 119.7 71.3 168 10759Co 3.008 2.6 116 10960Ni 31.02 31.4 99 10865Cu 62.43 59.2 105 10466Zn 42.69 38.1 112 11075As 146.9 111 132 10478Se 8.874 - - 113
111Cd 2.318 2.6 89 98114Cd 2.186 2.6 84 99208Pb 1.69 0.98 172 91
CASS-4 1:10
XSeriesII – New Proof Data (ppt)
Analyte Measured Known Rec% 500ppt Spike Rec%51V 581.5 514 113 9652Cr 39.61 36.6 108 10055Mn 323.5 322 100 10156Fe 161.8 113.6 142 10359Co 9.048 8.4 108 11160Ni 257.9 246 105 9865Cu 325.9 310 105 10166Zn 35.36 40.2 88 10375As 361.9 272 133 8978Se 23.91 - - 96
111Cd 9.736 9.6 101 100114Cd 9.642 9.6 100 101208Pb 2.275 1.8 126 96
SLEW-3 1:5
CCTED Evaluation of Performance - Summary
• Provides Ease of Set-up– Auto-tune, performance reports allow fully automated set-up and analysis
• Ultimate Flexibility– Single mode runs ( e.g.. Seawater example)
• Fast analysis
– Mode Switching runs • Ultimate Detection Limits
• Handles the most extreme matrices (seawater) to give interference free measurements on difficult analytes
• Retains excellent stability and accuracy