Inductively Coupled Plasma Mass Spectrometry
ICP‐MS is a fast, multi‐element, high sensitivity trace metals analysis technique
Key applications are:
• Environmental• Foods• Semiconductor• Clinical• Chemical/Petrochemical• Pharmaceutical• Consumer GoodsConsumer Goods• Forensic• Geological• Nuclear• Academic/Research
ICP‐MS market continues to grow as technology improves and GFAA and ICP‐OES instruments are replaced with ICP‐MS
Agilent ICP‐MS Instrument Development
Agilent 7700 SeriesThe new face of ICP‐MS
Agilent 7500 Series
Agilent 4500 SeriesThe new face of ICP MS
Agilent’s History of Innovation in ICP‐MS – 1987 to 20091987 – PMS 100 introduced – First computer‐controlled ICP‐MSp1988 – PMS 200 introduced – Second generation ICP‐MS with off‐axis Qpole lens1989 – 1st ETV accessory for semicon analysis by ICP‐MS1990 – PMS 2000 introduced – Omega off‐axis lens. Lowest random background ICP‐MS1992 – ShieldTorch interface developed ‐ Ar interferences virtually eliminated in cool
plasma enabling ppt analysis of K Ca Fe by ICP MSplasma, enabling ppt analysis of K, Ca, Fe by ICP‐MS1994 – 4500 Series introduced ‐World's first benchtop system. Hyperbolic profile quad,
motorized torch XYZ, cool plasma1998 – First real time ICP‐MS chromatographic software – PlasmaChrom. T‐mode
reaction interface introduced
Agilent 4500 Series
ShieldTorch System
Octopole Reaction1999 – 4500 Series 100, 200 & 300 introduced: 1st applications‐specific ICP‐MS.2000 – Agilent 7500 Series introduced ‐ 7500a, 7500i and 7500s ‐ the next generation in
ICP‐MS instrumentation. 9 orders detector range2001 – Agilent 7500c launched – 1st generation ORS for high matrix samples. 2002 – New digital generators and LAN control introduced First commercial GC‐ICP‐MS
Octopole Reaction System
2002 New digital generators and LAN control introduced. First commercial GC‐ICP‐MS interface.
2003 – Agilent 7500cs launched – 2nd generation ORS for high purity semicon samples. 2004 – Agilent 7500ce launched – 2nd generation ORS for high matrix samples. 2005 – Low flow cell gas MFC’s for Xe NH3, O2, etc added to 7500ce/cs.
Agilent 7500 Series
2006 – Agilent acquires 100% of Agilent/Yokogawa joint venture 2007 – Agilent 7500cx introduced: He only mode ICP‐MS2008 – High Matrix Interface developed – enables 2% TDS samples to be run by ICP‐MS2009 – Agilent 7700 Series introduced – replaces 7500 Series. MassHunter Software
introduced ‐ common platform with other Agilent MS. ISIS‐DS Discrete samplingintroduced common platform with other Agilent MS. ISIS DS Discrete sampling system, for ultra high throughput analysis Agilent 7700 Series
7700 Series – New Product HighlightsNew ORS3 Collision/Reaction CellNew ORS Collision/Reaction Cell
Longer, narrower rods, higher cell pressure and frequency – MUCH better performance in He mode
N RF G tNew RF GeneratorFast tuning 27MHz generator, for better tolerance to changing matrix (incl. organics)
Increased Matrix ToleranceHigh Matrix Introduction (HMI) standard on 7700x model
Much smaller cabinet>30% smaller footprint than any other ICP‐MS
Simple software; reliable Auto‐TuningMassHunter software – intuitive and easyto learn. Pre‐set plasma conditions and pfast lens auto‐tuning
Two 7700 Models
7700x 7700s7700x• High productivity system• Third generation ORS• HMI• Environmental, food, clinical, pharmaceutical and general purpose
7700s• Clean room ready• Third generation ORS• Cool plasma• Mineral acids, silicon matrices, organics, DIW h i lpharmaceutical and general purpose
applicationsDIW, process chemicals
Agilent 7700 ICP‐MS System in DetailOff‐axis ion lens 3rd generation
High matrix introduction (HMI) dilution
gas inlet
Off axis ion lensCell gas inlet
Fast, simultaneous dual mode
detector (9 orders d i )
gOctopole Reaction System (ORS3)
gas inlet
Low‐flow Sample Introduction
dynamic range)
Peltier‐cooled spray chamber
High‐frequency (3MHz)
hyperbolic quadrupole
p y
High‐performance
Fast, frequency‐matching 27MHz RF generator
vacuum system
High‐transmission, matrix tolerantmatrix tolerant
interface
Inorganic Analysis Techniques in a Typical Laboratory %
ICP‐OES – for majors and high matrix samples
Multi‐element, ~2 min/ sample
10’s ppb to 1000’s ppm
f l d l lICP‐MS – for trace elements and clean samples
Multi‐element, ~4min/ sample
Single ppt to 10’s ppmppm
GFAAS
Single element, ~6min/ppb
Hydride/AFS
Few elements,
LODIn many inorganic labs, several analytical techniques are used, to cover the range
f l i d d i6min/ sample
10’s ppt to 100’s ppb
pp ,~2min/ sample
Single ppt to 10’s ppb
of analytes, matrices and detection limits required. This is encouraged by
some vendors, who want to sell multiple instruments to each lab!
Few Elements/Samples
ppt
Many Elements/SamplesFew Elements/Samples Many Elements/Samples
Inorganic Analysis Techniques in a Typical Laboratory %
ICP‐OES
Multi‐element, ~2 min/ sample
10’ b t 1000’f l d l l
7700 ICP-MSMulti-element
10’s ppb to 1000’s ppmICP‐MS – for trace elements and clean samples
Multi‐element, ~4min/ sample
Single ppt to 10’s ppmppm
Single cell gas mode and productivity tools reduce run timeHMI for samples with % level solids
Single ppt (incl. hydride and Hg) to 100’s ppm (1000’s ppmith HMI)
GFAAS
Single element, ~6min/ppb
Hydride/AFS
Few elements,
LODwith HMI)
Uniquely, the Agilent 7700 can 6min/ sample
10’s ppt to 100’s ppb
pp ,~2min/ sample
Single ppt to 10’s ppb
q y, greplace all these separate techniques, providing high throughput, matrix tolerance, wide elemental coverage
Few Elements/Samples
ppt
Many Elements/Samples
and low LODs in a single run
Few Elements/Samples Many Elements/Samples
7700 ‐ Smaller Cabinet; Longer Ion Path!!
The 7700 has >30% smaller footprint than any other ICP MS butThe 7700 has >30% smaller footprint than any other ICP‐MS, but access for maintenance has been improved (all service from front)
Despite much smaller external cabinet size, the ion path of the 7700 i ll 30 l h h 7500is actually 30mm longer than the 7500
Extra length due to redesigned cell (longer octopole rods) and lens
30% smaller footprint
30mm longer ion path
Unique Performance of the 7700
Better matrix tolerance than any other ICP‐MS
• Higher plasma temperature (lower CeO/Ce ratio) under standard conditions than any other systemy y
Best performance with Helium cell gas – eliminates need for reaction gases in all common applications
7700 ORS3 improvements ‐ removes all7700 ORS improvements removes all polyatomics in He mode, giving accurate results in complex or variable sample types – impossible on ICP‐MS systems that use
i ll ireactive cell gases or mixtures
Wider dynamic range than any other quadrupole ICP‐MSq p
Full 9 orders dynamic range at the detector – linear to 500ppm without changing conditions or hardware
7700 Series Sample Introduction
• Low‐flow (typically 0.15mL/min)
• Temperature stabilized (Peltier cooled spray chamber)p y )
• Wide Torch Injector ID (2.5mm)
• No O‐rings in spray chamber end‐cap – reduced risk of contaminationcap – reduced risk of contamination
• Auto‐alignment of torch after maintenance
F f hi RF• Fast frequency‐matching RF generator
• Simple setup, using “pre‐set” l d dplasma conditions and auto‐tuning
Provides most robust plasma of any ICP‐MS under standard conditions
All New RF GeneratorThe new RF generator ofThe new RF generator of the 7700 operates using a
unique computer controlled fast tuning
design to instantly matchdesign, to instantly match to changing load.
This means that the 7700 can switch from pure
water to volatile organics without disturbing the
plasma
Comparison of Plasma Loading/Cooling Hottest part of Sample channel is Residence time is a ICP‐MS plasma must produceplasma ~ 8000K
By sample cone, analytes present as M+ ions
pat ~6700K few milliseconds
ICP MS plasma must produce ions – neutral atoms cannot be measured (unlike ICP‐OES where many of the best
+Highest M+ population should correspond to lowest polyatomic population
emission lines are atomic)Sample introduction must maintain high plasma
Conventional ICP MS Optimized ICP‐MS (7700)
Particles are decomposed and dissociated
Aerosol is Dried Atoms are formed and then ionised
temperature – monitored using CeO+/Ce+ ratio
++
Conventional ICP‐MS0.5 ‐ 1.0mL/min, 1.8‐2.0 mm Injector, no water vapor removal Low central channel temperature
Optimized ICP‐MS (7700)0.10 ‐ 0.25mL/min, 2.5mm Injector, water vapor removed High central channel temperature
++ + +
+
++
+
+++
++
High sample load, narrow central channelpoor matrix decomposition
Low sample load, wide central channelgood matrix decomposition
CeO/Ce Ratio – Effect on Matrix Suppression When a high sample matrix (e.g. 1/10 seawater) is introduced, the plasma isWhen a high sample matrix (e.g. 1/10 seawater) is introduced, the plasma is overloaded and analyte signal drops (suppression). Suppression is worse when the CeO/Ce ratio is higher (plasma temperature is lower)
Signal Suppression in 0.3% NaCl
90.0100.0
50.060.070.080.0
cove
ry
1% CeO/Ce
10 020.030.040.0
% R
ec 1.7 % CeO/Ce
Spike recovery in a high matrix is better with a robust
0.010.0
Sc-45 Cr-52 Fe-56 Zn-66 Mo-95 In -115
Elements
plasma (low CeO/Ce ratio)
7700 has the lowest CeO/Ce ratio in standard conditions of any ICP‐MS (<1%)
Other Benefits of High Plasma Temp.Reducing CeO+/Ce+ ratio from 3.0% to 1.0% (3x reduction) removes ~70% of many g / ( ) ymatrix‐based interferences (ArCl+, ClO+, CaO+, etc)
Hotter plasma is less affected by a variable matrix (more robust)
Better matrix decomposition reduces interface and lens contamination and therefore preduces maintenance
Hotter plasma improves the ionization of poorly ionized elements, so MUCH lower LODs possible for Be (right), B, As, Se, Cd, Hg (below), etc
S b t BSub ppt Be detection limit!
30ppt30ppt
10ppt
5ppt Hg BEC (ppt) LOD (ppt)
201 9.49 1.51Be BEC (ppt) LOD (ppt)9 0.465 0.235
High Matrix Introduction (HMI) – How it Works
HMI is a sample dilution technique but, uniquely, it dilutes the sample in thedilutes the sample in the gas state, using aerosol dilution.
This removes the main problems of liquid sample dilution:
•Time•ReagentsE•Errors
•Contamination
HMI – Automatic Setup of Plasma Conditions
Principle of HMI is simple –hardware comprises extrahardware comprises extra gas line to dilute aerosol.
However, requires very sophisticated softwaresophisticated software algorithm to map plasma conditions, and very
reproducible hardware toreproducible hardware to allow conditions to be recalled consistently
HMI Robust Plasma → Low Oxide Interferences
Recovery of a 1 ppb Cd spike in increasing Mo concentration (0, 2, 5 ppm Mo). Comparison of standard 7700x (1% oxides) and
7700x under HMI conditions (0 2% oxides)7700x under HMI conditions (0.2% oxides)
HMI – Effect on Matrix SuppressionHMI dilutes aerosol density & water vapour, as well as sample matrix.Gives much higher100
120
+/- 15% Gives much higher plasma temp; much better matrix decomposition. Matrix suppression is almost
80
100
0ppb
Spike
/ 15%
suppression is almost eliminated.
Plot shows % recovery in dil d
40
60
Recovery of 10
2% CeO/Ce
1% CeO/Ce
undiluted seawater vsaqueous calibrations. With HMI, ALL results are within +/‐ 15% 0
20
% R
0.2% CeO/Ce
/recovery (shaded area)Without HMI, ALL results are below 60% recovery
0
Elements
Other Benefits of HMI
HMI increases sample throughput
• Reduces sample prep time (no manual or auto‐dilution)• Reduces number of over range samples which have to be repeated• Reduces number of over‐range samples which have to be repeated
HMI decreases routine maintenance
• HMI dilution reduces the matrix loading on the plasmag p• This decreases the amount of matrix which reaches the interface cones and so less maintenance (cone cleaning) is required
• Lower matrix loading also improves long‐term stability, which decreases the o e at oad g a so p o es o g te stab ty, c dec eases t eneed to run repeated calibrations
– Further increases sample throughput
7700 Series Interface
• New interface provides simple access for maintenance – remove and refit cone without any tools
• Provides good ion i i d itransmission and matrix
tolerance
7700 Series standard interface provides high sensitivity and good matrix tolerance as standard – no need for a separate set of low‐sensitivity cones for high matrix samples!
7700 Series Ion Lens
• Ion Lens focuses ions into the cell, and rejects photons and neutrals
• 7700 uses a combined Extraction/Off‐axis Lens – located outside high‐vacuum region, so easy to access for maintenance
• Provides ideal combination of high transmission across the mass range, low random background, and protection from matrix contamination in the high vacuum
iregion
• No need to set up variable voltages to increase ion transmission at specific masses
ll i d ll h i !– all masses are transmitted all the time!
7700 Series has the highest ion transmission across the mass range of any ICP‐MS, in standard, matrix tolerant conditions
All New Octopole Reaction System (ORS3)
The 7700 uses a completely new collision/ reaction cell, with:
18% longer rods18% longer rods
15% smaller ID
and operates at
16% higher pressure
20% higher frequency
ORS3 also operates with a much larger energyORS3 also operates with a much larger energy discrimination step.
Result is much more effective removal of interferences in He mode with KED
Major improvement compared to 7500 Series, which already offered by far the best He mode performance of any ICP‐MS
Se Calibration (in 2% HCl + 100ppm Ca)Calibration for 78, 80, 82Se at 0, 0.5, 1, 10ppbCalibration for 78, 80, 82Se at 0, 0.5, 1, 10ppb
Sub‐ppb LOD shows interference removal on all Se isotopes – essential for accurate isotope ratio or isotope dilution measurementLOD shows 0ppb
Isotope BEC (ppt) LOD (ppt)78 7.95 <5ppt
80 301 133
82 252 210
dilution measurementppBlank was 2cps +/‐ 0cpsProbably <5ppt LOD
82 252 210
Improved performance for Se with ORS3 in He mode –li i t th d feliminates the need for reaction mode in routine applications.
No SeH or BrH formation (affects all reaction gases)No SeH or BrH formation (affects all reaction gases)
High‐Frequency Hyperbolic Quadrupole
7700 Series retains the renowned research‐grade
hyperbolic quadrupole of the 7500 Series Still the only7500 Series. Still the only
hyperbolic quadrupole used in any commercial ICP‐MS.Provides excellent peak
ti f th b tseparation, for the best abundance sensitivity
specification:Low Mass: 5 x 10‐7
High Mass: 1 X 10‐7
7700 Quadrupole & Abundance Sensitivity
3MHz hyperbolic quadrupole with alignment3MHz, hyperbolic quadrupole with alignment tolerance to 1 micron
• Winner of 2006 Bill Hewlett Innovation Awardf• U.S. Patent #6,926,783: Manufacturing Precision
Multipole Guides and Filters• "This invention is the most significant advance in quadrupole mass filter technology in 40 years." J D ll A il S i S ff S i iJerry Dowell, Agilent Senior Staff Scientist
Best Abundance Sensitivity Specification of any ICP‐MS – no need to set up custom resolution to separate adjacent peaks – all peaks are separated p j p p punder standard conditions!
(Factory performance certificate ships with every 7700 Series instrument)
Agilent 7700Low Mass Side 5x10‐7 (Cs)High Mass Side 1x10‐7 (Cs) Quadrupole with alignment mandrelHigh Mass Side 1x10 (Cs) p g
9 Orders Dynamic Range DetectorUnique Discrete Dynode Electron Multiplier (DDEM) detector, providing 9 orders dynamic range (6 orders in pulse mode, and 3 further
orders in analog).Also has shortest minimum dwell time 0.1ms in
both pulse and analog modesGenuine 9 orders dynamic range so major
elements at 100’s ppm can be measured in theelements at 100 s ppm can be measured in the same run as trace elements at ppt, without
operator having to change conditions or hardware configuration.
C lib i h N i 1 10 d 1 5 dil dCalibration shows Na in 1:10 and 1:5 diluted seawater – top point is 2360ppm
7700x – Largest Analytical Range of any ICP‐MS
Calibration ran esThese 4 plots were obtained under the same analytical conditions
Calibration rangesHg (10 – 200ppt) – NoGas ModeAs (10 – 200 ppt) – He ModeSe (10 – 200 ppt) – He ModeNa (0 05 1000 ppm) He Mode As
Hg
p yon the 7700x – only the gas mode (NoGas for Hg) changed
AsNa (0.05 – 1000 ppm) – He Mode
Overall calibration range 10ppt (Hg, As, Se) to 1000 ppm (Na) in a single method
As
10 ppt Mercury
10 ppt Arsenicmethod
‐ without attenuating ion transmission to increase working range
Na
Arsenic
NaTypically, ICP‐MS cannot measure above 200ppm Na without changing quad resolution or ion lens settingsHg
1000 ppm Sodium
Se NaSeGood fit at 0.2ppm
HgHg LOD on 7700x is about 2ppt –7700x can QUANTIFY at 10ppt!
7700x can do both of the above in the
10 ppt Selenium
fsame run!
7700 – 9 Orders Detector Dynamic Range
Original ICP MS pulse countDetector range comparison: The entire green‐shaded area is within the measurement range of the 7700 Series detector, but 90% of these concentrations would be over‐range on other detectors, requiring manual signal attenuation or dilution for these concentrations to be measured on other ICP‐MS instruments.
Original ICP‐MS pulse‐count detectors gave 6 orders dynamic range (up to 2Mcps)
Analog mode typically adds a1) 7700 Series detector – 9 orders dynamic range, from 0 to 500ppm
Analog mode typically adds a further 2 orders dynamic range (up to 400Mcps), equivalent to about 50ppm
Agilent 7700 Series detector adds another order of dynamic range in analog mode – up to 4,000Mcps or around 500ppm
2) Typical ICP‐MS detector – 8 orders dynamic range, from 0 to 50ppm
around 500ppm
Upper range is even higher for mineral elements in He mode, as low‐mass signal is reduced when
3) Older, pulse‐count only detector – 6 orders dynamic range, from 0 to 0.5ppm
gcell is pressurized.
7700 electronics increase detector lifetime to >2 years (around 6 months on other ICP MS)months on other ICP-MS)
New hardware
New x-lens
New sampling cone
ORS3New RF generator
Size – Foot print is more than 30% smaller than Agilent 7500
Agilent 7500 D600 ( 720 w/ plug ) x W 1100 ( 1210 included SC) x H575 ( 645 with Chimney)
Agilent 7700 D620 ( 720 w/ plug ) x W 730 ( 860 included SC) x H595 ( 655 with Chimney)
Weight ‐ more than 30% lighter 115kg (Agilent 7700 ) vs 175kg ( Agilent 7500)
Build Quality
The renowned build quality, durability and reliability of the 7500reliability of the 7500 has been further improved
This photo shows the high quality finish of g q ythe 7700 ICP‐MS –even the rear panel that is not seen bythat is not seen by users
Even Cleaner than the 75007700 k l i7700s takes clean‐room operation even further
Single exhaust duct (no need for–Single exhaust duct (no need for optional duct kit)
–No external air exhaust vents intoNo external air exhaust vents into clean‐room
–Lower exhaust flow requirement (5‐7m3/min, down from 7‐8m3/min)
–Much lower pressure drop (140Pa f 7500 t 40P f 7700)for 7500, to 40Pa for 7700), simplifies clean‐room installation and reduces air‐handling costs
Chromatographic ApplicationsSi l li k A il LCSimple link to Agilent LCDirect sequence control from ICP‐MS sample log tableMethod setup for LC/GC from ICP‐MS PC
Predefined application packs available, as for 7500Data Analysis software now integrated into main suiteSame service support for all units
Overview of Data Analysis Window (MassHunter)– Batch View Data table with real‐time update during sequence, on‐screen display of outlier/QC failures (e g flag for results outside calibration range)outlier/QC failures (e.g. flag for results outside calibration range)
Calibration Plots – 12 Plots or Single Plot– Calibration view can show 12 plots, single plot, or single plot with calib table
– Elements with outlier flags are highlighted with calib plot shading
– Current element in currently selected sample line is shown on calib curve
Highlight shows g gelement with outlier (e.g. over calib range)
Current sample result shown on calib plotshown on calib plot
ISTD Stability and LabQC Plots
G hi l– Graphical pane shows ISTD Plot (recovery)
– Can also show LabQC recovery (up to 3 can be defined)
– Same pane can be used to show spectrum or h t hichromatographic data – can be expanded to full screen orscreen, or minimised to default layout
Spectrum ‐MassHunter– Simple tools to view, zoom and scroll spectra, overlay files and tune steps, and process spectra to give semi quant dataspectra to give semi‐quant data
Overlay spectra or tune mode totune mode, to
quickly compare data
Peak ID – no limit to number of elements
Chromatographic Data Analysis ‐MassHunter– Chromatographic Data Analysis option is fully integrated into main Batch table view, including real time update calib display and outlier flags Familiar GUI (similar to LC/MS)including real‐time update, calib display and outlier flags. Familiar GUI (similar to LC/MS)
Chromatographic Data Analysis – Manual Integration
M l i t ti ith d t f th d/ t ith ll i t t d k( )– Manual integration, with update of method/report with manually integrated peak(s)
Chromatographic Data Analysis – Signal/NoiseSignal to Noise Calculation (per compound, per analyte or per sample)
Screen shows S/N for compound AB = S/N is shown above the selected peak.selected peak.
Noise region can be selected for all compounds and all Noise region – selected in
l li analyte masses, for all compounds of the selected mass, or just for the selected
lower pane – applies to selected compound and
mass only
Signal/Noise result displayed as peak label and printed in report
for the selected compound
MassHunter Software
Significant improvement in ease of use and functionality
Easier to learnEasier to learn
• Faster learning cycle = improved productivity.
New software capabilities for speciationNew software capabilities for speciation
• Chromatographic data analysis software integrated with main data table
Excel based reportingExcel based reporting
Common SW platform with other Agilent instruments – GC/MS, GC/MS/MS, LC/MS, and LC/MS/MS/ / , / , / /
• Reduced staff training costs
7700 Environmental Impact Reduction
L l t i l i t d t t d iLower electrical power requirement, due to new rotary pump design
Lower heat output and reduced exhaust vent flow (for 7700s), with redesigned cooling air‐flow management system
All stainless‐steel outer panels, requiring less paint and associated solvents
Reduction of toxic compounds in Printed Circuit Boards
Increased use of recyclable materials such as plastic componentsIncreased use of recyclable materials, such as plastic components
At only 110Kg, the 7700 mainframe weighs 30% less than the 7500 Series, so significantly reduced CO2 emissions from transportation
Th 7700 i th fi t i t ll f i dl ICP MSThe 7700 is the first environmentally friendly ICP‐MS
Agilent 7700 with ORS3 – The Most Powerful ICP‐MS for the Routine or Research LabICP‐MS for the Routine or Research Lab• Effective removal of polyatomic interferences using He mode only, even in unknown and variable sample matricesp
• Simple method development – same conditions used for all elements and all sample types
• No new interferences and no loss of analyte signal by reaction
• Highest data integrity in unknown matricesHighest data integrity in unknown matrices
• Unmatched sensitivity across the mass range
• Widest dynamic range low ppt to 1000ppm• Widest dynamic range – low ppt to 1000ppmThe 7700x simplifies ICP‐MS operation, while improving matrix tolerance and providing unparalleled interference removal in
complex and variable samples
Top Related