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Routine Determination of Elements at Sub-ppb
Concentrations in Heavy and Light
Petrochemical Matrixes using ICP-MS Single
and Triple Quad
L. Craig Jones
October 21, 2013
Presentation Outline
1. Background on ICP-QMS and ICP-MS/MS
2. Unique product design benefits of the Agilent 7700 ICP-MS and 8800 ICP-MS/MS for analysing petrochemical matrixes
3. Petrochemical matrixes analysis discussion using ICP-QMS
4. Petrochemical matrixes analysis discussion using ICP-MS/MS
October 21, 2013
General Capabilities of ICP-MS for Solving Analysis Problems in Organic Matrices
• Multi-elemental technique• High sensitivity• Low Detection Limits • Short analysis time (~ 3 min)• Wide linear dynamic range• Minimized interferences with Cell Technology• High Productivity
Agilent 7700 ICP-MS and 8800 ICP-MS/MS
7700 is Agilent’s high performance single quadrupole ICP-MS Many unique capabilities including HMI, ORS3
8800 is World’s first ICP-MS to offer MS/MS New modes of operation and performance with MS/MS modes Built upon the industry leading 7700 ICP-QMS platform with shared sample introduction, HMI, many
consumables, robustness, key hardware components and software platform
Agilent 7700 Single-quad ICP-QMS
Agilent 8800Triple Quad ICP-MS/MS
4 October 21, 2013
Page 5
Agilent 7700 ICP-MS System in Detail
High matrix introduction (HMI) dilution gas inlet
Peltier‐cooled spray chamber
Off‐axis ion lens
Low‐flow Sample Introduction
Fast, frequency‐matching 27MHz RF generator
High‐performance vacuum system
Cell gas inlet
High‐frequency (3MHz) hyperbolic quadrupole
Fast, simultaneous dual mode detector (9 orders dynamic range)
High‐transmission, matrix tolerant interface
3rd generation Octopole Reaction System (ORS3)
Key Benefits of High Matrix Interface (HMI)
Page 6
Sample Introduction is:• Low-flow (typically
0.15mL/min) • Temperature stabilized (Peltier
cooled spray chamber)
Now features HMI (High Matrix Introduction) Kit as standard on 7700x model, allowing auto setup of plasma conditions and much higher matrix tolerance
HMI shows good recoveries even in 3% Total Dissolved Solids
Page 7
Key Benefits of ORS3 and O2 Option Gas
ORS3 Octopole Reaction Cell• 3rd Generation Octopole, Helium
collision cell for removal of Polyatomic interferences
• Allows analyses of difficult elements -Si, P, S & Se
O2 Option Gas MFC • Added to Aux gas at torch
• Allows Organics to be analyzed directly by ICPMS
• Auto setup of conditions
ORS3 is a KED tool for removing Polyatomic Interferences. It is the single Most Effective Tool for Removal of Polyatomic Interferences on the MS market today.Without it, Interferences from a complex acid matrix go from this
Page 9
… to this, with it!!
And there’s still plenty of Sensitivity to obtain the lowest of Detection Limits
Page 10
Organic Analysis using ICP-QMS
October 21, 2013Page 11
Direct Elemental Analysis of Gasolineby Single Quad ICP-MS with ORS
Direct Elemental Analysis of Biodieselby Single Quad ICP-MS with ORS
Direct Elemental Analysis of Biodiesel
Page 12
Direct Elemental Analysis of Biodiesel
Page 13
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Direct Elemental Analysis of Gasoline by ICP-QMSLong Term Stability
Direct Elemental Analysis of Gasoline by ICP-QMSSpike Recovery of Organometals in Gasoline
15
Agilent 8800 ICP-MS/MS
World’s first “Triple Quadrupole” ICP-MS (tandem MS) New modes of operation and performance not possible with quadrupole ICP-MS Unique capabilities, based on proven technology (shared sample introduction, HMI,
many consumables, robustness, key hardware components and software platform)
16 October 21, 2013
Agilent 8800 ICP-MS/MS System in Detail
17
Low flow sample
introduction system
High matrix introduction
(HMI) technology
Fast, frequency-matching 27MHz
RF generator Efficient twin-turbo vacuum system
Dual conical Extraction and Omega lens focus ions across the mass range
9 orders dynamic range
electron multiplier (EM)
detector
Analyzer quad Q2: High frequency
hyperbolic quadrupole – selects ions that pass to detector
High-transmission, matrix tolerant interface
First quad Q1: High frequency hyperbolic quadrupole mass filter –
selects ions that enter the cell3rd generation collision/
reaction cell (ORS3) with up to 4 cell gas lines
Peltier-cooled spray
chamber
Robust, high-temperature plasma ion source
ASTS 2012
Reaction Gases for ICP-QMS and ICP-MS/MS
Limitations of reactive cell gases in quadrupole ICP-MS are well-documented: All ions enter the cell, affecting reaction processes. Gives variable results when
sample type/matrix or co-existing analytes change Product ions from matrix or other elements can create new overlaps on analytes Analyte product ions can be overlapped by other analytes/matrix elements
Tandem MS configuration eliminates the variability caused by co-existing elements and changing matrix components, as Q1 rejects all masses except the target analyte and on-mass interferences Results are consistent and reliable
18
Agilent 8800 ICP-MS/MS matches 7700 performance in He mode, but also
offers controlled and consistent MS/MS operation in reaction mode.
October 21, 2013
ICP-MS/MS: How Does it Work?
ICP (plasma) and Interface: Forms and extracts ions from the sample (just like the 7700)
EM (detector): Measures the ions that are scanned by Q2 (just like the 7700)
19
Q1 – controls ions that enter the cell • Consistent reactions even if sample composition changes
ORS3 – collision/ reaction gas added• Ions react and are neutralized or moved
• Product ions are formed
Q2 – selects the target analyte mass• Interference-free analyte ions passed to EM
October 21, 2013
Q1 – controls ions that enter the cell • Consistent reactions even if sample composition changes
ORS3 – collision/ reaction gas added• Ions react and are neutralized or moved
• Product ions are formed
Q2 – selects the target analyte mass• Interference-free analyte ions passed to EM
ICP-MS/MS: How Does it Work?
ICP (plasma) and Interface: Forms and extracts ions from the sample (just like the 7700)
EM (detector): Measures the ions that are scanned by Q2 (just like the 7700)
Unique aspect of 8800 is MS/MS Mode• Q1 controls the ions that enter the cell
With MS/MS, reaction processes in the cell are consistent and predictable, even if sample composition is complex or variable• Consistent cell conditions means reaction
mode method development is much easier than on single quad (same method can be used for different samples)
20 October 21, 2013
October 21, 201321
ICP-QQQ can function in Single-Quad ModeQ1 operates as an ion guide or bandpass filter; can be used in no gas, helium collision mode, reaction mode (just like single quad ICP-MS).
Two “single-quad” modes of operation are available with ICP-QQQ:
ICP-QQQ has approximately 2x higher sensitivity and >5x lower background than 7700, so DLs are better even in single-quad mode
ICP-QQQ: What Can It Do?
A. Q1 as an ion guideAllows all ions through, so system works like a single-quad ICP-MS
• Functions like a single-quad with a “passive” cell
“ICP-QQQ does everything ICP-QMS can, only better!” Plus…
B. Q1 as a bandpass filterAllows a “window” of masses through, above/below the Q2 set mass (mass range can be adjusted by the user)
• Functions like a single-quad with a “scanning” cell
MS/MS Mass-Shift Mode (Q1 and Q2 set to a different masses):Q1 is set to precursor ion mass, controlling the ions that enter ORS. Q2 is set to mass of a target reaction product ion (usually containing the original analyte)
MS/MS with Mass-Shift is used when the analyte is reactive and the interferences are not reactive with a particular cell gas.
22
ICP-MS/MS: Mass-Shift/Neutral Gain
ICP-MS/MS Mass Shift mode is simple and reliable, as Q1 rejects all non-target precursor ions, so the cell processes are consistent
Q1 – Rejects all masses except analyte mass (analyte and on-mass interferences)
ORS3 – Separates (reactive) analyte and (unreactive) interferences by moving analyte to a new product ion mass
Q2 – Rejects all cell-formed ions apart from target analyte product ion, leaving analyte free from overlap
October 21, 2013
Sulphur Measurement In Organic Solvents
The accurate measurement of sulphur at low concentrations by ICP-MS has been particularly difficult especially if isotopic information needs to be preserved.
This can be even more difficult when analysing organic solvents due to plasma stability, ionisation suppression and the unique interferences presented by a mostly carbon-based sample.
Assuming plasma performance can be optimised by modern generator designs and optimised sample introduction systems the interferences still remain.
October 21, 201323
Sulphur Measurement In Organic Solvents
With conventional Collision-Reaction Cell (CRC) ICP-MS interferences can be reduced but not necessarily to a level that is useful or for all isotopes of interest.Due to the intensity of the carbon and oxygen interferences a mass-shift (neutral gain) methodology is often employed.• S measured as SO at +16amu
– If another isotope resides at the +16 mass (e.g. 48Ca & 48Ti on32S16O) analysis will be impaired
– All S isotopes react with all O2 isotopes causing low mass S isotopes to interfere with higher mass isotopes• 32S17O+ interference on 33S16O+
• 32S18O+ & 33S17O+ interference on 34S16O+
October 21, 201324
Removal of 16O2+ overlap on 32S+ using O2 cell gas
32S+ + O2 48SO+
16O2+ + O2 no reaction
Allows measurement of SO+ at product ion mass(es), after removal of original O2
+ interference, and potential overlaps on SO+ product ion mass.
Example of MS/MS Mass-Shift with O2 Cell Gas
25 October 21, 2013
Q1 – Rejects all masses except analyte mass (32S+
and on-mass 16O2+
interference)
ORS3 – Converts S+ to SO+ product ion
Q2 – Rejects all cell-formed ions apart from target SO+ product ion
Reaction gas (O2)48Ca/48Ti,
36Ar12CO2S 48SO+
16O2+
48Ca/48Ti, 36Ar12C
MS/MS Mass-Shift Mode – Measurement of S as SO+
Q1 is set to precursor ion mass, controlling the ions that enter ORS. Q2 is set to mass of reaction product ion (Q1 + 16amu in O2 mode):
32S+ converted to 48SO+ using O2 cell gas
26
ICP-MS/MS: Mass Shift with O2 Cell Gas
MS/MS provides practical benefits in research and real applications and is unique to Tandem MS configuration
32S16O+
33S16O+
34S16O+
Single-quad can also use mass-shift mode to move S (as SO+) away from the O2
+ interference.
BUT single quad cannot completely remove the 48Ca/48Ti and 36Ar12C overlaps on 48SO+
Also, on single-quad ICP-MS 32S18O+ and 34S16O+ both appear at mass 50; ICP-MS/MS with mass-shift enables S isotope analysis, as only the target S isotope is measured
October 21, 2013
8800 ICPMS Calibrations – using MS/MS mode
Other Benefits of Tandem MS Configuration –Greatly Improved Abundance Sensitivity
28 October 21, 2013
Boron Measurement in Organic Matrix - Kerosene
Single Quad Mode –standard resolution settingBlank kerosene sample
Tail of 12C completely overlaps 11B isotope
October 21, 201329
12C (and 13C) over-range and skipped automatically
Boron Measurement in Organic Matrix - Kerosene
MS/MS Mode – standard resolution setting
Blank kerosene sample
Abundance Sensitivity improvement means both B isotopes can be used
October 21, 201330
12C over-range and skipped automatically
Boron Measurement in Organic Matrix - Kerosene
MS/MS Mode – standard resolution setting
Spiked Kerosene (5.77 µg Kg-1)
October 21, 201331
Boron BEC & DL Improvement MS/MS Mode
BEC and DL greatly improved particularly for 11B due to no contribution from 12C
October 21, 201332
Agilent 8800 ICP-MS/MS – Key Features
• Outperforms quadrupole ICP-MS for conventional applications
• Provides unique, high-performance MS/MS mode
• Tandem MS configuration ensures control of ions that enter the cell; controlled reaction processes deliver reliable results
• Offers ultimate flexibility for problem solving and advanced research
• Utilizes critical hardware and same MassHunter software platform as the proven 7700, ensuring reliability and supportability (global network of service and applications support)
33 October 21, 2013
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