chemical analysis, life sciences, and diagnostics - routine ......presentation outline 1. background...

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

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)

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

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

… to this, with it!!

And there’s still plenty of Sensitivity to obtain the lowest of Detection Limits

Organic Analysis using ICP-QMS

October 21, 2013

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

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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

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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

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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

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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)

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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.

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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

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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


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


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

chemical analysis, life sciences, and diagnostics - routine ......presentation outline 1. background...

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