An Introduction to ICP-MS

PerkinElmer Instruments 710 Bridgeport Avenue Shelton, CT 06848 203-944-2481

Agenda of the course 10.00 --- 10.30 10.30 --- 1.00 1.00 --- 2.00 2.00 --- 2.30 2.30 --- 3.00 3.00 --- 3.15 3.15 --- 5.00 5.00 --- 5.30 ICPMS- Introduction & Benefits Instrumentation Lunch Interferences & how to overcome it Maintenance procedures Tea Break Elan s/w Q-A & Feedback

The ELAN DRC II

What Is ICP-MS?

A metal detector A technique used to measure metals

Capable of measuring ppt (ng/L) to ppm (mg/L) levels

How its done

Sample introduced into an Inductively Coupled Plasma (ICP) Ions are formed in the plasma Ions are sorted by mass Ions are detected

Benefit of ICPMS over other techniques

1) Speed 2) Good Detection limit detection limit upto PPT level for most elements 3)Can handle complex samples

4) Solid sampling possible with help of Laser ablation accessory

5) Can detect each isotope of all elements giving possibility to carry out isotope dilution & isotope ratio

Elements ICPMS measure with detection limits

ELAN family specifications

DRC-e better than 9000 Same low background, slightly less sensitive than DRC II ELAN 9000
Detection Limits (ng/L) <9 59Co < 2 115In < 0.5 238U < 0.5
9Be

ELAN DRC-e
<9 59Co < 1 80Se < 10 DRC 115In < 0.5 238U < 0.5 >5 115In > 25 238U > 20
24Mg 9Be

ELAN DRC II
<6 40Ca < 2.0 DRC 56Fe < 0.7 DRC 59Co < 1 115In < 0.2 238U < 0.2 >8 56Fe > 40 DRC 115In > 40 238U > 30
24Mg 9Be

Sensitivity Mcps/ppm

24Mg

> 10 115In > 40 238U > 30

CeO+/Ce+
Ba2+/Ba+ Background Stability
Mass 220 < 5 (sd)

< 3%
< 3%
Mass 220<2cps Mass 220<2cps

< 4% over 4 hours

Note: DRC-e values are preliminary target mfg. Specifications not final at this time

Components of Every ICP-MS System Sample introduction system Ionization source Interface Ion focusing system Mass filter Ion detection system Control software

ICP-MS - Component Diagram

Plasma Spectrometer Interface Electron Multiplier ICP Torch Ion Lens

Spray Chamber

Quadrupole Mass Filter

Sample

Turbo Pump

Turbo Pump

RF

Mech Pump

Supply

ICP-MS Computer and Control Electronics

Sample Introduction System

Function
To get the sample into the plasma

How its done

Liquid is pumped into a nebulizer An aerosol mist is created The mist droplets are separated by size in the spray chamber Only the finest droplets are carried into the ICP

Ionization Source The Inductively Coupled Plasma (ICP)

Function
To create ions from the elements in the sample

Ions Created Here

How its done

The plasma temperature is about 6000K The aerosol is dried Positive Ions are created by stripping electrons from the aerosol particles which are directed into mass analyzer for quantification in ICPMS. It is generation, transportation, & detection of significant nos of these positively charged ions that give ICPMS its characteristic ultratrace detection capabilities.

Mechanism of conversion of a droplet to + ion in ICP

Different temperature zones in Plasma

The Interface

Function
To transfer ions from the ICP to the area for mass separation Atmospheric pressure to 10-6 torr Sampler Skimmer Atmospheric Pressure

10 -6 torr

How its done

Ions are extracted from the plasma via differential pressures Use cones and vacuum pumps 10 -3 torr ICP

Interface Region and Cones

Both Ni and Pt available Large diameter orifices to minimize clogging while maintaining vacuum
Sampler - 1.1 mm Skimmer - 0.9 mm

Very easy maintenance: removal, cleaning, reinstallation.

skimmer cone sampler cone

Ion Focusing System - The Ion Lens

Function
To corral the ions after the Interface and send them to the mass filter
Differential Aperture Rf Only Mass Filter Filter Shadow Stop Sampler Skimmer

How its done

An electric field focuses the ions into the mass filter The electric field originates from an Ion Lens Ion Lens A metal cylinder

Cylinder Lens

Mass Filter

Ion Optic

Interface

Ion Beam Focusing

Aperture

Cylinder Lens

Shadow Stop

Skimmer

AutoLens - Dynamic Lens Optimization

1.2

Normalized Signal

1
Li

0.8 0.6 0.4 0.2 1 3 5 Lens Voltage, V 7 9

Co Y In Pb U

Ion Lens

One piece Lens

Shadow Stop Voltage can be changed to accommodate different masses Shadow Stop blocks photons and non-ionized particles since they are neutral & unaffected by electrostatic field & pass straight on the photon stop.

Mass Filtering System - The Quadrupole

Function
To separate one elements (ions)

How its done

Electro-magnetic fields of the quadrupole rods allow only one mass (m/z) to pass through it at a time Many masses enter, only one makes it out

Mass Filtering - How a Quadrupole Works

1 amu lighter
=> Driven into rods

Set mass Transit successfully

1 amu heavier => Collide with rods

Ion Detection - The Electron Multiplier

Function
To count the number of ions leaving the mass filter.
Pulse Signal Out

How its done

Ions leaving the quadrupole collide with the detector A cascade of electrons results which can be measured by the electronics.

Analog Signal Out

Operates Simultaneously
In Pulse and Analog modes for increased dynamic range Measures low and high concentrations together

Ions In

Interferences in ICP-MS

Spectral
Elemental-Isobaric Molecular-Polyatomic

Physical Matrix

ICP-MS Spectral Interferences

Some common anions can form interferences which adversely effect detection limits Interference
40Ar 40Ar16O, 40Ca16O 40Ar12C 40Ar13C

Analyte
40Ca 56Fe 52Cr 53Cr 75As 31P 60Ni 51V 80Se

, 35Cl16O1H , 40Ar12C 1H

35Cl40Ar, 35Cl40Ca 15N16O, 14N16O1H 44Ca16O 35Cl16O 40Ar40Ar

Ways to overcome spectral interference 1)Removal of matrix & analyte preconcentration 2) Mathematical correction 3)Cold Plasma technology 4)Reaction Cell-DRC technology 5)High resolution mass analyzerMagnetic sector 6) Use of alternate mass number

What is the ELAN DRC ?

ELAN ICP-MS system with a quadrupole located between lens and analytical quadrupole (mass analyzer) Dynamic Reaction Cell can be pressurized with a reaction gas
Interferences (e.g. ArCl+, ArC+) eliminated by reactions with a reaction gas

Dynamic Bandpass Tuning - Actively controls the mass bandpass inside the DRC - Controls interference reduction chemistry - New interferences cannot form

ICP-MS with a Dynamic Reaction Cell

Mass Analyzer Quad

Detector

Reaction Cell Quad

Cones

Lens

Example of a Reaction Inside the DRC

Removal of

40Ar35Cl

from 75As
Gas Inlet

DRC Quadrupole

Gas (H2)
40Ar35Cl

75As

+
+

+ + ++ + + + + +

+ + + + + + +

75As

Analyzer Quadrupole

Ion-Molecule Reactions and Collisions

For Ultra-trace ICP-MS Analyses of Cr, V, As, and Se in Biochemical Matrices Analyte 52Cr 53Cr 51V 75As 80Se DRC Eliminates 40Ar12C, 35Cl16OH, 36Ar16O 40Ar12CH, 40Ar13C, 37Cl16O 36Ar17O 35Cl16O 40Ar35Cl 40Ar40Ar

Matrix interference Suppression of signal due to matrix itself like in case of organic samples the sample introduction of samples is affected due to viscosity of the samples. Compensation for this interference is the use of internal standardization.

Space Charge interference Defocusing of low mass analytes in presence of high mass analytes ions. Proper application of lens voltage helps in removing the high mass analyte ions while steering low mass ions towards the quadrapole.

Maintenance 1) Aspirate 2%hno3 for 10-15 min after the analysis is over. 2)Check & replace if necessary pump tubing. 3)Clean spray chamber, injector , torch. 4)Replace load coil if required. 5)Check & clean both cones in 1% hno3 in ultrasonic bath. 6) Clean or replace lens. 7) change pump oil after 3-6 months. 8) Replace Detector.