Basic and Application of ICP-MS

By Pankaj Kumar
Water Lab

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 Basic and Application of ICP-MS
 Introduction.
 Fundamentals.
 ICP-MS Theory
 Interferences
 ICP-MS new update

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. Introduction.
ICP-MS (inductively coupled plasma-mass-spectrometry) is a technique to
determine low-concentrations (ppb) and ultra-low-concentrations of elements
(ppt) are widely applied of samples, such as Petrochemical, agriculture chemical,
clinical and biochemistry, minerals, food and drugs, environmental and other.

Criterion ICP MS ICP OES Flame AA S/ Flame Photometer

GTA
Detection limit ppb-ppt ppb to ppm ppm-ppb ppm

Analytical capability Multi element Multi element Single element Single element

Sample throughput 4 min 4 min 45 sec 10 sec

Dissolved solids < 0.2 %- 20.0 % 5% 5%

Handling 25%
Sample volume required 1.0 ml per 2.0 ml per 4 -5 ml per 4 -5 ml per minute
minute minute minute

Element applicable to > 70 >70 40 5

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 Fundamentals of ICP-MS & ICP-
MS Main Components

 Principles of atoms, ions and ion energy.

 The plasma (ICP) source and why we need it.
 Cones and lenses.
 Basics of quadrupole mass spectrometers.
 Measuring atomic ions with an electron
multiplier.
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ICP-MS PARTS

 Sample tubing
0.86 mm diameter

 Nebulizer ( Micromist \Ultrasonic and concentric)

 Spray Chamber

 Torch Connector 5
ICP-MS PARTS

 Torch (2.5mm and 1.0 mm)

 Sampler cone (Pt,Ni)

1 mm diameter orifice
 Skimmer Cone(Pt,Ni)
0.4 mm diameter orifice

 Drain tube
1.5 mm diameter

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ICP-MS PARTS

 Octopole Reaction cell

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 Quadrupole :
The quadrupole mass analyzer (QMS) is one type of mass analyzer used in
mass spectrometry. It is also known as a transmission quadrupole mass
spectrometer, quadrupole mass filter, or quadrupole mass spectrometer. As
the name implies, it consists of four cylindrical rods, set parallel to each
other.[1] In a quadrupole mass spectrometer the quadrupole is the component
of the instrument responsible for filtering sample ions, based on their
mass-to-charge ratio (m/z).

 Detector.

The detector measures the value of an indicator quantity and thus provides data for
calculating the abundances of each ion present (dynamic range 9 order)

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Liquid Sample Introduction
◦ Properly functioning front-end components are key to achieving optimal
ICP-MS performance. PTFE( Polytetrafluoroethylene ) Sample uptake line.
Allow no crimps or blockages.
◦ Peristaltic pump and tubing. Solution is forced via peristaltic action –
only if tubing and clamp pressure are correctly set.
◦ Nebulizer. Numerous types exist in both design and material.
◦ Spray-chamber. Creates uniform aerosol.

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 Nebulizer Basics

 The general term nebulizer refers to an apparatus that converts liquids into a fine
mist. Nozzles also convert liquids into a fine mist, but do so by pressure through
small holes. Nebulizers generally use gas flows to deliver the mist. Efficiency of
conversion from liquid to aerosol in ICP torch .
 Micromist Nebulizer (aqueous sample).
 Most operate between 0.1 - 1.0 mL/min of liquid sample.
 Concentric Nebulizer (Organic sample)
Refers to the ability to uptake sample without peri-pump assistance.
 Ultrasonic Nebulizer : The Ultrasonic Nebulizer is ideal for the trace level
determinations required in a wide range of environmental applications. It provides
a 5 to 50 fold enhancement in performance compared to a pneumatic type
nebulizer. Sound can be used instead of a gas as the energy source for converting a
liquid to a mist.

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Spraychamber Overview

A sample solution mist forms and passes through a double- pass

spray chamber where the larger sample droplets are removed by
collision with the spray chamber wall.
To prevent the spray chamber from filling up with liquid, the
peristaltic pump drain channel constantly removes excess sample
solution.
In addition, cooling the sample aerosol also removes some of the
water from the sample, reducing the level of polyatomic oxide
species formed, which in turn reduces the interference on certain
analytes

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ICP Torch

 Torch body provides containment of argon flows.

 The fixed, centered torch injector functions as a pipeline for
the aerosol. Dimensions and material of the injector can be
tailored for the application.

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Inductively Coupled Plasma: Basics
Sample cone
Ignition process begins by dry argon filling the
volume of torch. RF (27 Mhz) voltage is applied
to load coil.
High voltage arc ignites plasma.
RF oscillating field maintains a plasma in the
torch area. ≈ 8000°C temperature attained.

Once lit, sample aerosol can be admitted to

center of plasma noted visually by slightly
darker central channel. A common electrical
ground of the shield
makes a uniform,
.
reduced potential across
the plasma and narrows
the spread of ion energy.

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 ICP-MS: Technology
Principle:
 Liquid sample is sprayed into superheated plasma 8000ºC.
 Energy from the plasma ejects electron from shell (ionization). The result
is a positively charged analyte ion.
 Ions are separated by the mass spectrometer and measured. Ions
measured are directly proportional to analyte concentration.

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Atomic Ions
Ions are atoms that have had an electron expelled.
 Collisions within the ICP bring about removal of the electron.

 Since electrons carry negative charge, atomic ions exist with a

positive charge.

Shown: With one electron removed, the ion is

“singly charged.”
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 Ionization Potential
IP (ionization potential, units of eV) is the value
describing the amount of energy required to form an
ion.

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Ionization Potential

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Quadrupole Analyzers (QP) Measure
According to Mass to Charge
 Termed m/z ratio, where m = mass, z = charge (integer
value).
 We have learned that only ions are directed by lenses
into the QP.
 Most analyte ions (99% or more) are singly charged.
Therefore, m/z = m/1 = m.
 Example: 140Ce+ is measured at mass 140.

 Those few ions with +2 charge are measured at m/2 or

half the mass of the “parent” element. Example:
140Ce++ will be present in the spectrum at mass 70 (at
much lower signal than 140 peak).
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Analytical Benefits of ICP-MS

 Rapid multi-element quantitative analysis

 Very low detection limits
 Wide dynamic range
 Isotopic analysis
 Spectral simplicity
 Speciation (with HPLC) chlorate,chlorite

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 Following Type of samples analysis by ICP-MS
Sample
Nature sample Type Pre-Treatment Plant/source Metal Metal Source Unit
CPP/MEG Na contamination
Water Direct ( D-5673) PLANT ppb/ppm
Sample Direct (IS-3025 P- Water/ Na,K,Ca,Mg Mineral
Liquid 65) Wastewater ppm
Sample Naphtha
Organic Diluted with solvent sample Na,Pb,As,Hg Crude oil ppb
Sample
Diluted with solvent C7-C8 Pb,As,Cu Crude oil ppb
Ash then acid
digestion Cast Ca Raw material mg/L,%
Ash then acid
Polymer digestion Znst Zn Raw material mg/L,%
Additive Ash then acid
digestion DHT4A Mg , Al, Fe Raw material mg/L,%
Ash then acid
digestion NA27 Li Raw material mg/L
Solid Ash then acid
Sample digestion PP-1,PP-2 Mg,Al,Ti,Fe mg/L
Polymer Ash then acid Catalyst
sample digestion SW Al,Ti,V contamination mg/L
Ash then acid Catalyst
digestion HD Al,Ti,V contamination mg/L
Ash then acid
digestion Pd Cat Pd Raw material %
Catalyst
Ash then acid
digestion Silver Cat Ag Raw material %
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ICP-MS Interferences

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ICP-MS Interferences:

Interferences fall under two main categories:

 Physical and matrix-related. Solution dependency,

e.g. salts, solvents, anions present, and so on.

 Spectroscopic. Element based. Peak overlap with the

analyte of interest.

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How can physical/matrix interferences affect ICP-MS analyses?

 Loss of signal sensitivity.

 Potential for degraded accuracy.
 Poor precision and drift in results.
 Increased maintenance if deposits result.

.”

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How can spectral interferences affect
ICP-MS analyses?
 Inaccurate results (analyte dependent).
 Usually manifested as a positive error in results – that is, a
“false positive.”

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Impact of Dissolved Solids
 Total Dissolved Solids (tds) is the term referring primarily to salts
dissolved in the liquid sample.
 Typically cause a suppression of signal. Subsequent sample (if
cleaner matrix) should return to original sensitivity.
 Dissolved salts are prone to return to their solid form. Can deposit
on nebulizer or even in glassware if aerosol allowed to dry.
 May deposit on cones, reducing size dimensions and affecting
signal.
 Form insulating layers on ion lenses.
 In the plasma, salts and matrix can change the chemical
environment. Various minor effects can occur.
 If salts are exceptionally high, tuning can be de-optimized.

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Overcoming Physical Matrix Effects
 Use of an internal standard (ISTD) is the most common tool
for dealing with matrix effects.
 It has been in widespread use since ICP-MS was developed.
 ISTD overcome signal suppression/enhancement interferences
when used properly.

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What Is a Spectral Interference?
Interferences arise from two primary sources:
 Elemental presence .

Isobaric overlap of more than one element sharing a

single nominal mass.
 Molecular species detected .

Polyatomic (molecular) species from matrix and

gases.

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Elemental Isobaric Interferences
Element could originate from the sample (for
example, 64Ni and 64Zn) or the plasma (40Ar).

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Molecular Polyatomic Spectral Interferences
Overlap of a molecular ion on the analyte of interest

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Managing Spectral Interferences
Approaches to reducing interference problems:
 Simply choose the best isotope for the sample.

Example: If measuring Ti and sample has high

phosphate content, avoid 47Ti (PO).
 Change sample preparation. Example: To avoid

carbon interferences from organic sample, digest the

material.
 Or, eliminate the interference with the ORS.

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Applying ORS Technology
Shown are just some of the spectral interferences reduced or
removed with the use of the ORS cell.

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ICP-MS (7800)
 The Agilent 7800 ICP-MS combines , auto-optimization tools,
and Pre-set Methods to simplify routine analysis. With high
matrix tolerance, wide dynamic range, and effective control of
polyatomic interferences. The 7800 ICP-MS is easy to set up
and use, so you can quickly produce reliable results in the
widest range of sample types.
 Reduce sample preparation – Unique High Matrix
Introduction (HMI) technology, standard on the 7800 ICP-MS,
lets you analyze samples containing up to 3% total dissolved
solids (TDS) without dilution, reducing sample preparation
and saving time.

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ICP-MS (7900)

 The Agilent 7900 ICP-MS opens up a new dimension in ICP-

MS, with 10x higher matrix tolerance, 10x wider dynamic
range and 10x better signal to noise than the 7700 ICP-MS
Series,.
 Unprecedented matrix tolerance—Agilent’s 7900 ICP-MS has
a robust plasma and optional Ultra High Matrix Introduction
(UHMI) technology that enable you to routinely measure
samples containing up to 25% total dissolved solids (TDS)—
100 times higher than the traditional matrix limit for ICP-MS,
and far beyond the capability of any other current system.

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