PV - Ijddr
PV - Ijddr
Ramyalakshmi G*1, Venkatesh P1,Hepcy kalarani D1, Ravindra reddy K1, Archana E1,
Manjuvani S2
1
P.Rami Reddy Memorial College of Pharmacy-Kadapa-516 003. Andhra Pradesh. India.
2
Raghavendra Institute of Pharmaceutical Educational and Research-Anantapur-515001.Andhra Pradesh. India.
Covered in Index Copernicus with IC Value 4.68 for 2010
INTRODUCTION
*Corresponding author, Mailing address:
Ramyalakshmi G Inductively coupled plasma mass spectrometry (ICP-
P. R. R. M. College of Pharmacy,
MS) is an analytical technique that performs
1/35-1, Prakruthi nagar,
Kadapa - 516 003. (A.P) - India. elemental analysis with excellent sensitivity. The
E-mail: ramya.pharma89@gmail.com
ICP-MS instrument employs argon plasma (ICP) as
the ionization source and a mass spectrometer (MS),
Key words: usually with a quadrupole mass filter, to separate the
Inductively coupled plasma mass spectroscopy; ions produced.
sample introduction, element speciation, separation It can simultaneously measure most elements in the
technique. periodic table and determine analyte concentrations
down to the sub nanogram per litre or parts per individual atoms. These atoms will lose electrons and
trillion (ppt), level. It can perform qualitative, semi become (singly) charged positive ions. Most elements
quantitative, and quantitative analysis, and compute ionize very efficiently (>90) in the hot plasma.
isotopic ratios on water samples, and in waste The layout of an ICP-MS is shown in (fig.1).To allow
extracts and digest In an ICP-MS instrument, liquid their identification, the elemental ions produced in
samples are introduced by a peristaltic pump to the the plasma (ICP)must be transferred from 7000K to
Covered in Index Copernicus with IC Value 4.68 for 2010
nebulizer where a sample aerosol is formed. room temperature and from atmospheric pressure to
A double-pass spray chamber ensures that a high vacuum. To do so, the ions are extracted
consistent aerosol is introduced to the plasma. through a number of apertures. Besides ions also
Argon gas is introduced through a series of photons are produced in the plasma. Photons also
concentric quartz tubes, known as the ICP torch. The pass through the apertures. They are not removed by
torch is located in the Se centre of a RF coil. A Tesla vacuum and produce high background signal when
coil ionizes the argon gas and free electrons are they reach the detector. To minimize this
accelerated by a 27 MHz radio frequency field. background, also called photon stop is present this
Collisions between the accelerated electrons and the is a small metal plate placed in the centre of the ion
argon gas generate high temperature plasma. The beam, which reflects the photons away from the
Review Paper
PRINCIPLE OF ICP-MS
Using ICP-MS, all kinds of materials can be
measured. Solutions are vaporized using a nebulizer,
while solids can be sampled using laser ablation.
Gasses can be sampled directly. The sampled
material is introduced into high-energy argon plasma
that consists of electrons and positively charged
Fig 1: Lay out of an ICP and Detailed layout of
argon ion. In the plasma, the material is split into cylinder lens
ICP-MS ANALYSIS work best with simple liquid samples (i.e. solutions).
An ICP-MS consists of the following component. However, there have been instances of their use with
• Sample introduction system – composed of a more complex materials like slurry. Many varieties of
nebulizer and spray chamber and provides the nebulizers have been coupled to ICP-MS, including
means of getting samples into the instrument pneumatic, cross-flow, Babington, ultrasonic, and
• ICP torch and RF coil–generates the argon desolvating types. The aerosol generated is often
Covered in Index Copernicus with IC Value 4.68 for 2010
plasma, which serves as the ion source of the treated to limit it to only smallest droplets,
ICP-MS commonly by means of a double pass or cyclonic
• Interface – links the atmospheric pressure ICP spray chamber. Use of auto samplers makes this
ion source to the high vacuum mass easier and faster.
spectrometer Less commonly, the laser ablation has been used as a
• Vacuum system – provides high vacuum for ion means of sample introduction. In this method, a laser
optics, quadrupole, and detector is focused on the sample and creates a plume of
• Collision/reaction cell – precedes the mass ablated material which can be swept into the plasma.
spectrometer and is used to remove This is particularly useful for solid samples, though
interferences that can degrade the detection can be difficult to create standards for leading the
Review Paper
can be caused both in the collision cell and Other methods of sample introduction are also
reaction cell modes, which is referred to as a utilized. Electro thermal vaporization (ETV) and in
between the two outermost tubes of the torch and an the right of the skimmer cone) operates at a very low
electrical spark is applied for a short time to pressure. With a two-cone design, there can only be a
introduce free electronsintothe gas stream. These two-step reduction in the pressure between the
electrons interact with the radio-frequency magnetic plasma and filtering quadrupole.
field of the induction coil and are accelerated first in A recent innovation has introduced a third cone into
one direction, then the other, as the field changes at the interface which greatly reduces the divergence of
Covered in Index Copernicus with IC Value 4.68 for 2010
high frequency (usually 27.12 MHz). The accelerated the ion beam as it exits the interface region. The third
electrons collide with argon atoms, and sometimes a cone, called the hyper-skimmer, provides a three-
collision causes an argon atom to part with one of its step reduction in pressure between the plasma and
electrons. The released electron is in turn accelerated the filtering quadrupole, resulting in a substantial
by the rapidly changing magnetic field. The process reduction in the divergence of the emerging ion
continues until the rate of release of new electrons in beam. With the three-cone design, conventional ion
collisions is balanced by the rate of recombination of lenses can be completely eliminated from the
electrons with argon ions (atoms that have lost an instrument, resulting in greater ion transmission,
electron). This produces a ‘fireball’ that consists improved long-term stability, and reduced
mostly of argon atoms with a rather small fraction of instrument maintenance. In the three-cone design,
Review Paper
free electrons and argon ions none of the cones has a voltage applied such as
may exist on an extraction lens. Since the cones are
INTERFACE SAMPLING IONS electrically neutral, any build up of material on their
Placing a plasma, operating at 6000 °C, near an ion surfaces will not significantly impact their function.
focusing device operating near room temperature is a In addition, experience has shown that the three-
bit like placing the earth about a half-mile away from cone design requires no more maintenance than a
the sun. In addition to a large temperature conventional two-cone design. Cones are most often
difference, the plasma operates at a pressure that is produced from nickel or platinum. While nickel
much higher than the vacuum required by the ion cones have a lower purchase price, platinum cones
lens and allows mass spectrometer portions of the provide longer life, are more resistant to some acids,
instrument. The interface the plasma and the ion lens and provide a small improvement in instrument
system to coexist and the ions generated by the performance. The orifice openings of the cones
plasma to pass into the ion lens region. The interface should be large enough to allow for the passage of the
consists of two or three inverted funnel-like devices ion beam while, at the same time, not allow so much
called cones. gas to enter the instrument that the instrument’s
Until recently, all commercially available ICP-MS vacuum system is taxed. Experience has shown that
systems used the two-cone design. Such a design orifice openings of approximately 1 mm are ideal[3].
requires down-stream focusing of the beam that exits
the interface region.
This focusing has been achieved through the use of a
single or a series of charged devices called ion lenses.
The need for these ion lenses can be explained in fig
no 2 . A mentioned earlier, the plasma (located to the
Fig 2: Two cone design on the left shows a wide
left of the sampler cone) operates at atmospheric beam divergence resulting from a single,
pressure, while the filtering quadrupole (located to largepressure reduction.Three cone design on the
right shows a small ion beam divergence, resulting in the Bruker(former Varian) ICP-MS is another
from two small pressure reduction
effective approach to removing ions.
Axial field technology (AFT) is a DRC modification by
TRANSFER OF IONS INTO VACUUM
Perkin-Elmer, which consists in two supplementary
The carrier gas is sent through the central channel
rods placed in the DRC cell that move the ions faster
and into the very hot plasma. The sample is then
through the cell and improving analysis speed.
exposed to radio frequency which converts the gas
Covered in Index Copernicus with IC Value 4.68 for 2010
arrangements for this purpose. Examples include the measure the elements of interest in the sample
Einzel lens,the Barrel lens, Agilent's Omega Lens [7] analyse.
and Perkin-Elmer's Shadow stop.
Another approach is to use ion guides (quadrupoles, DATA HANDLING AND SYSTEM
hexapoles, or octopoles) to guide the ions into mass CONTROLLER
analyzer along a path away from the trajectory of All ICP-MS instruments require computers and
Covered in Index Copernicus with IC Value 4.68 for 2010
photons or neutral particles. Yet another approach is sophisticated software to control the mass
Varian patented used by Bruker[8] 90 degrees spectrometer as well as perform calculations on the
reflecting "Ion Mirror" optics, which are claimed to data collected. Additionally, the operating
provide more efficient ion transport into the mass- parameters of the spectrometer, including proper
analyzer, resulting in better sensitivity and reduced ignition of the plasma, pressure within the high
background[9]. vacuum region, and the voltage applied to the
detector, are to be constantly monitored by the
THE MASS SPECTROMETER-SEPERATING controller, and the operator is to be alerted if any
ION parameter falls outside of the proper working range
and mass response of the instrument. All in all, the
Review Paper
and mass 65.The natural ratio of the different subtracting the appropriate correction factor from
isotopes of an element is constant in nature. the intensity of the interfered isotope.
Therefore it is not difficult to correct for overlap of
isotopes of different elements. In addition, a non- MOLECULAR INTERFERENCES
interfered isotope is present for almost all elements. Are due to the recombination of sample and matrix
Remaining interfering signals are removed by “in- ions with Ar or other matrix components (e.g. O, N,
Covered in Index Copernicus with IC Value 4.68 for 2010
house” software. This approach makes fast overview Cl, etc.) in the cooler regions of the plasma. Examples
analysis of the total elemental composition (10) include the following:
40Ar16O on 56Fe,47Ti16O on 63Cu,40Ar35Cl on 75As ,40Ar2
on 80Se.
Most molecular ions formed by matrix components
are predictable and may be corrected for by applying
correction factors determined by analysing
interference solutions. Molecular interferences may
also be avoided by using alternative, non-interfered
analyte isotopes. In some cases they can be reduced
Review Paper
other analytical techniques such as for example Are due to relatively rare doubly-charged matrix or
inductively coupled plasma atomic emission sample ions with twice the mass of the analyte and
spectrometry, ICP-AES), generally predictable and hence the same mass/charge ratio. The following is
interferences that occur are isobaric, molecular (or generally be minimized by optimizing instrument
polyatomic) and doubly-charged ion interferences. operating conditions. Luckily, the first ionisation
potential of Ar, although high enough to efficiently
Occur for equal mass isotopes of different elements. produce doubly-charged ions of most elements, thus
interfered analyte isotopes, if available. Given Clogging of the orifices in either or both of the
acknowledge of the natural abundances of the interface cones may be a problem when samples with
isotopes of all elements, isobaric interferences are high total dissolved solid (TDS) contents are
easily corrected by measuring the intensity of analysed. The high salt content of seawater samples
another isotope of the interfering element and represents a common example of this type of matrix-
dependent effect. The problem may be overcome by
sample dilution or by avoiding solutions with TDS Agilent Technologies currently markets the 7500
concentrations above 0.1 wt.%. Alternatively, a series2, including the 7500cx, which is a wide-range
sample introduction system capable of removing sampler, whereas the 7500csis specifically for the
dissolved salts may be used (e.g. an ultrasonic semiconductor industry. ICP-MS systems from
nebuliser with a desolvation unit). Thermo Fisher Scientific include the XSERIES 2,
The presence of abundant, easily ionised matrix ELEMENT GD, ELEMENT XR, and ELEMENT2 HR-
Covered in Index Copernicus with IC Value 4.68 for 2010
components such as Na in seawater may lead to a ICP-MS. The ELEMENT models are sector field ICP-
suppression in the ionisation efficiency of analytes. MS units. In July 2008, Thermo Fisher published a
Once again, this effect may be reduced by sample poster demonstrating the capability of collision cell-
dilution or by removal of the easily ionised matrix based ICP-MS to analyze multi elemental
component. environmental and geological samples with the use of
Mass-charge effectsbetween abundant heavy matrix the XSERIES 2 collision cell-based ICP-MS analyzer.
ions (e.g. Pb, U) with high kinetic energies and Varian currently offers the 810-MS, for trace and
lighter analyte ions may also result in decreased elemental analysis, and the 820-MS, which uses a
analyte signal intensities[11]. collision reaction interface system to overcome
spectroscopic interferences.
Review Paper
sample tubes and caps from the ICP-MS The market size for the number of ICP-MS units sold,
CURRENT ICP-MS OFFERS been widely used for testing drinking water,
There are several ICP-MS systems that are presently wastewater, soil and other parts of the environment,
promoted for various application markets. Although body fluids, tissues, and the materials that make
quadrupole ICP-MS is the vast majority of ICP-MS electronic chips. ICP-MS technology has
instruments produced and sold ,the other two types revolutionized many industries, including the
of ICP-MS instruments available include sector field semiconductor and environmental industries, by
and time-of-flight (TOF). “In terms of the numbers enabling laboratories to run more precise, sensitive
produced, you can think of quadrupole ICP-MS as analyses, more economically and more quickly. In
being like gasoline engine cars, sector field ICP-MS fact, today’s three major applications served by ICP-
as diesel cars, and TOF-ICP-MS as being like hybrid MS technology include environmental monitoring,
cars,”according to Steven Beres, Perkin Elmer ICP- biomonitoring, and elemental analysis in the
system is continually evolving. The current ICP-MS Environmental monitoring and biomonitoring go
instruments offered include the ELAN 9000, ELAN somewhat hand-in-hand, since both involve testing
DRC-e, and ELAN DRC II. for chemicals in the environment. Environmental
monitoring is of fundamental importance because it analysis. These standards are analyzed to establish
provides the basis on which we make our the calibration curve. The unknown samples are then
assessments of the quality of our environment. run, and the signal intensities are compared to the
Biomonitoring is an important application on a calibration curve to determine the concentration of
personal level since it involves testing human blood, the unknown.
urine, and other body fluids and tissue samples to
Covered in Index Copernicus with IC Value 4.68 for 2010
chips has allowed semiconductor chips to become Isotope dilution experiments can also be performed
more powerful, smaller, and affordable. “ICP-MS has by ICP-MS. In isotope dilution, the sample is spiked
allowed them to achieve greater densities with fewer with an enriched isotope of the element of interest.
defects per wafer so that the cost per chip could The enriched isotope acts as both a calibration
decrease,” noted Steven Beres. standard and an internal standard. Because the
ICP-MS is influencing new ways of thinking in other enriched isotope has the same chemical and physical
markets. One market involves the observation of life properties as the analyte element, it is the best
science and biological applications. Cells and other possible internal standard. For this reason, isotope
intracellular components interact with elements and dilution is recognized as being the most accurate type
metals for signaling, function, and maintenance. As a of all analyses and is often used to certify standard
result, ICP-MS would be a potential tool to analyze reference materials.
molecular interactions occurring within the cells,
which includes binding interactions between proteins SEMI-QUANTITATIVE ANALYSIS
and other metals For some analyses, it is not necessary to calibrate the
ICP-MS for each element. After the instrument has
APPLICATIONS been calibrated using a single solution containing as
QUANTITATIVE ANALYSIS few as three elements, a high-quality semi-
The ICP-MS accurately determines how much of a quantitative analysis for 82 elements can be
specific element is in the material analyzed. In a performed in just a few minutes. Semi-quantitative
typical quantitative analysis, the concentration of analysis provides a fingerprint of the elements
each element is determined by comparing the counts present in a sample and the approximate
measured for a selected isotope to an external concentrations of each element. This information can
calibration curve that was generated for that help determine what standards are necessary for
element. Liquid calibration standards are prepared in quantitative analysis. Additionally, semi- quantitative
the same manner as used in AA and ICP-OES analysis can provide valuable information on what
other elements are present in a sample that could element analysis of fresh, saline and sediment
cause interferences and potentially affect the results. pore waters.
The software does this by comparing the measured
spectrum of the unknown sample to the known
REFERENCES
isotopic fingerprints for each element and mass
1) valdimir, N.Epov, R. Douglas Evans, Jian
response of the instrument. When a match is
Zheng,Masatoshiyamada,chemistryof322Lma
Covered in Index Copernicus with IC Value 4.68 for 2010
Mo, Cd, Sn, Sb, Cs, Ba, rare earth elements, Hf, Ta,
uide.pdf,2001,2
W, Re, Tl, Pb, Th, U
4) V. Baranov, S. Tanner , "A dynamic reaction
cell for ICP-MS. Part 1: The rf-field energy
Examples:
contribution in thermodynamics of ion-
• chemical analysis of meteorites and lunar
molecule reactions". J. Anal. At. Spectrom.
rocks(10)
http://en.wikipedia.org/wiki/Inductively_cou
• high-precision determination of ultra-trace pled_plasma_mass_spectrometry, 1993 1133–
levels of rare earth elements in a wide range of 1142,
rocks, minerals and natural waters 5) A beginner's Guide to ICP-MS R.
• determination of rare earth and other trace Thomas,http://en.wikipedia.org/wiki/Inducti
elements in peat samples as tracers of climate vely_coupled_plasma_mass_spectrometry
change 6) Wang, XueDong; Iouri Kalinitchenko,
• biomonitoring using rare earth and other trace "Principles and performance of the Collision
elements in lichens Reaction Interface for the"
• detection of ultra-trace levels of metals using (PDF),Varian.Jan,http://en.wikipedia.org/wik
diffusive gradients in thin films (DGT) i/Inductively_coupled_plasma_mass_spectro
• detection of titanium and silver in experimental metry, 2010
solutions 7) Kenichi Sakata et al., Inductively coupled
• study of elemental tracers in biological samples - plasma mass spectrometer and method, US
gadolinium in cell lysates, for example patent 6265717
• survey analysis of main and ultratrace elements B1,http://en.wikipedia.org/wiki/Inductively_c
in both organic and inorganic samples. oupled_plasma_mass_spectrometry
• Depth profiles of elements in solids by using 8) Iouri Kalinitchenko Ion Optical System for a
laser abalation as a sampling technique, Trace Mass Spectrometer, United States Patent
Number 6,614,021B1,
http://en.wikipedia.org/wiki/Inductively_cou
pled_plasma_mass_spectrometry,2003
9) Shane Elliott, Michael Knowles, and Iouri
Kalinitchenko, A Change in Direction in ICP-
Covered in Index Copernicus with IC Value 4.68 for 2010
http://web.uct.ac.za/depts/geolsci/facilities/ic
pms/lectures/lec2.html, 1987, 575-586
12) Valdimir N. Epov, R. Douglas Evans, Jian
Zheng, Masatoshi yamada, chemistry of 322L
manual,
http://www.csun.edu/~hcchm003/322l/322l
micp.pdf,45
13) Maugh, T. H.
http://shop.perkinelmer.com/content/related
materials/articles/atl_icpms25years-american
laboratory september 2008.pdf, 1983, 178-9