Date: July 29, 2014
Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass spectrometry which is capable of detecting metals and several non-metals at
concentrations as low as one part in 1012 (part per trillion). This is achieved by ionizing the sample with inductively coupled plasma and then using a mass
spectrometer to separate and quantify those ions. Compared to atomic absorption techniques, ICP-MS has greater speed, precision, and sensitivity. However, analysis by ICP-MS is also more susceptible to trace contaminants from glassware and reagents. In addition, the presence of some ions can interfere with the detection of other ions. The variety of applications exceeds that of inductively coupled plasma atomic emission spectroscopy and includes isotopic speciation. Due to possible applications in nuclear technologies, ICP-MS hardware is a subject for special exporting regulations.
Inductively coupled plasma An inductively coupled plasma is a plasma that is energized (ionized) by inductively heating the gas with an electromagnetic coil, and contains a sufficient concentration of ions and electrons to make the gas electrically conductive. Even a partially ionized gas in which as little as 1% of the particles are ionized can have the characteristics of a plasma (i.e., response to magnetic fields and high electrical conductivity).
The plasmas used in spectrochemical analysis are essentially electrically neutral, with each positive charge on an ion balanced by a free electron. In these plasmas the positive ions are almost all singly charged and there are few negative ions, so there are nearly equal amounts of ions and electrons in each unit volume of plasma. An inductively coupled plasma (ICP) for spectrometry is sustained in a torch that
consists of three concentric tubes, usually made of quartz. The end of this torch is placed inside an induction coil supplied with a radio-frequency electric current. A
flow of argon gas (usually 14 to 18 liters per minute) is introduced between the two outermost tubes of the torch and an electric spark is applied for a short time to introduce free electrons into the gas stream. These electrons interact with the radio frequency magnetic field of the induction coil and are accelerated first in one
direction, then the other, as the field changes at high frequency (usually 27.12 million cycles per second). The accelerated electrons collide with argon atoms, and sometimes a collision causes an argon atom to part with one of its electrons. The released electron is in turn accelerated by the rapidly changing magnetic field. The process continues until the rate of release of new electrons in collisions is balanced by the rate of recombination of electrons with argon ions (atoms that have lost an electron). This produces a ‘fireball’ that consists mostly of argon atoms with a rather small fraction of free electrons and argon ions. The temperature of the plasma is very high, of the order of 10,000 K. The ICP can be retained in the quartz torch because the flow of gas between the two outermost tubes keeps the plasma away from the walls of the torch. A second flow of argon (around 1 liter per minute) is usually introduced between the central tube and the intermediate tube to keep the plasma away from the end of the central tube. A third flow (again usually around 1 liter per minute) of gas is introduced into the central tube of the torch. This gas flow passes through the center of the plasma, where it forms a channel that is cooler than the surrounding plasma but still much hotter than a chemical flame. Samples to be analyzed are introduced into this central channel, usually as a mist of liquid formed by passing the liquid sample into a nebulizer.
As a droplet of nebulized sample enters the central channel of the ICP, it evaporates and any solids that were dissolved in the liquid vaporize and then break down into atoms. At the temperatures prevailing in the plasma a significant proportion of the atoms of many chemical elements are ionized, each atom losing its most loosely bound electron to form a singly charged ion.
For coupling to mass spectrometry, the ions from the plasma are extracted through a series of cones into a mass spectrometer, usually a quadrupole. The ions are separated on the basis of their mass-to-charge ratio and a detector receives an ion signal proportional to the concentration. The concentration of a sample can be determined through calibration with certified reference material such as single or
multi-element reference standards. ICP-MS also lends itself to quantitative determinations through isotope dilution, a single point method based on an isotopically enriched standard. Other mass analyzers coupled to ICP systems include double focusing magnetic-electrostatic sector systems with both single and multiple collector, as well as time of flight systems (both axial and orthogonal accelerators have been used).
One of the largest volume uses for ICP-MS is in the medical and forensic field, specifically, toxicology. A physician may
order a metal assay for a number of reasons, such as suspicion of heavy metal poisoning, metabolic concerns, and even
hepatological issues. Depending on the specific parameters unique to each patient’s diagnostic plan, samples collected
for analysis can range from whole blood, urine, plasma, serum, to even packed red blood cells. Another primary use for
this instrument lies in the environmental field. Such applications include water testing for municipalities or private
individuals all the way to soil, water and other material analysis for industrial purposes.
In recent years, industrial and biological monitoring has presented another major need for metal analysis via ICP-MS. Individuals working in plants where exposure to metals is likely and unavoidable, such as a battery factory, are required by their employer to have their blood or urine analyzed for metal toxicity on a regular basis. This monitoring has become a mandatory practice implemented by OSHA, in an effort to protect workers from their work environment and ensure proper rotation of work duties (i.e. rotating employees from a high exposure position to a low exposure position).
Regardless of the sample type, blood, water, etc., it is important that it be free of clots or other particulate matter, as even the smallest clot can disrupt sample flow and block or clog the sample tips within the spray chamber.
Very high concentrations of salts, e.g. sodium chloride in sea water, can eventually lead to blockages as some of the ions reunite after leaving the torch and build up around the orifice of the skimmer cone. This can be avoided by diluting samples whenever high salt concentrations are suspected, though at a cost to detection limits.
Quantification of proteins and biomolecules
There is an increasing trend of using ICP-MS as a tool in speciation analysis, which normally involves a front end chromatograph separation and an elemental selective detector, such as AAS and ICP-MS. For example, ICP-MS may be
combined with size exclusion chromatography and quantitative preparative native continuous polyacrylamide gel electrophoresis (QPNC-PAGE) for identifying and quantifying native metal cofactor containing proteins in biofluids. Also the phosphorylation status of proteins can be analyzed.
The ICP-MS allows determination of with atomic mass ranges 7 to 250. This encompasses to . Some masses are prohibited such as 40 due to the abundance of argon in the sample. Other blocked regions may include mass 80 (due to the argon dimer), and mass 56 (due to ArO), the latter of which greatly hinders analysis unless the instrumentation is fitted with a reaction chamber.
4 Routine maintenance
As with any piece of instrumentation or equipment, there are many aspects of maintenance that need to be encompassed by daily, weekly and annual procedures. The frequency of maintenance is typically determined by the sample volume and cumulative run time that the instrument is subjected to.One of the first things that should be carried out before the calibration of the ICP-MS is a sensitivity check and optimization. This ensures that the operator is aware of any possible issues with the instrument and if so, may address them before beginning a calibration. Typical indicators of sensitivity are Rhodium levels, Cerium/Oxide ratios and DI
water blanks.One of the most frequent forms of routine maintenance is replacing sample and waste tubing on the peristaltic pump, as these tubes can get worn fairly quickly resulting in holes and clogs in the sample line, resulting in skewed results. Other parts that will need regular cleaning and/or replacing are sample tips, nebulizer tips, sample cones, skimmer cones, injector tubes, torches and lenses. It may also be necessary to change the oil in the interface roughing pump as well as
the vacuum backing pump, depending on the workload put on the instrument
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