Inductively Coupled Plasma

Inductively Coupled Plasma
From Wikipedia, the free encyclopedia
Type of mass spectrometry that uses an inductively coupled plasma to ionize the sample

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^ Tatiana. T, Waleska. C; Jose. R. : Elemental Analysis of Glass and Paint Materials by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) for Forensic Application, 2006

^ Degueldre, C.; Favarger, P.-Y. (2003). "Colloid analysis by single particle inductively coupled plasma-mass spectroscopy: A feasibility study". Colloids and Surfaces A: Physicochemical and Engineering Aspects . 217 (1–3): 137–142. doi : 10.1016/S0927-7757(02)00568-X .

^ Degueldre, C.; Favarger, P. Y. (2004). "Thorium colloid analysis by single particle inductively coupled plasma-mass spectrometry". Talanta . 62 (5): 1051–1054. doi : 10.1016/j.talanta.2003.10.016 . PMID 18969397 .

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^ Degueldre, C.; Favarger, P.-Y.; Rossé, R.; Wold, S. (2006). "Uranium colloid analysis by single particle inductively coupled plasma-mass spectrometry". Talanta . 68 (3): 623–628. doi : 10.1016/j.talanta.2005.05.006 . PMID 18970366 .

^ Berry, Jonna Elizabeth (2o15). Trace metal analysis by laser ablation inductively coupled plasma-mass spectrometry and x-ray K-edge densitometry of forensic samples.Graduate Theses and Dissertations. Paper 14675.

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^ Greenfield, S. (1994). "Inductively coupled plasmas in atomic fluorescence spectrometry. A review". Journal of Analytical Atomic Spectrometry . 9 (5): 565. doi : 10.1039/ja9940900565 . ISSN 0267-9477 .

^ Caruso, Joseph A.; Davidson, Timothy M.; Shen, Wei-Lung; Sheppard, Brenda S. (1990-01-01). "Helium-argon inductively coupled plasma for plasma source mass spectrometry". Journal of Analytical Atomic Spectrometry . 5 (8): 697–700. doi : 10.1039/JA9900500697 . ISSN 1364-5544 .

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^ Nam, Sang Ho.; Masamba, Wellington R. L.; Montaser, Akbar. (1993-10-15). "Investigation of helium inductively coupled plasma-mass spectrometry for the detection of metals and nonmetals in aqueous solutions". Analytical Chemistry . 65 (20): 2784–2790. doi : 10.1021/ac00068a014 . ISSN 0003-2700 .

^ Kenichi Sakata et al., Inductively coupled plasma mass spectrometer and method, US patent 6265717 B1.

^ Scott D. Tanner et al. , Device and method preventing ion source gases from entering reaction cell, US patent 6639665 B2.

^ Iouri Kalinitchenko Ion Optical System for a Mass Spectrometer, United States Patent Number 6,614,021 B1 (2003).

^ Shane Elliott; Michael Knowles; Iouri Kalinitchenko (Mar 2004). "A Change in Direction in ICP-MS" (PDF) . American Laboratory . Archived from the original (PDF) on 2007-12-13.

^ Shane Elliott; Barry Sturman; Stephen Anderson; Elke Brouwers; Jos Beijnen (April 1, 2007). "ICP-MS: When Sensitivity Does Matter" . Spectroscopy Magazine . Archived from the original on 2007-12-02 . Retrieved 2007-10-16 .

^ Vladimir N. Epov; R. Douglas Evans; Jian Zheng; O. F. X. Donard; Masatoshi Yamada (2007). "Rapid fingerprinting of 239 Pu and 240 Pu in environmental samples with high U levels using on-line ion chromatography coupled with high-sensitivity quadrupole ICP-MS detection". J. Anal. At. Spectrom. 22 (9): 1131–1137. doi : 10.1039/b704901c .

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^ Thomas, Robert (2001). "A Beginner's Guide to ICP-MS" (PDF) . Spectroscopy . Advanstar Communications . Retrieved 2014-05-09 .

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^ I. Kalinitchenko, Patent WO 2004/012223 A1

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Wikimedia Commons has media related to ICP-MS .
Inductively coupled plasma mass spectrometry ( ICP-MS ) is a type of mass spectrometry that uses an inductively coupled plasma to ionize the sample. It atomizes the sample and creates atomic and small polyatomic ions , which are then detected. It is known and used for its ability to detect metals and several non-metals in liquid samples at very low concentrations. It can detect different isotopes of the same element, which makes it a versatile tool in isotopic labeling .

Compared to atomic absorption spectroscopy , ICP-MS has greater speed, precision, and sensitivity. However, compared with other types of mass spectrometry, such as thermal ionization mass spectrometry (TIMS) and glow discharge mass spectrometry (GD-MS), ICP-MS introduces many interfering species: argon from the plasma, component gases of air that leak through the cone orifices, and contamination from glassware and the cones.

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 . Not all of the gas needs to be ionized for the gas to have the characteristics of a plasma; as little as 1% ionization creates a plasma. [1] 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 numbers of ions and electrons in each unit volume of plasma.

The ICPs have two operation modes, called capacitive (E) mode with low plasma density and inductive (H) mode with high plasma density, and E to H heating mode transition occurs with external inputs. [2] The Inductively Coupled Plasma Mass Spectrometry is operated in the H mode.

What makes Inductively Coupled Plasma Mass Spectrometry (ICP-MS) unique to other forms of inorganic mass spectrometry is its ability to sample the analyte continuously, without interruption. This is in contrast to other forms of inorganic mass spectrometry; Glow Discharge Mass Spectrometry (GDMS) and Thermal Ionization Mass Spectrometry (TIMS), that require a two-stage process: Insert sample(s) into a vacuum chamber, seal the vacuum chamber, pump down the vacuum, energize sample, thereby sending ions into the mass analyzer. With ICP-MS the sample to be analyzed is sitting at atmospheric pressure. Through the effective use of differential pumping; multiple vacuum stages separate by differential apertures (holes), the ions created in the argon plasma are, with the aid of various electrostatic focusing techniques, transmitted through the mass analyzer to the detector(s) and counted. Not only does this enable the analyst to radically increase sample throughput (amount of samples over time), but has also made it possible to do what is called "time resolved acquisition". Hyphenated techniques like Liquid Chromatography ICP-MS (LC-ICP-MS); Laser Ablation ICP-MS (LA-ICP-MS); Flow Injection ICP-MS (FIA-ICP-MS), etc. have benefited from this relatively new technology. It has stimulated the development new tools for research including geochemistry and forensic chemistry; biochemistry and oceanography. Additionally, increases in sample throughput from dozens of samples a day to hundreds of samples a day have revolutionized environmental analysis, reducing costs. Fundamentally, this is all due to the fact that while the sample resides at environmental pressure, the analyzer and detector are at 1/10,000,000 of that same pressure during normal operation.

An inductively coupled plasma (ICP) for spectrometry is sustained in a torch that consists of three concentric tubes, usually made of quartz , although the inner tube (injector) can be sapphire if hydrofluoric acid is being used. The end of this torch is placed inside an induction coil supplied with a radio-frequency electric current. A flow of argon gas (usually 13 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 plasma also produces ultraviolet light, so for safety should not be viewed directly.

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 centre 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.

To maximise plasma temperature (and hence ionisation efficiency) and stability, the sample should be introduced through the central tube with as little liquid (solvent load) as possible, and with consistent droplet sizes. A nebuliser can be used for liquid samples, followed by a spray chamber to remove larger droplets, or a desolvating nebuliser can be used to evaporate most of the solvent before it reaches the torch. Solid samples can also be introduced using laser ablation. The sample enters the central channel of the ICP, evaporates, molecules break apart, and then the constituent atoms ionise. 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. The plasma temperature is selected to maximise ionisation efficiency for elements with a high first ionisation energy, while minimising second ionisation (double charging) for elements that have a low second ionisation energy.

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. [ citation needed ] 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 the forensic field, glass ICP-MS is popular for glass analysis. [ citation needed ] Trace elements on glass can be detected using the LA-ICP-MS. The trace elements from the glass can be used to match a sample found at the crime scene to a suspect.

In recent years, industrial and biological monitoring has presented another major need for metal analysis via ICP-MS. Individuals working in factories 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).

ICP-MS is also used widely in the geochemistry field for radiometric dating, in which it is used to analyze relative abundance of different isotopes, in particular uranium and lead. ICP-MS is more suitable for this application than the previously used thermal ionization mass spectrometry , as species with high ionization energy such as osmium and tungsten can be easily ionized. For high precision ratio work, multiple collector instruments are normally used to reduce the effect noise on the calculated ratios.

In the field of flow cytometry , a new technique uses ICP-MS to replace the traditional fluorochromes . Briefly, instead of labelling antibodies (or other biological probes) with fluorochromes, each antibody is labelled with a distinct combinations of lanthanides . When the sample of interest is analysed by ICP-MS in a specialised flow cytometer, each antibody can be identified and quantitated by virtue of a distinct ICP "footprint". In theory, hundreds of different biological probes can thus be analysed in an individual cell, at a rate of ca. 1,000 cells per second. Because elements are easily distinguished in ICP-MS, the problem of compensation in multiplex flow cytometry is effectively eliminated.

In the pharmaceutical industry, ICP-MS is used for detecting inorganic impurities in pharmaceuticals and their ingredients. New and reduced maximum permitted exposure levels of heavy metals from dietary supplements, introduced in USP ( United States Pharmacopeia ) « 〈232〉Elemental Impurities—Limits » [3] and USP « 〈232〉Elemental Impurities—Procedures », [4] will increase the need for ICP-MS technology, where, previously, other analytic methods have been sufficient.
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful technique for the elemental analysis of a wide variety of materials encountered in forensic casework. (LA-ICP-MS) has already successfully been applied to applications in forensics, metals, glasses, soils, car paints, bones and teeth, printing inks, trace elemental, fingerprint, and Paper. Among these, forensic glass analysis stands out as an application for which this technique has great utility to provide highly.
Car hit and runs, burglaries, assaults, drive-by shootings and bombings such as these situations may cause glass fragments that could be used as evidence of association in glass transfer conditions. LA-ICP-MS is considered one of the best techniques for analysis of glass due to the short time for sample preparation and sample, small sample size of less than 250 nanograms. In addition there is no need for complex procedure and handling of dangerous materials that is used for digestion of the samples. This allows detecting major, minor and tracing elements with high level of precision and accuracy. There are set of properties that are used to measure glass sample such as physical and optical properties including color, thickness, density, refractive index (RI) and also, if necessary, elemental analysis can be conducted in order to enhance the value of an association. [5]
Cosmetics, such as lipstick, recovered from a crime scene may provide valuable forensic information. Lipstick smears left on cigarette butts, glassware, clothing, bedding; napkins, paper, etc. may be valuable evidence. Lipstick recovered from clothing or skin may also indicate physical contact between individuals. Forensic analysis of recovered lipstick smear evidence can provide valuable information on the recent activities of a victim or suspect. Trace elemental analysis
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Inductively Coupled Plasma

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