Principle of ICP-MS
Inductively coupled plasma - mass spectrometry (ICP-MS) is undoubtedly the fastest growing trace element technique available today. Since its commercialization in 1983, 3500 - 4000 ICP-MS systems have been installed worldwide, covering a diverse range of application areas including environmental, geochemical, semiconductor, clinical, nuclear, chemical, and metallurgical. The major reason for the technique’s unparalleled growth is its ability to carry out rapid multielement determinations at the ultra-trace level. Even though it can broadly determine the same suite of elements as other atomic spectroscopic techniques such as flame atomic absorption (FAA), graphite furnace atomic absorption (GFAA), and inductively coupled plasma - optical emission spectrometry (ICP-OES), ICP-MS has clear advantages in its multielement characteristics, speed of analysis, detection limits, and isotopic capabilities. Figure 1 shows approximate detection limits of all the elements that can be detected by ICP-MS
Principles of Operation
A number of different ICP-MS designs are commercially available today, each with its own strengths and limitations. They all share similar components such as the nebulizer, spray chamber, plasma torch, interface, and detector, but can differ significantly in the design of the mass spectrometer and in particular the mass separation device. This chart describes those differences in greater detail. But first, here is an overview of the principles of operation of ICP-MS. Figure 2 shows the basic instrumental components that make up an ICP-MS system. The sample, which must be in a liquid form, is pumped at 1 mL/min (usually with a peristaltic pump) into a nebulizer, where it is converted into a fine aerosol with argon gas at about 1 L/min. The fine droplets of the aerosol, which represent only 1 - 2% of the sample, are separated from larger droplets using a spray chamber. The fine aerosol then emerges from the exit tube of the spray chamber and is transported into the plasma torch via a sample injector.
Figure 2: Basic instrumental components of ICP-MS
The plasma torch plays a very different role in ICP-MS than it does in ICP-OES. In both techniques, the plasma is produced by the interaction of an intense magnetic field (produced by radio frequency [rf] passing through a copper coil) on a tangential flow of gas (normally argon), at about 15 L/min flowing through a concentric quartz tube (torch). This ionizes the gas and, when seeded with a source of electrons from a high-voltage spark, forms a very high temperature plasma discharge (~10,000 K) at the open end of the tube. However, this is where the similarity ends. In ICP-OES, the plasma, usually oriented vertically, is used to generate photons of light by the excitation of electrons of a ground-state atom to a higher energy level. When the electrons “fall” back to ground state, wavelength-specific photons are
emitted that are characteristic of the element of interest. In ICP-MS, the plasma torch is positioned horizontally, and is used to generate positively charged ions rather than photons. In fact, every attempt is made to stop the photons reaching the detector because they have the potential to increase signal noise. It is the production and detection of large quantities of these ions
that gives ICP-MS its characteristic ultratrace detection capability - about three to four orders of magnitude better than ICP-OES.
Once the ions are produced in the plasma, they are directed into the mass spectrometer via the interface region, which is maintained at a vacuum of 1 - 2 torr with a mechanical roughing pump. This interface region consists of two metallic cones (usually made of nickel), called the sampler and a skimmer cone. Each cone features a small (0.6 - 1.2 mm) orifice to allow the ions through to the ion optics, where they are guided into the mass separation device.
The interface region is one of the most critical areas of an ICP mass spectrometer. Its role is to help the ions be transported efficiently and with electrical integrity from the plasma, which is at atmospheric pressure (760 torr)
-6to the mass spectrometer analyzer region at approximately 10 torr.
Unfortunately, there is capacitive coupling between the rf coil and the plasma, producing a potential difference of a few hundred volts. If this wasn’t eliminated, an electrical discharge (called a secondary discharge or pinch effect) would appear between the plasma and the sampler cone. This discharge increases the formation of interfering species and also dramatically affects the kinetic energy of the ions entering the mass spectrometer, making optimization of the ion optics very erratic and unpredictable. For this reason, the secondary charge must be eliminated by using some kind of rf coil grounding mechanism. A number of approaches have been used over the years to achieve this, including placing a grounding strap between the coil and the interface; balancing the oscillator inside the rf generator circuitry; positioning a grounded shield or plate between the coil and the plasma torch; or using a double-interlaced coil where rf fields go in opposing directions. They all work differently but achieve a similar result - reducing or eliminating the secondary discharge.
Once the ions have been successfully extracted from the interface region, they are directed into the main vacuum chamber by a series of electrostatic lenses called ion optics. A turbomolecular pump maintains the operating
-2vacuum in this region at about 10 torr. There are many different designs of
the ion optic region, but they serve exactly the same function - to electrostatically focus the ion beam towards the mass separation device and to stop photons, particulates, and neutral species from reaching the detector.
The ion beam containing all the analyte and matrix ions exit the ion optics and now pass into the heart of the mass spectrometer - the mass separation device, where a second turbomolecular pump maintains an operating vacuum
-6of approximately 10 torr. There are many different mass separation devices, all with their own benefits and limitations. Five of the most common types are presented in this poster - quadrupole, magnetic sector, time of flight, collision/reaction cells, and dynamic reaction cell technology. They all work differently but all serve the same basic purpose - to allow analyte ions of a particular mass-to-charge ratio (m/z) through to the detector and to filter out all the non-analyte, interfering, and matrix ions. Depending on the design of the mass spectrometer, this is either a scanning process where the ions arrive at the detector sequentially, or a simultaneous process where the ions are sampled at the same time.
In the final process, an ion detector converts the ions into an electrical signal. The most common design used today is a discrete dynode detector, which contains a series of metal dynodes along the length of the detector. In this design, when the ions emerge from the mass filter, they impinge on the first dynode and are converted into electrons. As the electrons are attracted to the next dynode, electron multiplication takes place, resulting in a very high stream of electrons emerging from the final dynode. This electronic signal is then processed by the data handling system in the conventional way and converted into analyte concentration using ICP-MS calibration standards. Most detection systems used can handle up to eight orders of dynamic range, which means they can be used to analyze samples from low parts-per-trillion (ppt) levels, up to hundreds of parts-per-million (ppm). Most commercial ICP mass spectrometers, particularly the quadrupole models, use just one detector. However, specialized magnetic-sector ICP-MS instrumentation with multiple detectors is available for isotopic ratio analysis.
There is a lot more to the ICP-MS technique than can be covered in a poster format. This guide has attempted to provide a general overview of this important technique and the most common types of commercial
instrumentation. A series of articles featuring more detailed discussion of the fundamental principles of ICP-MS will appear in Spectroscopy magazine during 2001.
Developed in the early 1980s, quadrupole-based systems represent approximately 95% of all ICP mass spectrometers used today. This design was the first to be commercialized and, as a result, quadrupole ICP-MS is considered a mature, routine, high-throughput ultratrace element analytical tool. Quadrupole technology is also popular because its flexibility and performance can be enhanced by adding sampling accessories such as ultrasonic/micro-concentric nebulizers, membrane desolvators, flow injection, laser samplers, and (more recently) collision, reaction and dynamic reaction cells.
A quadrupole consists of four cylindrical or hyperbolic rods of the same length and diameter. Quadrupoles used in ICP-MS are typically 8 - 12 cm in length and about 1 cm in diameter. By placing a direct current (dc) field on one pair of rods and an rf field on the other opposite pair, ions of a selected mass are allowed to pass through the rods to the detector, while the others are ejected from the quadrupole. Figure 3 shows this in greater detail. In this simplified example, five colored ions have arrived at the entrance to the four rods of the quadrupole. When a particular rf/dc voltage is applied to the rods (represented by the positive and negative signs) the black analyte ion of a particular mass will be allowed to travel down the middle of the four rods to the end and be detected, while the other colored ions will pass through the spaces between the rods and be ejected from the quadrupole.
Figure 3: Principles of quadrupole technology (figure courtesy of PerkinElmer Instruments)
This scanning process is then repeated for another analyte at a completely different mass-to-charge ratio until all the analytes in a multielement analysis have been detected. Quadrupole scan rates are typically in the order of 2500 atomic mass units (amu) per second - in practice, 25 elements can be determined with good precision in 30 - 60 seconds. On the other hand, quadrupole technology can only separate masses that are approximately 1 amu apart. If there is a severe spectral interference very close to the analyte mass, the resolution will not be sufficient to resolve the interference away. Still, if routine, high-throughput trace element analysis is required, quadrupole ICP-MS technology has clear advantages.
Selected Manufacturers (North American Market): PerkinElmer Instruments (Norwalk, CT), Agilent Technologies (Palo Alto, CA), Thermo Elemental [VG] (Franklin, MA), Varian (Walnut Creek, CA), Spectro Analytical Instruments Inc. (Fitchburg, MA).
Double-Focusing Magnetic-Sector Technology
Quadrupole instrumentation’s limited resolving power led to the development
of high-resolution systems based on double-focusing magnetic-sector mass technology. This design typically offers a resolving power of up 10,000, which is significantly higher than a quadrupole (quad at 1 amu = ~ 400 resolving power). The magnetic-sector design was first used in molecular spectroscopy for the structural analysis of complex organic compounds. However, to use this technology with an ICP, changes had to be made to the ion acceleration mechanism. This was a significant challenge when magnetic-sector systems were first developed in late 1980s. However, by the early 1990s, instrument designers solved this problem by moving the high-voltage components away from the plasma and interface closer to the mass spectrometer.
Today’s instrumentation is based on reverse Nier-Johnson geometry (Figure
4). This design consists of two analyzers - a traditional electromagnet and an electrostatic analyzer (ESA). The ions are sampled from the plasma in a conventional manner and then accelerated in the ion optic region to a few kilovolts (kV) before they enter the magnet. The magnetic field, which is dispersive with respect to ion energy and mass, then focuses all the ions with diverging angles of motion from the entrance slit to the intermediate slit. The
ESA, which is only dispersive with respect to ion energy, then focuses all the ions from the intermediate slit on to the exit slit, where the electron multiplier detector is positioned. If the energy dispersion of the magnet and ESA are equal in magnitude but opposite in direction, they will focus both ion angles (first focusing) and ion energies (double focusing), when combined. Changing the electrical field in the opposite direction during the cycle time of the magnet (in terms of the mass passing the exit slit) has the effect of “freezing” the
mass for detection. Then as soon as a certain magnetic field strength is passed, the electric field is set to its original value and the next mass is “frozen.” The voltage is varied on a per-mass basis, allowing the operator to
scan only the mass peaks of interest rather than the full mass range. This represents an enormous time saving over traditional sector instruments, but these systems are still significantly slower than quadrupole-based instruments. So, although double-focusing systems are perhaps not ideally suited for rapid, high-throughput applications, they do offer the advantages of high resolving power and significantly lower background counts than a quadrupole. Typical background levels are in the order of 1 count every 10 seconds, providing exceptional detection limits, particularly at the high mass end. Thus, these systems are popular for challenging applications that require good detection capability, exceptional resolving power, or very high precision. In fact the demand for high-precision isotope ratio analysis, particularly in the geochemical field, has led to the commercialization of dedicated multi-detector instruments.
Figure 4: Typical double focusing magnetic sector mass spectrometer (figure courtesy of
Selected Manufacturers (North American Market): ThermoQuest [Finnigan MAT] (San Jose, CA); Thermo Elemental [VG] (Franklin, MA); Micromass Ltd. (Beverly, MA).
Quadrupole-based instruments are scanning devices and therefore limited in their suitability for applications that require simultaneous detection of the ions. This makes them less than ideal for isotope ratio analysis that requires very high precision and in multielement analysis on a rapid transient signal generated by sampling accessories like laser ablation and electrothermal vaporization (ETV) systems. This led to the development of time-of-flight (TOF) ICP mass spectrometers, which were designed for this type of work. Figure 5 shows the basic principles of this technique. In a TOF mass analyzer, all ions that contribute to the mass spectrum are sampled through the interface. But instead of being focused into the mass filter in the conventional way, packets (groups) of ions are electrostatically injected into either an orthogonal flight tube (right angles to the sampled ion beam) or an axial flight tube (same axis as the ion beam) at exactly the same time. Once in the flight tube, they are steered into a reflectron, where they are reflected back in the opposite direction to the detector. As the mass of the ion is related to the time taken to reach the detector, given by the equation: t = K x –m (where t = time, K =
constant, and M = mass), then ions of different mass can be filtered (separated) in the time domain. The main advantage of this approach is that the ions are sampled and detected at exactly the same moment in time, which means TOF systems can collect a full mass spectrum significantly faster than a scanning device like a quadrupole. Although TOF-ICP mass spectrometry is relatively new and has not yet proved itself as a routine tool, its rapid, simultaneous detection capability is ideally suited for high-precision work and fast transient analysis that requires the best multielement signal-to-noise performance.
Figure 5: Schematic of an orthogonal-design TOF-ICP-MS
Selected Manufacturers (North American Market): Leco Corporation (St. Joseph, MI); GBC Scientific (Arlington Heights, IL).
Collision / Reaction Cell Technology
A small number of elements are renowned for poor detection limits by ICP-MS. These are predominantly elements that suffer from a major spectral interference produced by ions generated from the argon gas, solvent, or
4016sample matrix. Examples of these interferences would be ArO on the
56383940determination of Fe; ArH on the determination of K; Ar on the
40402+804035determination of Ca; Ar on the determination of Se; ArCl on the
75401252determination of As; and ArC on the determination of Cr. The cold/cool
plasma approach, which uses a lower temperature to reduce the formation of the interferences, has been one way around some of these problems. However, this solution can be cumbersome to optimize, is time consuming, and is not effective on many of the interferences. Collision/reaction cells were developed for ICP-MS in the late 1990s to deal with these limitations. Designed originally for organic MS to generate daughter species to confirm identification of the structure of the parent molecule, they found a use in