Spark ionization (also known as spark source ionization) is a method used to produce gas phase ions from a solid sample. The prepared solid sample is vaporized and partially ionized by an intermittent discharge or spark. [1] This technique is primarily used in the field of mass spectrometry. When incorporated with a mass spectrometer the complete instrument is referred to as a spark ionization mass spectrometer or as a spark source mass spectrometer (SSMS). [2]
The use of spark ionization for analysis of impurities in solids was indicated by Dempster's work in 1935. [3] Metals were a class of material that could not be previously ionized by thermal ionization (the method formerly used for ionizing solid sample). Spark ion sources were not commercially produced until after 1954 when Hannay demonstrated its capability for analysis of trace impurities (sub-part per million detection sensitivity) in semiconducting materials. [4] The prototype spark source instrument was the MS7 mass spectrometer produced by Metropolitan-Vickers Electrical Company, Ltd. in 1959. Commercial production of spark source instruments continued throughout the 50s, 60s, and 70s, but they were phased out when other trace element detection techniques with improved resolution and accuracy were invented (circa 1960s). [5] Successors of the spark ion source for trace element analysis are the laser ion source, glow discharge ion source, and inductively coupled plasma ion source. Today, very few laboratories use spark ionization worldwide.
The spark ion source consists of a vacuum chamber containing the electrodes, which is called the spark housing. The tips of the electrodes are composed of or containing the sample and are electrically connected to the power supply. Extraction electrodes create an electric field that accelerate the generated ions through the exit slit.
For spark ionization, there exist two ion sources: the low-voltage direct-current (DC) arc source and the high-voltage radio-frequency (rf) spark source. The arc source has better reproducibility and the ions produced have a narrower energy spread compared to the spark source; however, the spark source has the ability to ionize both conducting and non-conducting samples while the arc source can only ionize conducting samples. [6]
In the low-voltage DC arc source, a high voltage is applied to the two conducting electrodes to initiate the spark, followed by application of a low-voltage direct current to maintain an arc between the spark gap. The duration of the arc is usually only a few hundred microseconds to prevent overheating of the electrodes, and it repeated 50-100 times per second. [2] This method can only be used to ionize conducting samples, e.g. metals.
The high-voltage rf spark source is the one that was used in commercial SSMS instruments due to its ability to ionize both conducting and non-conducting materials. Typically, samples are physically incorporated into two conductive electrodes between which an intermittent (1 MHz) high-voltage (50-100 kV using a Tesla transformer) electric spark is produced, ionizing the material at the tips of the pin-shaped electrodes. [2] When the pulsed current is applied to the electrodes under ultra-high vacuum, a spark discharge plasma occurs in the spark gap in which ions are generated via electron impact. Within the discharge plasma, the sample evaporates, atomizes, and ionizes via electron impact. [7] The total ion current may be optimized by adjusting the distance between the electrodes. This mode of ionization can be used to ionize conducting, semi-conducting, and non-conducting samples.
Conducting and semi-conducting samples may be directly analyzed after being formed into electrodes. Non-conductive samples are first powdered, mixed with a conducting powder (usually high purity graphite or silver), homogenized, and then formed into electrodes. Even liquids can be analyzed if they are frozen or after impregnating a conducting powder. [8] Sample homogeneity is important for reproducibility.
The rf spark source creates ions with a wide energy spread (2-3 kV), which necessitates a double focusing mass analyzer. Mass analyzers are typically Mattauch-Herzog geometry, which achieve velocity and directional focusing onto a plane with either photosensitive plates for ion detection or linear channeltron detector arrays. [9] SSMS has several unique features that make it a useful technique for various applications. Merits of SSMS include high sensitivity with detection limits in the ppb range, simultaneous detection of all elements in a sample, and simple sample preparation. However, the rf spark ion current is discontinuous and erratic, which results in fair resolution and accuracy when standards are not implemented. Other drawbacks include expensive equipment, long analysis time, and the need for highly trained personnel to analyze the spectrum. [5]
Spark source mass spectrometry has been used for trace analysis and multielement analysis applications for highly conducting, semiconducting, and nonconducting materials. Some examples of SSMS applications are the trace element analysis of high-purity materials, multielement analysis of elements in technical alloys, geochemical and cosmochemical samples, biological samples, industrial stream samples, and radioactive material. [8]
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.
Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a mass spectrum, a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is used in many different fields and is applied to pure samples as well as complex mixtures.
An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines.
Electron ionization is an ionization method in which energetic electrons interact with solid or gas phase atoms or molecules to produce ions. EI was one of the first ionization techniques developed for mass spectrometry. However, this method is still a popular ionization technique. This technique is considered a hard ionization method, since it uses highly energetic electrons to produce ions. This leads to extensive fragmentation, which can be helpful for structure determination of unknown compounds. EI is the most useful for organic compounds which have a molecular weight below 600. Also, several other thermally stable and volatile compounds in solid, liquid and gas states can be detected with the use of this technique when coupled with various separation methods.
Gas chromatography–mass spectrometry (GC–MS) is an analytical method that combines the features of gas-chromatography and mass spectrometry to identify different substances within a test sample. Applications of GC–MS include drug detection, fire investigation, environmental analysis, explosives investigation, food and flavor analysis, and identification of unknown samples, including that of material samples obtained from planet Mars during probe missions as early as the 1970s. GC–MS can also be used in airport security to detect substances in luggage or on human beings. Additionally, it can identify trace elements in materials that were previously thought to have disintegrated beyond identification. Like liquid chromatography–mass spectrometry, it allows analysis and detection even of tiny amounts of a substance.
A glow discharge is a plasma formed by the passage of electric current through a gas. It is often created by applying a voltage between two electrodes in a glass tube containing a low-pressure gas. When the voltage exceeds a value called the striking voltage, the gas ionization becomes self-sustaining, and the tube glows with a colored light. The color depends on the gas used.
Ion mobility spectrometry (IMS) It is a method of conducting analytical research that separates and identifies ionized molecules present in the gas phase based on the mobility of the molecules in a carrier buffer gas. Even though it is used extensively for military or security objectives, such as detecting drugs and explosives, the technology also has many applications in laboratory analysis, including studying small and big biomolecules. IMS instruments are extremely sensitive stand-alone devices, but are often coupled with mass spectrometry, gas chromatography or high-performance liquid chromatography in order to achieve a multi-dimensional separation. They come in various sizes, ranging from a few millimeters to several meters depending on the specific application, and are capable of operating under a broad range of conditions. IMS instruments such as microscale high-field asymmetric-waveform ion mobility spectrometry can be palm-portable for use in a range of applications including volatile organic compound (VOC) monitoring, biological sample analysis, medical diagnosis and food quality monitoring. Systems operated at higher pressure are often accompanied by elevated temperature, while lower pressure systems (1–20 hPa) do not require heating.
Atmospheric pressure chemical ionization (APCI) is an ionization method used in mass spectrometry which utilizes gas-phase ion-molecule reactions at atmospheric pressure (105 Pa), commonly coupled with high-performance liquid chromatography (HPLC). APCI is a soft ionization method similar to chemical ionization where primary ions are produced on a solvent spray. The main usage of APCI is for polar and relatively less polar thermally stable compounds with molecular weight less than 1500 Da. The application of APCI with HPLC has gained a large popularity in trace analysis detection such as steroids, pesticides and also in pharmacology for drug metabolites.
Isotope-ratio mass spectrometry (IRMS) is a specialization of mass spectrometry, in which mass spectrometric methods are used to measure the relative abundance of isotopes in a given sample.
In mass spectrometry, Orbitrap is an ion trap mass analyzer consisting of an outer barrel-like electrode and a coaxial inner spindle-like electrode that traps ions in an orbital motion around the spindle. The image current from the trapped ions is detected and converted to a mass spectrum by first using the Fourier transform of time domain of the harmonic to create a frequency signal which is converted to mass.
In mass spectrometry, direct analysis in real time (DART) is an ion source that produces electronically or vibronically excited-state species from gases such as helium, argon, or nitrogen that ionize atmospheric molecules or dopant molecules. The ions generated from atmospheric or dopant molecules undergo ion-molecule reactions with the sample molecules to produce analyte ions. Analytes with low ionization energy may be ionized directly. The DART ionization process can produce positive or negative ions depending on the potential applied to the exit electrode.
Ion mobility spectrometry–mass spectrometry (IMS-MS) is an analytical chemistry method that separates gas phase ions based on their interaction with a collision gas and their masses. In the first step, the ions are separated according to their mobility through a buffer gas on a millisecond timescale using an ion mobility spectrometer. The separated ions are then introduced into a mass analyzer in a second step where their mass-to-charge ratios can be determined on a microsecond timescale. The effective separation of analytes achieved with this method makes it widely applicable in the analysis of complex samples such as in proteomics and metabolomics.
Atomic emission spectroscopy (AES) is a method of chemical analysis that uses the intensity of light emitted from a flame, plasma, arc, or spark at a particular wavelength to determine the quantity of an element in a sample. The wavelength of the atomic spectral line in the emission spectrum gives the identity of the element while the intensity of the emitted light is proportional to the number of atoms of the element. The sample may be excited by various methods.
Ambient ionization is a form of ionization in which ions are formed in an ion source outside the mass spectrometer without sample preparation or separation. Ions can be formed by extraction into charged electrospray droplets, thermally desorbed and ionized by chemical ionization, or laser desorbed or ablated and post-ionized before they enter the mass spectrometer.
A triple quadrupole mass spectrometer (TQMS), is a tandem mass spectrometer consisting of two quadrupole mass analyzers in series, with a (non-mass-resolving) radio frequency (RF)–only quadrupole between them to act as a cell for collision-induced dissociation. This configuration is often abbreviated QqQ, here Q1q2Q3.
The linear ion trap (LIT) is a type of ion trap mass spectrometer.
Atmospheric pressure photoionization (APPI) is a soft ionization method used in mass spectrometry (MS) usually coupled to liquid chromatography (LC). Molecules are ionized using a vacuum ultraviolet (VUV) light source operating at atmospheric pressure, either by direct absorption followed by electron ejection or through ionization of a dopant molecule that leads to chemical ionization of target molecules. The sample is usually a solvent spray that is vaporized by nebulization and heat. The benefit of APPI is that it ionizes molecules across a broad range of polarity and is particularly useful for ionization of low polarity molecules for which other popular ionization methods such as electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) are less suitable. It is also less prone to ion suppression and matrix effects compared to ESI and APCI and typically has a wide linear dynamic range. The application of APPI with LC/MS is commonly used for analysis of petroleum compounds, pesticides, steroids, and drug metabolites lacking polar functional groups and is being extensively deployed for ambient ionization particularly for explosives detection in security applications.
A miniature mass spectrometer (MMS) is a type of mass spectrometer (MS) which has small size and weight and can be understood as a portable or handheld device. Current lab-scale mass spectrometers however, usually weigh hundreds of pounds and can cost on the range from thousands to millions of dollars. One purpose of producing MMS is for in situ analysis. This in situ analysis can lead to much simpler mass spectrometer operation such that non-technical personnel like physicians at the bedside, firefighters in a burning factory, food safety inspectors in a warehouse, or airport security at airport checkpoints, etc. can analyze samples themselves saving the time, effort, and cost of having the sample run by a trained MS technician offsite. Although, reducing the size of MS can lead to a poorer performance of the instrument versus current analytical laboratory standards, MMS is designed to maintain sufficient resolutions, detection limits, accuracy, and especially the capability of automatic operation. These features are necessary for the specific in-situ applications of MMS mentioned above.
Resonance ionization is a process in optical physics used to excite a specific atom beyond its ionization potential to form an ion using a beam of photons irradiated from a pulsed laser light. In resonance ionization, the absorption or emission properties of the emitted photons are not considered, rather only the resulting excited ions are mass-selected, detected and measured. Depending on the laser light source used, one electron can be removed from each atom so that resonance ionization produces an efficient selectivity in two ways: elemental selectivity in ionization and isotopic selectivity in measurement.
Probe electrospray ionization (PESI) is an electrospray-based ambient ionization technique which is coupled with mass spectrometry for sample analysis. Unlike traditional mass spectrometry ion sources which must be maintained in a vacuum, ambient ionization techniques permit sample ionization under ambient conditions, allowing for the high-throughput analysis of samples in their native state, often with minimal or no sample pre-treatment. The PESI ion source simply consists of a needle to which a high voltage is applied following sample pick-up, initiating electrospray directly from the solid needle.
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