Radioanalytical chemistry

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Radioanalytical chemistry focuses on the analysis of sample for their radionuclide content. Various methods are employed to purify and identify the radioelement of interest through chemical methods and sample measurement techniques.

Contents

History

The field of radioanalytical chemistry was originally developed by Marie Curie with contributions by Ernest Rutherford and Frederick Soddy. They developed chemical separation and radiation measurement techniques on terrestrial radioactive substances. During the twenty years that followed 1897 the concepts of radionuclides was born. [1] Since Curie's time, applications of radioanalytical chemistry have proliferated. Modern advances in nuclear and radiochemistry research have allowed practitioners to apply chemistry and nuclear procedures to elucidate nuclear properties and reactions, used radioactive substances as tracers, and measure radionuclides in many different types of samples. [2]

The importance of radioanalytical chemistry spans many fields including chemistry, physics, medicine, pharmacology, biology, ecology, hydrology, geology, forensics, atmospheric sciences, health protection, archeology, and engineering. Applications include: forming and characterizing new elements, determining the age of materials, and creating radioactive reagents for specific tracer use in tissues and organs. The ongoing goal of radioanalytical researchers is to develop more radionuclides and lower concentrations in people and the environment.

Radiation decay modes

Alpha-particle decay

Alpha decay is characterized by the emission of an alpha particle, a 4He nucleus. The mode of this decay causes the parent nucleus to decrease by two protons and two neutrons. This type of decay follows the relation:

[3]

Beta-particle decay

Beta decay is characterized by the emission of a neutrino and a negatron which is equivalent to an electron. This process occurs when a nucleus has an excess of neutrons with respect to protons, as compared to the stable isobar. This type of transition converts a neutron into a proton; similarly, a positron is released when a proton is converted into a neutron. These decays follows the relation:


[4]

Gamma-ray decay

Gamma ray emission follows the previously discussed modes of decay when the decay leaves a daughter nucleus in an excited state. This nucleus is capable of further de-excitation to a lower energy state by the release of a photon. This decay follows the relation:

[5]

Radiation detection principles

Gas ionization detectors

Schematic of an ionization detector Gas det.JPG
Schematic of an ionization detector

Gaseous ionization detectors collect and record the electrons freed from gaseous atoms and molecules by the interaction of radiation released by the source. A voltage potential is applied between two electrodes within a sealed system. Since the gaseous atoms are ionized after they interact with radiation they are attracted to the anode which produces a signal. It is important to vary the applied voltage such that the response falls within a critical proportional range.

Solid-state detectors

Schematic of a solid-state detector Solid det.JPG
Schematic of a solid-state detector

The operating principle of Semiconductor detectors is similar to gas ionization detectors: expect instead of ionization gas atoms, free electrons and holes are produced which create a signal at the electrodes. The advantage of solid state detectors is the greater resolution of the resultant energy spectrum. Usually NaI(Tl) detectors are used; for more precise applications Ge(Li) and Si(Li) detectors have been developed. For extra sensitive measurements high-pure germanium detectors are used under a liquid nitrogen environment. [6]

Scintillation detectors

Scintillation detectors uses a photo luminescent source (such as ZnS) which interacts with radiation. When a radioactive particle decays and strikes the photo luminescent material a photon is released. This photon is multiplied in a photomultiplier tube which converts light into an electrical signal. This signal is then processed and converted into a channel. By comparing the number of counts to the energy level (typically in keV or MeV) the type of decay can be determined.

Chemical separation techniques

Due to radioactive nucleotides have similar properties to their stable, inactive, counterparts similar analytical chemistry separation techniques can be used. These separation methods include precipitation, Ion Exchange, Liquid Liquid extraction, Solid Phase extraction, Distillation, and Electrodeposition.

Radioanalytical chemistry principles

Sample loss by radiocolloidal behaviour

Samples with very low concentrations are difficult to measure accurately due to the radioactive atoms unexpectedly depositing on surfaces. Sample loss at trace levels may be due to adhesion to container walls and filter surface sites by ionic or electrostatic adsorption, as well as metal foils and glass slides. Sample loss is an ever present concern, especially at the beginning of the analysis path where sequential steps may compound these losses.

Various solutions are known to circumvent these losses which include adding an inactive carrier or adding a tracer. Research has also shown that pretreatment of glassware and plastic surfaces can reduce radionuclide sorption by saturating the sites. [7]

Carrier or tracer addition

Since small amounts of radionuclides are typically being analyzed, the mechanics of manipulating tiny quantities is challenging. This problem is classically addressed by the use of carrier ions. Thus, carrier addition involves the addition of a known mass of stable ion to radionuclide-containing sample solution. The carrier is of the identical element but is non-radioactive. The carrier and the radionuclide of interest have identical chemical properties. Typically the amount of carrier added is conventionally selected for the ease of weighing such that the accuracy of the resultant weight is within 1%. For alpha particles, special techniques must be applied to obtain the required thin sample sources. The use of carries was heavily used by Marie Curie and was employed in the first demonstration of nuclear fission. [8]

Isotope dilution is the reverse of tracer addition. It involves the addition of a known (small) amount of radionuclide to the sample that contains a known stable element. This additive is the "tracer." It is added at the start of the analysis procedure. After the final measurements are recorded, sample loss can be determined quantitatively. This procedure avoids the need for any quantitative recovery, greatly simplifying the analytical process.

Typical radionuclides of interest

Commonly measured long lived cosmogenic isotopes
Element Mass Half-life (years)Typical source
Helium 3- stable -Air, water, and biota samples for bioassays
Carbon 145,730 Radiocarbon dating of organic matter, water
Iron 552.7Produced in iron and steel casings, vessels, or supports for nuclear weapons and reactors
Strontium 9028.8Common fission product
Technetium 99214,000Common fission product
Iodine 12915.7 millionGroundwater tracer
Cesium 13730.2Nuclear weapons and nuclear reactors (accidents)
Promethium 1472.62Naturally occurring fission product
Radon 2261,600Rain and groundwater, atmosphere
Uranium 232, 233, 234, 235, 236, 238VariesTerrestrial element
Plutonium 238, 239, 240, 241, 242VariesNuclear weapons and reactors
Americium 241433Result of neutron interactions with uranium and plutonium

Quality assurance

As this is an analytical chemistry technique quality control is an important factor to maintain. A laboratory must produce trustworthy results. This can be accomplished by a laboratories continual effort to maintain instrument calibration, measurement reproducibility, and applicability of analytical methods. [9] In all laboratories there must be a quality assurance plan. This plan describes the quality system and procedures in place to obtain consistent results. Such results must be authentic, appropriately documented, and technically defensible." [10] Such elements of quality assurance include organization, personnel training, laboratory operating procedures, procurement documents, chain of custody records, standard certificates, analytical records, standard procedures, QC sample analysis program and results, instrument testing and maintenance records, results of performance demonstration projects, results of data assessment, audit reports, and record retention policies.

The cost of quality assurance is continually on the rise but the benefits far outweigh this cost. The average quality assurance workload was risen from 10% to a modern load of 20-30%. This heightened focus on quality assurance ensures that quality measurements that are reliable are achieved. The cost of failure far outweighs the cost of prevention and appraisal. Finally, results must be scientifically defensible by adhering to stringent regulations in the event of a lawsuit.

Related Research Articles

Alpha decay Emission of alpha particles by a decaying radioactive atom

Alpha decay or α-decay is a type of radioactive decay in which an atomic nucleus emits an alpha particle and thereby transforms or 'decays' into a different atomic nucleus, with a mass number that is reduced by four and an atomic number that is reduced by two. An alpha particle is identical to the nucleus of a helium-4 atom, which consists of two protons and two neutrons. It has a charge of +2 e and a mass of 4 u. For example, uranium-238 decays to form thorium-234. Alpha particles have a charge +2 e, but as a nuclear equation describes a nuclear reaction without considering the electrons – a convention that does not imply that the nuclei necessarily occur in neutral atoms – the charge is not usually shown. Alpha decay typically occurs in the heaviest nuclides. Theoretically, it can occur only in nuclei somewhat heavier than nickel, where the overall binding energy per nucleon is no longer a minimum and the nuclides are therefore unstable toward spontaneous fission-type processes. In practice, this mode of decay has only been observed in nuclides considerably heavier than nickel, with the lightest known alpha emitters being the lightest isotopes of tellurium. Exceptionally, however, beryllium-8 decays to two alpha particles. Alpha decay is by far the most common form of cluster decay, where the parent atom ejects a defined daughter collection of nucleons, leaving another defined product behind. It is the most common form because of the combined extremely high nuclear binding energy and a relatively small mass of the alpha particle. Like other cluster decays, alpha decay is fundamentally a quantum tunneling process. Unlike beta decay, it is governed by the interplay between both the nuclear force and the electromagnetic force. Alpha particles have a typical kinetic energy of 5 MeV and have a speed of about 15,000,000 m/s, or 5% of the speed of light. There is surprisingly small variation around this energy, due to the heavy dependence of the half-life of this process on the energy produced. Because of their relatively large mass, the electric charge of +2 e and relatively low velocity, alpha particles are very likely to interact with other atoms and lose their energy, and their forward motion can be stopped by a few centimeters of air. Approximately 99% of the helium produced on Earth is the result of the alpha decay of underground deposits of minerals containing uranium or thorium. The helium is brought to the surface as a by-product of natural gas production.

Beta decay type of radioactive decay

In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle is emitted from an atomic nucleus, transforming the original nuclide to an isobar. For example, beta decay of a neutron transforms it into a proton by the emission of an electron accompanied by an antineutrino; or, conversely a proton is converted into a neutron by the emission of a positron with a neutrino in so-called positron emission. Neither the beta particle nor its associated (anti-)neutrino exist within the nucleus prior to beta decay, but are created in the decay process. By this process, unstable atoms obtain a more stable ratio of protons to neutrons. The probability of a nuclide decaying due to beta and other forms of decay is determined by its nuclear binding energy. The binding energies of all existing nuclides form what is called the nuclear band or valley of stability. For either electron or positron emission to be energetically possible, the energy release or Q value must be positive.

Neutron Subatomic particle with no electric charge

The neutron is a subatomic particle, symbol
n
or
n0
, which has a neutral charge and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons behave similarly within the nucleus, and each has a mass of approximately one atomic mass unit, they are both referred to as nucleons. Their properties and interactions are described by nuclear physics.

Neutron activation analysis

Neutron activation analysis (NAA) is the nuclear process used for determining the concentrations of elements in a vast amount of materials. NAA allows discrete sampling of elements as it disregards the chemical form of a sample, and focuses solely on its nucleus. The method is based on neutron activation and therefore requires a source of neutrons. The sample is bombarded with neutrons, causing the elements to form radioactive isotopes. The radioactive emissions and radioactive decay paths for each element are well known. Using this information, it is possible to study spectra of the emissions of the radioactive sample, and determine the concentrations of the elements within it. A particular advantage of this technique is that it does not destroy the sample, and thus has been used for analysis of works of art and historical artifacts. NAA can also be used to determine the activity of a radioactive sample.

A radionuclide is an atom that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferred to one of its electrons to release it as a conversion electron; or used to create and emit a new particle from the nucleus. During those processes, the radionuclide is said to undergo radioactive decay. These emissions are considered ionizing radiation because they are powerful enough to liberate an electron from another atom. The radioactive decay can produce a stable nuclide or will sometimes produce a new unstable radionuclide which may undergo further decay. Radioactive decay is a random process at the level of single atoms: it is impossible to predict when one particular atom will decay. However, for a collection of atoms of a single element the decay rate, and thus the half-life (t1/2) for that collection, can be calculated from their measured decay constants. The range of the half-lives of radioactive atoms has no known limits and spans a time range of over 55 orders of magnitude.

Beta particle Ionizing radiation

A beta particle, also called beta ray or beta radiation, is a high-energy, high-speed electron or positron emitted by the radioactive decay of an atomic nucleus during the process of beta decay. There are two forms of beta decay, β decay and β+ decay, which produce electrons and positrons respectively.

A synthetic radioisotope is a radionuclide that is not found in nature: no natural process or mechanism exists which produces it, or it is so unstable that it decays away in a very short period of time. Examples include technetium-95 and promethium-146. Many of these are found in, and harvested from, spent nuclear fuel assemblies. Some must be manufactured in particle accelerators.

Nuclear technology Technology that involves the reactions of atomic nuclei

Nuclear technology is technology that involves the nuclear reactions of atomic nuclei. Among the notable nuclear technologies are nuclear reactors, nuclear medicine and nuclear weapons. It is also used, among other things, in smoke detectors and gun sights.

Nuclide

A nuclide is an atom characterized by its number of protons, Z, its number of neutrons, N, and its nuclear energy state.

Radioactive decay Physical mechanism

Radioactive decay is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is considered radioactive. Three of the most common types of decay are alpha decay, beta decay, and gamma decay, all of which involve emitting one or more particles or photons. The weak force is the mechanism that is responsible for beta decay.

Ionizing radiation Radiation that carries enough light energy to liberate electrons from atoms or molecules

Ionizing radiation is radiation, traveling as a particle or electromagnetic wave, that carries sufficient energy to detach electrons from atoms or molecules, thereby ionizing an atom or a molecule. Ionizing radiation is made up of energetic subatomic particles, ions or atoms moving at high speeds, and electromagnetic waves on the high-energy end of the electromagnetic spectrum.

Nuclear chemistry branch of chemistry concerned with radioactivity, transmutation and other nuclear processes

Nuclear chemistry is the sub-field of chemistry dealing with radioactivity, nuclear processes, and transformations in the nuclei of atoms, such as nuclear transmutation and nuclear properties.

A radioactive tracer, radiotracer, or radioactive label, is a chemical compound in which one or more atoms have been replaced by a radionuclide so by virtue of its radioactive decay it can be used to explore the mechanism of chemical reactions by tracing the path that the radioisotope follows from reactants to products. Radiolabeling or radiotracing is thus the radioactive form of isotopic labeling.

Radiopharmacology

Radiopharmacology is radiochemistry applied to medicine and thus the pharmacology of radiopharmaceuticals. Radiopharmaceuticals are used in the field of nuclear medicine as radioactive tracers in medical imaging and in therapy for many diseases. Many radiopharmaceuticals use technetium-99m (Tc-99m) which has many useful properties as a gamma-emitting tracer nuclide. In the book Technetium a total of 31 different radiopharmaceuticals based on Tc-99m are listed for imaging and functional studies of the brain, myocardium, thyroid, lungs, liver, gallbladder, kidneys, skeleton, blood and tumors.

Radiochemistry is the chemistry of radioactive materials, where radioactive isotopes of elements are used to study the properties and chemical reactions of non-radioactive isotopes. Much of radiochemistry deals with the use of radioactivity to study ordinary chemical reactions. This is very different from radiation chemistry where the radiation levels are kept too low to influence the chemistry.

Coprecipitation

In chemistry, coprecipitation (CPT) or co-precipitation is the carrying down by a precipitate of substances normally soluble under the conditions employed. Analogously, in medicine, coprecipitation is specifically the precipitation of an unbound "antigen along with an antigen-antibody complex".

Isotope nuclides having the same atomic number but different mass numbers

Isotopes are variants of a particular chemical element which differ in neutron number, and consequently in nucleon number. All isotopes of a given element have the same number of protons but different numbers of neutrons in each atom.

Alpha particle helium-4 nucleus; a particle consisting of two protons and two neutrons bound together

Alpha particles, also called alpha rays or alpha radiation, consist of two protons and two neutrons bound together into a particle identical to a helium-4 nucleus. They are generally produced in the process of alpha decay, but may also be produced in other ways. Alpha particles are named after the first letter in the Greek alphabet, α. The symbol for the alpha particle is α or α2+. Because they are identical to helium nuclei, they are also sometimes written as He2+
or 4
2
He2+
indicating a helium ion with a +2 charge. If the ion gains electrons from its environment, the alpha particle becomes a normal helium atom 4
2
He
.

Nuclear forensics is the investigation of nuclear materials to find evidence for the source, the trafficking, and the enrichment of the material. The material can be recovered from various sources including dust from the vicinity of a nuclear facility, or from the radioactive debris following a nuclear explosion.

Radioactive source

A radioactive source is a known quantity of a radionuclide which emits ionizing radiation; typically one or more of the radiation types gamma rays, alpha particles, beta particles, and neutron radiation.

References

  1. Ehmann, W.D., Vance, D. E. Radiochemistry and Nuclear Methods of Analysis, 1991, 1-20
  2. Krane, K.S. Introductory Nuclear Physics, 1988, John Wiley & Sons, 3-4.
  3. "Archived copy". Archived from the original on 2009-08-06. Retrieved 2009-07-11.CS1 maint: archived copy as title (link)
  4. "ChemTeam: Writing Alpha and Beta Equations". chemteam.info.
  5. Loveland, W., Morrissey, D. J., Seaborg, G. T., Modern Nuclear Chemistry, 2006, John Wiley & Sons, 221.
  6. Ehmann, W.D., Vance, D. E. Radiochemistry and Nuclear Methods of Analysis, 1991, 220-236.
  7. Theirs, R. E., Separation, Concentration, and Contamination in Trace Analysis, 1957, John Wiley, 637-666.
  8. O. Hahn & F. Strassmann (1939). "Über den Nachweis und das Verhalten der bei der Bestrahlung des Urans mittels Neutronen entstehenden Erdalkalimetalle ("On the detection and characteristics of the alkaline earth metals formed by irradiation of uranium with neutrons")". Naturwissenschaften. 27 (1): 11–15. Bibcode:1939NW.....27...11H. doi:10.1007/BF01488241. S2CID   5920336..
  9. Khan, B. Radioanalytical Chemistry, 2007, Springer, 220-243.
  10. EPA. US Environmental Protection Agency Report 402-R-97-016, 2000, QA/G-4

Further reading