Actinide neptunium

Elements 43 (technetium), 61 (promethium), 85 (astatine), and all elements with Z > 92 do not exist naturally on the Earth, because no isotopes of these elements are stable. After the discovery of nuclear reactions early in the twentieth century, scientists set out to make these missing elements. Between 1937 and 1945, the gaps were filled and three actinides, neptunium (Z = 93), plutonium (Z = 94), and americium (Z = 95) also were made. 

The transuranic elements are a subseries within the actinide series with atomic numbers higher than uranium They include the actinides neptunium (53NP) up to... 

After a few years of storage, the main radioactive heat emitters in HLW are 90Sr and 137Cs. In addition, extremely long-lived actinides—neptunium, plutonium, americium, and curium—should be collected for transmutation in the future. Therefore, different flowsheets can be proposed for waste processing. It is possible to extract each radionuclide in the special extraction (sorption) cycle, for example, uranium and plutonium in the PUREX process, and after that, minor actinides (MAs) by the TRUEX process,4 strontium by the SREX process,5,6 and cesium by sorption7 or extraction.8... 

Recently much attention has been given to the accelerator driven systems, burning in inert matrices, and the use of thorium to burn plutonium. The concept of a closed nuclear fuel cycle was traditionally considered as transmutation (burning) of only plutonium and recycled uranium, with minor actinides (neptunium, americium, curium) destined for final geological disposal. But as time goes on, a new understanding is emerging reduction of the quantity of actinides would ease requirements for final repositories and make them relatively less expensive. 

From 1992, the role of Phenix as an irradiation facility has been emphasized, particularly in support of the CEA R D programme in the context of line 1 of the December 30th 1991 law on long-lived radioactive waste management. The first experiment, called SUPERFACT, led to the incineration of minor actinides (neptunium and americium). This programme was further strengthened in 1997, to compensate for the shutdown of Superphenix. It involves transmutation of Minor Actinides and Long-Lived Fission Products. 

In the Reprocessing Fuel Cycle (RFC) option, the unused uranium and the plutonium produced in the reactor are recovered leaving the minor actinides with the fission products as HLW. (The radiotoxicity of these wastes will be significantly less than that of the spent fuel although the toxic lifetime is determined by the minor actinides - neptunium, americium, curium - and, to a lesser extent, by some of the long-lived fission products content of the waste.) As mentioned previously, this was the scenario initially envisioned by the nuclear power industry to reprocess fuel for two reasons ... 

Planet pluto) Plutonium was the second transuranium element of the actinide series to be discovered. The isotope 238pu was produced in 1940 by Seaborg, McMillan, Kennedy, and Wahl by deuteron bombardment of uranium in the 60-inch cyclotron at Berkeley, California. Plutonium also exists in trace quantities in naturally occurring uranium ores. It is formed in much the same manner as neptunium, by irradiation of natural uranium with the neutrons which are present. 

Each of the elements has a number of isotopes (2,4), all radioactive and some of which can be obtained in isotopicaHy pure form. More than 200 in number and mosdy synthetic in origin, they are produced by neutron or charged-particle induced transmutations (2,4). The known radioactive isotopes are distributed among the 15 elements approximately as follows actinium and thorium, 25 each protactinium, 20 uranium, neptunium, plutonium, americium, curium, californium, einsteinium, and fermium, 15 each herkelium, mendelevium, nobehum, and lawrencium, 10 each. There is frequently a need for values to be assigned for the atomic weights of the actinide elements. Any precise experimental work would require a value for the isotope or isotopic mixture being used, but where there is a purely formal demand for atomic weights, mass numbers that are chosen on the basis of half-life and availabiUty have customarily been used. A Hst of these is provided in Table 1. 

In general, the absorption bands of the actinide ions are some ten times more intense than those of the lanthanide ions. Fluorescence, for example, is observed in the trichlorides of uranium, neptunium, americium, and curium, diluted with lanthanum chloride (15). 

Actinide Peroxides. Many peroxo compounds of thorium, protactinium, uranium, neptunium, plutonium, and americium are known (82,89). The crystal stmctures of a number of these have been deterrnined. Perhaps the best known are uranium peroxide dihydrate [1344-60-1/, UO 2H20, and, the uranium peroxide tetrahydrate [15737-4-5] UO 4H2O, which are formed when hydrogen peroxide is added to an acid solution of a uranyl salt. 

That magnetic measurements often raise more problems than they solve, is demonstrated for the indicated compound. We prepared a series of [ (C2H5N] i,An(NSC) e compounds (An = Th, U, Np, Pu) with cubic coordination of the actinide ion. We derived a consistent interpretation of the magnetic and optical properties of the uranium and the neptunium compounds (6 ). In the case of Pu we expect an isolated T1 ground state and a first excited state at about 728 cm-1. To our surprise we found a magnetic ground state much more pronounced than in the case of the hexachloro-complex, Fig. 4. 

The chemical similarity between lanthanide and actinide metals suggests that C2H I2 might also react with actinide metals. Preliminary experiments found no reaction between thorium or uranium metals and a THF solution of Plutonium and neptunium... 

The problem could be stated from another point of view. In an isostructural series the uranium and neptunium compounds tend to be itinerant electron magnets or band magnets (like iron) and their orbital contribution is at least partially quenched. For much heavier actinides we know that the compounds will make local moment magnets with orbital contributions. It is quite possible that in between these two clear cut forms of magnetism that the intermediate case could be dominated by fluctuations, and no recognizable form of magnetism would occur. To state that the... 

The Table shows a great spread in Kd-values even at the same location. This is due to the fact that the environmental conditions influence the partition of plutonium species between different valency states and complexes. For the different actinides, it is found that the Kd-values under otherwise identical conditions (e.g. for the uptake of plutonium on geologic materials or in organisms) decrease in the order Pu>Am>U>Np (15). Because neptunium is usually pentavalent, uranium hexavalent and americium trivalent, while plutonium in natural systems is mainly tetravalent, it is clear from the actinide homologue properties that the oxidation state of plutonium will affect the observed Kd-value. The oxidation state of plutonium depends on the redox potential (Eh-value) of the ground water and its content of oxidants or reductants. It is also found that natural ligands like C032- and fulvic acids, which complex plutonium (see next section), also influence the Kd-value. 

Most of the larger actinides do not exist in nature. Scientists have created them artificially in the laboratory. Neptunium was first created in 1940, but lawrencium not until 1961. While these artificial elements are interesting, they are not particularly useful because they are so costly to make and because, being very unstable, they do not last very long. 

Holm et al. [74] used a spectrometry for the determination of 237neptunium in seawater. The actinides are preconcentrated from a large seawater sample by hydroxide precipitation. The neptunium was isolated by ion exchange, fluoride precipitation, and extraction with TTA. 238Neptunium or 235neptunium was used to determine the radiochemical yield. 

Since plutonium is the actinide generating most concern at the moment this review will be concerned primarily with this element. However, in the event of the fast breeder reactors being introduced the behaviour of americium and curium will be emphasised. As neptunium is of no major concern in comparison to plutonium there has been little research conducted on its behaviour in the biosphere. This review will not discuss the behaviour of berkelium, californium, einsteinium, fermium, mendelevium, nobelium and lawrencium which are of no concern in the nuclear power programme although some of these actinides may be used in nuclear powered pacemakers. Occasionally other actinides, and some lanthanides, are referred to but merely to illustrate a particular fact of the actinides with greater clarity. 

The chemistry of neptunium (jjNp) is somewhat similar to that of uranium (gjU) and plutonium (g4Pu), which immediately precede and follow it in the actinide series on the periodic table. The discovery of neptunium provided a solution to a puzzle as to the missing decay products of the thorium decay series, in which all the elements have mass numbers evenly divisible by four the elements in the uranium series have mass numbers divisible by four with a remainder of two. The actinium series elements have mass numbers divisible by four with a remainder of three. It was not until the neptunium series was discovered that a decay series with a mass number divisible by four and a remainder of one was found. The neptunium decay series proceeds as follows, starting with the isotope plutonium-241 Pu-24l—> Am-24l Np-237 Pa-233 U-233 Th-229 Ra-225 Ac-225 Fr-221 At-217 Bi-213 Ti-209 Pb-209 Bi-209. 

Neptunium is the first of the subseries of the actinide series known as the traiisuratiic elements—those heavy, synthetic (man-made) radioactive elements that have an atomic number greater than uranium in the actinide series of the periodic table. An interesting fact is that neptunium was artificially synthesized before small traces of it were discovered in nature. More is produced by scientists every year than exists in nature. 

The first actinide metals to be prepared were those of the three members of the actinide series present in nature in macro amounts, namely, thorium (Th), protactinium (Pa), and uranium (U). Until the discovery of neptunium (Np) and plutonium (Pu) and the subsequent manufacture of milligram amounts of these metals during the hectic World War II years (i.e., the early 1940s), no other actinide element was known. The demand for Pu metal for military purposes resulted in rapid development of preparative methods and considerable study of the chemical and physical properties of the other actinide metals in order to obtain basic knowledge of these unusual metallic elements. 

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