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Occurrence

The longest-lived isotope of neptunium, Np, has a half-life of 2.14 million years, which is more than 2,000 times shorter than the age of the Earth. Therefore, any primordial neptunium would have decayed in the distant past. After only about 80 million years, the concentration of even the longest-lived isotope, Np, would have been reduced to less than one-trillionth (10) of its original amount. Thus neptunium is present in nature only in negligible amounts produced as intermediate decay products of other isotopes.

Trace amounts of the neptunium isotopes neptunium-237 and -239 are found naturally as decay products from transmutation reactions in uranium ores. Np and Np are the most common of these isotopes; they are directly formed from neutron capture by uranium-238 atoms. These neutrons come from the spontaneous fission of uranium-238, naturally neutron-induced fission of uranium-235, cosmic ray spallation of nuclei, and light elements absorbing alpha particles and emitting a neutron. The half-life of Np is very short, although the detection of its much longer-lived daughter Pu in nature in 1951 definitively established its natural occurrence. In 1952, Np was identified and isolated from concentrates of uranium ore from the Belgian Congo: in these minerals, the ratio of neptunium-237 to uranium is less than or equal to about 10 to 1. Additionally, Np must also occur as an intermediate decay product of Pu, which has been detected in meteorite dust in marine sediments on Earth.

Most neptunium (and plutonium) now encountered in the environment is due to atmospheric nuclear explosions that took place between the detonation of the first atomic bomb in 1945 and the ratification of the Partial Nuclear Test Ban Treaty in 1963. The total amount of neptunium released by these explosions and the few atmospheric tests that have been carried out since 1963 is estimated to be around 2500 kg. The overwhelming majority of this is composed of the long-lived isotopes Np and Np since even the moderately long-lived Np (half-life 396 days) would have decayed to less than one-billionth (10) its original concentration over the intervening decades. An additional very small amount of neptunium, produced by neutron irradiation of natural uranium in nuclear reactor cooling water, is released when the water is discharged into rivers or lakes. The concentration of Np in seawater is approximately 6.5 × 10 millibecquerels per liter: this concentration is between 0.1% and 1% that of plutonium.

Once released in the surface environment, in contact with atmospheric oxygen, neptunium generally oxidizes fairly quickly, usually to the +4 or +5 state. Regardless of its oxidation state, the element exhibits much greater mobility than the other actinides, largely due to its ability to readily form aqueous solutions with various other elements. In one study comparing the diffusion rates of neptunium(V), plutonium(IV), and americium(III) in sandstone and limestone, neptunium penetrated more than ten times as well as the other elements. Np(V) will also react efficiently in pH levels greater than 5.5 if there are no carbonates present and in these conditions it has also been observed to readily bond with quartz. It has also been observed to bond well with goethite, ferric oxide colloids, and several clays including kaolinite and smectite. Np(V) does not bond as readily to soil particles in mildly acidic conditions as its fellow actinides americium and curium by nearly an order of magnitude. This behavior enables it to migrate rapidly through the soil while in solution without becoming fixed in place, contributing further to its mobility. Np(V) is also readily absorbed by concrete, which because of the element's radioactivity is a consideration that must be addressed when building nuclear waste storage facilities. When absorbed in concrete, it is reduced to Np(IV) in a relatively short period of time. Np(V) is also reduced by humic acids if they are present on the surface of goethite, hematite, and magnetite. Np(IV) is less mobile and efficiently adsorbed by tuff, granodiorite, and bentonite; although uptake by the latter is most pronounced in mildly acidic conditions. It also exhibits a strong tendency to bind to colloidal particulates, an effect that is enhanced when in surface soil with high clay content. The behavior provides an additional aid in the element's observed high mobility.