Isotopes of neptunium

Neptunium (93Np) is usually considered an artificial element, although trace quantities are found in nature, so a standard atomic weight cannot be given. Like all trace or artificial elements, it has no stable isotopes. The first isotope to be synthesized and identified was 239Np in 1940, produced by bombarding 238Uranium with neutrons to produce 239Uranium, which then underwent beta decay to 239Neptunium.

Trace quantities are found in nature from neutron capture reactions by uranium atoms, a fact not discovered until 1951.

Twenty-five neptunium radioisotopes have been characterized, with the most stable being 237Neptunium with a half-life of 2.14 million years, 236Neptunium with a half-life of 154,000 years, and 235Neptunium with a half-life of 396.1 days. All of the remaining radioactive isotopes have half-lives that are less than 4.5 days, and the majority of these have half-lives that are less than 50 minutes. This element also has five meta states, with the most stable being 236mNeptunium (t1/2 22.5 hours).

The isotopes of neptunium range from 219Neptunium to 244Neptunium, though the intermediate isotope 221Neptunium has not yet been observed. The primary decay mode before the most stable isotope, 237Neptunium, is electron capture (with a good deal of alpha emission), and the primary mode after is beta emission. The primary decay products before 237Neptunium are isotopes of uranium and protactinium, and the primary products after are isotopes of plutonium. Neptunium is the heaviest element for which the location of the proton drip line is known; the lightest bound isotope is 220Np.

List of isotopes

 * 219Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 126
 * 219.03162(9)
 * α
 * 215Pa
 * (9/2−)
 * 220Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 127
 * 220.03254(21)#
 * α
 * 216Pa
 * 1−#
 * 222Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 129
 * α
 * 218Pa
 * 1-#
 * 223Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 130
 * 223.03285(21)#
 * α
 * 219Pa
 * 9/2−
 * rowspan=2|224Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 131
 * rowspan=2|224.03422(21)#
 * rowspan=2|$0.15 ms$
 * α (83%)
 * 220m1Pa
 * rowspan=2|1−#
 * rowspan=2|
 * α (17%)
 * 220m2Pa
 * 225Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 132
 * 225.03391(8)
 * 6(5) ms
 * α
 * 221Pa
 * 9/2−#
 * 226Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 133
 * 226.03515(10)#
 * 35(10) ms
 * α
 * 222Pa
 * rowspan=2|227Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 134
 * rowspan=2|227.03496(8)
 * rowspan=2|510(60) ms
 * α (99.95%)
 * 223Pa
 * rowspan=2|5/2−#
 * rowspan=2|
 * β+ (.05%)
 * 227U
 * rowspan=3|228Neptunium
 * rowspan=3 style="text-align:right" | 93
 * rowspan=3 style="text-align:right" | 135
 * rowspan=3|228.03618(21)#
 * rowspan=3|61.4(14) s
 * β+ (59%)
 * 228U
 * rowspan=3|
 * rowspan=3|
 * α (41%)
 * 224Pa
 * β+, SF (.012%)
 * (various)
 * rowspan=2|229Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 136
 * rowspan=2|229.03626(9)
 * rowspan=2|4.0(2) min
 * α (51%)
 * 225Pa
 * rowspan=2|5/2+#
 * rowspan=2|
 * β+ (49%)
 * 229U
 * rowspan=2|230Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 137
 * rowspan=2|230.03783(6)
 * rowspan=2|4.6(3) min
 * β+ (97%)
 * 230U
 * rowspan=2|
 * rowspan=2|
 * α (3%)
 * 226Pa
 * rowspan=2|231Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 138
 * rowspan=2|231.03825(5)
 * rowspan=2|48.8(2) min
 * β+ (98%)
 * 231U
 * rowspan=2|(5/2)(+#)
 * rowspan=2|
 * α (2%)
 * 227Pa
 * rowspan=2|232Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 139
 * rowspan=2|232.04011(11)#
 * rowspan=2|14.7(3) min
 * β+ (99.99%)
 * 232U
 * rowspan=2|(4+)
 * rowspan=2|
 * α (.003%)
 * 228Pa
 * rowspan=2|233Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 140
 * rowspan=2|233.04074(5)
 * rowspan=2|36.2(1) min
 * β+ (99.99%)
 * 233U
 * rowspan=2|(5/2+)
 * rowspan=2|
 * α (.001%)
 * 229Pa
 * 234Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 141
 * 234.042895(9)
 * 4.4(1) d
 * β+
 * 234U
 * (0+)
 * rowspan=2 style="text-indent:1em" |234mNeptunium
 * rowspan=2 colspan="3" style="text-indent:2em" |
 * rowspan=2|~9 min
 * IT
 * 234Np
 * rowspan=2|5+
 * rowspan=2|
 * EC
 * 234U
 * rowspan=2|235Neptunium
 * rowspan=2 style="text-align:right" | 93
 * rowspan=2 style="text-align:right" | 142
 * rowspan=2|235.0440633(21)
 * rowspan=2|396.1(12) d
 * EC
 * 235U
 * rowspan=2|5/2+
 * rowspan=2|
 * α (.0026%)
 * 231Pa
 * rowspan=3|236Neptunium
 * rowspan=3 style="text-align:right" | 93
 * rowspan=3 style="text-align:right" | 143
 * rowspan=3|236.04657(5)
 * rowspan=3|1.54(6)×105 y
 * EC (87.3%)
 * 236U
 * rowspan=3|(6−)
 * rowspan=3|
 * β− (12.5%)
 * 236Pu
 * α (.16%)
 * 232Pa
 * rowspan=2 style="text-indent:1em" | 236mNeptunium
 * rowspan=2 colspan="3" style="text-indent:2em" | 60(50) keV
 * rowspan=2|22.5(4) h
 * EC (52%)
 * 236U
 * rowspan=2|1
 * rowspan=2|
 * β− (48%)
 * 236Pu
 * rowspan=3|237Neptunium
 * rowspan=3 style="text-align:right" | 93
 * rowspan=3 style="text-align:right" | 144
 * rowspan=3|237.0481734(20)
 * rowspan=3|2.144(7)×106 y
 * α
 * 233Pa
 * rowspan=3|5/2+
 * rowspan=3|Trace
 * SF (2×10−10%)
 * (various)
 * CD (4×10−12%)
 * 207Tl 30Mg
 * 238Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 145
 * 238.0509464(20)
 * 2.117(2) d
 * β−
 * 238Pu
 * 2+
 * style="text-indent:1em" | 238mNeptunium
 * colspan="3" style="text-indent:2em" | 2300(200)# keV
 * 112(39) ns
 * 239Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 146
 * 239.0529390(22)
 * 2.356(3) d
 * β−
 * 239Pu
 * 5/2+
 * Trace
 * 240Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 147
 * 240.056162(16)
 * 61.9(2) min
 * β−
 * 240Pu
 * (5+)
 * Trace
 * rowspan=2 style="text-indent:1em" | 240mNeptunium
 * rowspan=2 colspan="3" style="text-indent:2em" | 20(15) keV
 * rowspan=2|7.22(2) min
 * β− (99.89%)
 * 240Pu
 * rowspan=2|1(+)
 * rowspan=2|
 * IT (.11%)
 * 240Np
 * 241Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 148
 * 241.05825(8)
 * 13.9(2) min
 * β−
 * 241Pu
 * (5/2+)
 * 242Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 149
 * 242.06164(21)
 * 2.2(2) min
 * β−
 * 242Pu
 * (1+)
 * style="text-indent:1em" | 242mNeptunium
 * colspan="3" style="text-indent:2em" | 0(50)# keV
 * 5.5(1) min
 * 6+#
 * 243Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 150
 * 243.06428(3)#
 * 1.85(15) min
 * β−
 * 243Pu
 * (5/2−)
 * 244Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 151
 * 244.06785(32)#
 * 2.29(16) min
 * β−
 * 244Pu
 * (7−)
 * 239Pu
 * 5/2+
 * Trace
 * 240Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 147
 * 240.056162(16)
 * 61.9(2) min
 * β−
 * 240Pu
 * (5+)
 * Trace
 * rowspan=2 style="text-indent:1em" | 240mNeptunium
 * rowspan=2 colspan="3" style="text-indent:2em" | 20(15) keV
 * rowspan=2|7.22(2) min
 * β− (99.89%)
 * 240Pu
 * rowspan=2|1(+)
 * rowspan=2|
 * IT (.11%)
 * 240Np
 * 241Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 148
 * 241.05825(8)
 * 13.9(2) min
 * β−
 * 241Pu
 * (5/2+)
 * 242Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 149
 * 242.06164(21)
 * 2.2(2) min
 * β−
 * 242Pu
 * (1+)
 * style="text-indent:1em" | 242mNeptunium
 * colspan="3" style="text-indent:2em" | 0(50)# keV
 * 5.5(1) min
 * 6+#
 * 243Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 150
 * 243.06428(3)#
 * 1.85(15) min
 * β−
 * 243Pu
 * (5/2−)
 * 244Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 151
 * 244.06785(32)#
 * 2.29(16) min
 * β−
 * 244Pu
 * (7−)
 * 1.85(15) min
 * β−
 * 243Pu
 * (5/2−)
 * 244Neptunium
 * style="text-align:right" | 93
 * style="text-align:right" | 151
 * 244.06785(32)#
 * 2.29(16) min
 * β−
 * 244Pu
 * (7−)
 * 244Pu
 * (7−)

Neptunium-235
Neptunium-235 has 142 neutrons and a half-life of 396.1 days. This isotope decays by:
 * Alpha emission: the decay energy is 5.2 MeV and the decay product is protactinium-231.
 * Electron capture: the decay energy is 0.125 MeV and the decay product is uranium-235

This isotope of neptunium has a weight of 235.044 063 3 u.

Neptunium-236
Neptunium-236 has 143 neutrons and a half-life of 154,000 years. It can decay by the following methods:
 * Electron capture: the decay energy is 0.93 MeV and the decay product is uranium-236. This usually decays (with a half-life of 23 million years) to thorium-232.
 * Beta emission: the decay energy is 0.48 MeV and the decay product is plutonium-236. This usually decays (half-life 2.8 years) to uranium-232, which usually decays (half-life 69 years) to thorium-228, which decays in a few years to lead-208.
 * Alpha emission: the decay energy is 5.007 MeV and the decay product is protactinium-232. This decays with a half-life of 1.3 days to uranium-232.

This particular isotope of neptunium has a mass of 236.04657 u. It is a fissile material; it has an estimated critical mass of 6.79 kg, though precise experimental data is not available.

236Neptunium is produced in small quantities via the (n,2n) and (γ,n) capture reactions of 237Neptunium, however, it is nearly impossible to separate in any significant quantities from its parent 237Neptunium. It is for this reason that despite its low critical mass and high neutron cross section, it has not been researched extensively as a nuclear fuel in weapons or reactors. Nevertheless, 236Neptunium has been considered for use in mass spectrometry and as a radioactive tracer, because it decays predominantly by beta emission with a long half-life. Several alternative production routes for this isotope have been investigated, namely those that reduce isotopic separation from 237Neptunium or the isomer 236mNeptunium. The most favorable reactions to accumulate 236Neptunium were shown to be proton and deuteron irradiation of uranium-238.

Neptunium-237
237Neptunium decays via the neptunium series, which terminates with thallium-205, which is stable, unlike most other actinides, which decay to stable isotopes of lead.

In 2002, 237Neptunium was shown to be capable of sustaining a chain reaction with fast neutrons, as in a nuclear weapon, with a critical mass of around 60 kg. However, it has a low probability of fission on bombardment with thermal neutrons, which makes it unsuitable as a fuel for light water nuclear power plants (as opposed to fast reactor or accelerator-driven systems, for example).

Inventory in spent nuclear fuel
237Neptunium is the only neptunium isotope produced in significant quantity in the nuclear fuel cycle, both by successive neutron capture by uranium-235 (which fissions most but not all of the time) and uranium-236, or (n,2n) reactions where a fast neutron occasionally knocks a neutron loose from uranium-238 or isotopes of plutonium. Over the long term, 237Neptunium also forms in spent nuclear fuel as the decay product of americium-241.

237Neptunium is considered to be one of the most mobile radionuclides at the site of the Yucca Mountain nuclear waste repository (Nevada) where oxidizing conditions prevail in the unsaturated zone of the volcanic tuff above the water table.

Raw material for production
When exposed to neutron bombardment 237Neptunium can capture a neutron, undergo beta decay, and become 238Plutonium, this product being useful as a thermal energy source in a radioisotope thermoelectric generator (RTG or RITEG) for the production of electricity and heat. The first type of thermoelectric generator SNAP (Systems for Nuclear Auxiliary Power) was developed and used by NASA in the 1960's and during the Apollo missions to power the instruments left on the Moon surface by the astronauts. Thermoelectric generators were also embarked on board of deep space probes such as for the Pioneer 10 and 11 missions, the Voyager program, the Cassini–Huygens mission, and New Horizons. They also deliver electrical and thermal power to the Mars Science Laboratory (Curiosity rover) and Mars 2020 mission (Perseverance rover) both exploring the cold surface of Mars. Curiosity and Perseverance rovers are both equipped with the last version of multi-mission RTG, a more efficient and standardized system dubbed MMRTG.

These applications are economically practical where photovoltaic power sources are weak or inconsistent due to probes being too far from the sun or rovers facing climate events that may obstruct sunlight for long periods (like Martian dust storms). Space probes and rovers also make use of the heat output of the generator to keep their instruments and internals warm.

Shortage of stockpiles
The long half-life (T$25 μs$ ~ 88 years) of 238Plutonium and the absence of γ-radiation that could interfere with the operation of on-board electronic components, or irradiate people, makes it the radionuclide of choice for electric thermogenerators.

237Neptunium is therefore a key radionuclide for the production of 238Plutonium, which is essential for deep space probes requiring a reliable and long-lasting source of energy without maintenance.

Stockpiles of 238Plutonium built up in the United States since the Manhattan Project, thanks to the Hanford nuclear complex (operating in Washington State from 1943 to 1977) and the development of atomic weapons, are now almost exhausted. The extraction and purification of sufficient new quantities of 237Neptunium from irradiated nuclear fuels is therefore necessary for the resumption of 238Plutonium production in order to replenish the stocks needed for space exploration by robotic probes.

Neptunium-239
Neptunium-239 has 146 neutrons and a half-life of 2.356 days. It is produced via β− decay of the short-lived uranium-239, and undergoes another β− decay to plutonium-239. This is the primary route for making plutonium, as 239U can be made by neutron capture in uranium-238.

Uranium-237 and neptunium-239 are regarded as the leading hazardous radioisotopes in the first hour-to-week period following nuclear fallout from a nuclear detonation, with 239Np dominating "the spectrum for several days."