U

Uranium The specific gravity of U is 18.95 g/cm3, which makes it the

Vincent J. M. Salters
National High Magnetic Field Laboratory and Department of
Earth, Ocean and Atmospheric Sciences, Florida State
University, Tallahassee, FL, USA
fourth in line with respect to density after Pt, Au, and
W. Uranium is a white silvery metal which is pyrophoric
when finely divided. It is malleable, ductile, and slightly
paramagnetic. Its metal has three forms a (ortZorombιw), b
(tetragonal), and g (cubic) with transition temperatures of
961 K and 1,049 K.

History and Use

Element Data
Atomic symbol: U
Uranium was first recognized as an unknown element by
Atomic number: 92
Klaproth in 1789, and the metal was first isolated by Peligot
Atomic weight: 238.029
in 1841. Uranium is used for inertial guidance devices, gyro-
Isotopes and abundances: 238U, 99.2745%, 235U
compasses, and ballast for missile reentry vehicles. Depleted
0.7255%, 234U, 223U
uranium (depleted in 235U) is used for shielding for tanks as
1 atm melting point: 1,132  C
well as armor-piercing bullets. Its metal is also used for X-ray
1 atm boiling point: 4,131  C
target to produce high-energy X-rays. Enriched uranium has
Common valences: 4+, 6+
higher than natural abundance of 235U and is used as fuel for
Ionic radii tetravalent U: sixfold, 108 pm; fourfold,
nuclear reactors.
112 pm
Pauling electronegativity: 1.38
First ionization energy: 597.6 kJ/mol
Chemistry
Chondritic (CI) abundance: 8.1 ppb
Silicate Earth abundance: 20.3 ppb
Uranium is an actinide and can be di-, tri-, tetra-, penta-, and
Crustal abundance: 1.3 ppm
hexavalent. Its ground-state electronic configuration is [Rn]
Seawater abundance: 3.2 ppb
5f36d17s2. In nature, the two common valence states are
Core abundance: ~0
tetravalent under reducing and hexavalent under oxidizing
conditions as in the oceans. In its tetravalent state, it behaves
much like Th and is particle reactive and insoluble in water.
Properties Under oxidizing conditions, it is soluble in water resulting in
relatively high concentrations in surface and ocean waters. In
The element is named after the planet Uranus. Its symbol is U, solution, the dominant form of U is the uranyl ion, UO22+, but
its atomic number is 92, and its atomic weight is 238.0289. Its U is also complexed by F , OH , SO42 , NO3 , and carbox-
melting point is 1,408 K and its boiling point is 4,404 K and is ylates. In most minerals, it is tetravalent with an ionic radius
considered a refractory lithophile element, with a 50% nebu- 8.9 nm in sixfold coordination and 10 nm in eightfold
lar condensation temperature of 1,010 K (Lodders, 2003). coordination.

# Springer International Publishing AG 2016

W.M. White (ed.), Encyclopedia of Geochemistry,
DOI 10.1007/978-3-319-39193-9_280-1
2 Uranium
Concentrations of U in bulk samples are generally low, in
the ppm to ppb range, and are mostly measured by inductively
coupled plasma mass spectrometry (ICP-MS) or by isotope
dilution. Its first ionization potential is relatively high, 6.3 eV,
making it more difficult to analyze by flame photometry.
Before the era of ICP-MS, U concentrations were analyzed
by neutron activation or by XRF. 234U abundance (activity) is
also measured by alpha counting or by thermal ionization
mass spectrometry (Chen et al., 1992).
Isotopes and Applications
Natural occurring uranium isotopes are 238U (99.2745%),
235
U (0.720%), and 234U (0.0055%). The present-day
238 235
U/ U isotope abundance ratio is 137.88; at secular equi-
librium, the 238U/234U isotope abundance ratio is 18236. All
three natural occurring isotopes are unstable and have half-
lives of 245,250  490 years (234U), 0.70381  0.00096 G
years (235U), and 4.468  0.0048 G years (238U). The stable
daughter isotope in the 238U-series is 206Pb; during this decay
scheme, eight alpha particles are released. The 235U decay
series ends at 207Pb and seven alpha particles are released. At
the start of the solar system, the 238U/235U was 3.3. Any
significant variations in 206Pb/207Pb have to be produced
early in Earth’s history as for the last 2Ga 207Pb/204Pb has
changed little due to the now low abundance of 235U.
Except for at the Oklo nuclear reactor (Bros et al., 1993),
the present-day 235U/238U was long thought to be constant.
Natural fractionation of uranium isotopes was first exploited
by Stirling et al. (2007) and Weyer et al. (2008). Isotopic
compositions are reported as d238U, which is the relative
deviation, reported in per mil, of the 238U/235U of the sample
compared to that of a standard. For most analyses, samples are
spiked with 233U–236U for mass bias correction. The natural
variation in d238U is approximately 3 ‰. These natural var-
iations occur through low-temperature processes, and the
largest differences are between oxidizing and reducing envi-
ronments. Black shales are approximately 0.4 ‰ heavier than
seawater. These fractionations are thought to be related to
volume-dependent equilibrium fractionation where U in sea-
water is reduced and the 238U is preferentially concentrated in
the reduced U(IV) and concentrates in the sediment. During
microbial reduction, the heavy isotope is also concentrated in
the reduced fraction (Bopp et al., 2010). The magnitude and
direction of the fractionation is consistent with theoretical
prediction of the fractionations being related to differences
in nuclear volume (Schauble, 2007). Kinetic isotope fraction-
ations would predict enrichments in the light isotope in the
reduced phase, which is opposite to the observations. Except
for near the basalt-seawater interface, altered oceanic crust
also shows heavy isotope enrichment which is attributed to
the penetration of seawater to deeper levels, reduction of U
(VI), and addition of U to the crust (Andersen et al., 2015).
Absorption of U to Fe-Mn hydroxides also results in an
isotope fractionation whereby the absorbed fraction is lighter
(Weyer et al., 2008). The absorption, as observed with Mn
nodules, is not associated with a change in valence state
(Brennecka et al., 2011), and kinetic fractionation is expected
and consistent with the sense of the observed mass
fractionation.
Ores and Distribution in Rocks
Uranium is a trace element in all rocks and is mostly present in
tetravalent state. Due to its large ionic radius and high charge,
uranium is not easily incorporated in crystal structures of
common rock-forming minerals. Therefore, during melting,
uranium enters the melt very early, and mineral melt partition
coefficient is typically less than 10 3. U is a large ion
lithophile element as well as a high field strength element. It
enters the melt easily and during crystallization is concen-
trated in the residual melt and is incorporated in late-stage
crystallizing trace phases like zircon, apatite, xenotime, or
sphene. The tendency for U to substitute in zircon makes it
the premier geochronometer because, as well as being U-rich,
it typically contains little or no Ph initially, it is a common
accessory mineral in many rocks, and it extremely chemically
and mechanically stabile. Although there are significant
uncertainties, approximately 16% of the Earth’s U is seques-
tered in the continental crust, which comprises only 0.2% of
Earth’s mass.
Uranium concentrations in igneous rocks are low in most
mafic and ultramafic rocks, but have higher concentrations in
alkaline and silica-undersaturated magmas, but can be as high
as 50 ppm in carbonatites and up to 100 ppm in syenites.
Marine phosphorites are the highest in U concentration
(100 ppm) of sedimentary rocks. High silica granites can
have 10–20 ppm of U. In most other natural materials, the
concentration of uranium is low. For example, mid-ocean
ridge basalts have U concentrations generally below 1 ppm.
Concentrations of U in ultramafic rocks are very low, often
less than 10 ppb. It is, however, unclear where the U resides.
The sum of the uranium content of the individual mineral
phases is often less than the bulk rock content, indicating U is
probably residing along grain boundaries or in fluid
inclusions.
Uranium ores can be formed under a wide variety of
conditions with uraninite (UO2) or pitchblende as the main
mineral. Ores can be formed by concentration in late-stage
melts or in sedimentary rocks by being transported by fluids
and precipitated at a reaction front due to more reducing
conditions resulting in UO2 precipitation.
Uranium
Uranium together with Th and K are presently the three
elements responsible for almost all the radiogenic heat pro-
duction in the Earth, therefore knowing its concentration in
the mantle because the heat production in the mantle contrib-
utes to convection, plate motion, and magmatism. A novel
and expensive way to measure U concentration in the Earth is
with the placement of giant liquid scintillators-based detec-
tors deep in the crust to measure geoneutrinos (McDonough
and Šrámek, 2014), but this will ultimately provide a better
estimate of the U content of Earth.
High-Temperature Geochemistry
In subduction zones, U is mobilized by dehydration of the
slab and enriches the overlying mantle wedge with U. This
conclusion is supported by the low Th/U ratios and
230
Th/238U showing U excesses in island arc magmas
(Turner et al., 2003). Mass balance calculations and the var-
iations in U/Th ratios indicate that the addition of slab com-
ponents is a two-step process: first bulk addition of sediment
or sediment melt with unfractionated U/Th followed by a fluid
addition from the altered oceanic crust more enriched in
U than Th resulting in U excesses in the magmas (Turner
et al., 2003).
During melting, U concentrates in the melt phase together
with other highly incompatible elements. The Nb/U is con-
stant in mid-ocean ridge basalts over a wide range of concen-
trations indication that their behavior is very similar during
melting of a peridotite and subsequent crystallization at lower
pressures. Its behavior under these conditions is also very
similar to Th. One of the major shallow mantle minerals
able to fractionate U from Th is garnet in which DTh<DU.
The cycling of Th and U in the Earth through time is
constrained by the Pb isotope variations of the different
Earth reservoirs. An example is that Th/U of the upper mantle
is lower that what is expected based its Pb-isotopic composi-
tion measured in mid-ocean ridge basalts (Elliott et al., 1999).
It has been argued that a change in behavior of U is the cause
of this in that the early Earth had an anoxic atmosphere and
U behaved very much like Th. With the increase in oxygen of
the atmosphere, U behavior on the Earth’s surface changed,
and presently U is preferentially lost over Th from the slab,
while in the early Earth when the ocean was anoxic, U in the
altered subducted slab was tetravalent. Thus, on the early
Earth, there was no low Th/U flux in to the upper mantle,
like there is nowadays. The recent discovery of U isotope
fractionation, including on the ocean floor (Stirling et al.,
2007; Weyer et al., 2008), provides a tracer for U that has
been in an oxygenated environment and allows for testing the
U/Th cycle (Andersen et al., 2015). Present-day MORB are
heavy in d238U ( 0.268  0.005 ‰) versus ocean island
basalts ( 0.308  0.005 ‰) and island arcs (~ 0.4 ‰),
3
while altered oceanic crust d238U is 0.17 ‰ with
Th/U = 0.44. This is explained as preferential loss of light,
mostly sediment-derived U, to the island arc while at greater
depth heavier U from the altered oceanic crust which also has
low Th/U. Although there is much evidence for sediment and
oceanic crust recycling in OIB sources, it is argued these
sources are established before the oceans were oxygenated
and therefore do not have fractionated 235U/238U (Andersen
et al., 2015).
Low-Temperature Geochemistry
Under oxygenated conditions, U is hexavalent and is rela-
tively soluble in concentrations in freshwater and in the
oceans is relatively high. Seawater has over 3 ppb of
U which is high compared to elements with similar behavior
in magmatic systems. Groundwaters have high 234U as
b-decay of 238U results in recoil of the daughter product
234
Th in the groundwater which subsequently decays with a
24.1 day half-life through 234Pa to 234U. This results in an
excess of 234U. The exact amount of excess is dependent on
the nature of the aquifer, the degree of interaction between the
dissolved fraction and the aquifer matrix, as well as the
colloidal fraction (Porcelli and Swarzenski, 2003). 234U
excesses in the oceans are about 15% (Chen et al., 1986).
Rivers can have larger excesses, and the excess 234U in
groundwaters can be extreme with (234U/238U) up to
11 (Porcelli and Swarzenski, 2003). In groundwater, the
234
U excesses have been useful in tracing flow through sub-
surface conduits. In marine sediment, the 234U/238U is often
measured as a check on the age disequilibria involving
shorter-lived U-series radionuclides. 234U has the longest
half-life of the daughter isotopes in the U-series decay
scheme, and thus if the disequilibrium dates the time at
which it is separated from seawater, then the 234U should
still be present.
Biological Utilization and Toxicity
In the subsurface, a large variety of bacteria, dissimilatory
metal-reducing and sulfur-reducing bacteria, have the ability
to reduce hexavalent uranium. These uranium reducers seem
to have in common that they thrive in anaerobic conditions
where the redox potential is low enough for the reduction of U
(VI) to take place (Wall and Krumholz, 2006). The bacterial
reduction to U(IV) renders U immobile, and stimulating bac-
teria in the subsurface to immobilize U have been
experimented with (Anderson et al., 2003) and have shown
to be effective in bioremediation by containing
U contamination in the subsurface.
4 Uranium
Uranium is toxic at intake levels of 20–40 mg and can
result in kidney damage and failure. Radiological toxicity is
due to the U decay that produces alpha particles. Due to the
limited penetration depth of alpha particles ingestion or inha-
lation of uranium are the main hazards.
Summary
The geochemical behavior of uranium is strongly dependent
on its valence state: hexavalent U goes in solution, while
tetravalent is near insoluble. Presently U is in the hexavalent
state at the oxygen-rich Earth’s surface. But, before the
Earth’s surface was oxygenated, its behavior was markedly
different. U is the parent in the U-series that ultimately lead to
stable lead isotopes. This provides the opportunity for dating
processes over a large range of time scales. Because of its
large ionic radius, U is not easily accommodated in most
crystal lattices and is incompatible, concentrates in trace
phases like zircon, and enters a melt early and crystallizes
out late in a sequence.
Cross-References
▶ Atmospheric Chemical Evolution
▶ Atomic Number, Mass Number and Isotopes
▶ Earth’s Continental Crust
▶ Geochronology and Radiogenic Isotopes
▶ Geoneutrinos
▶ Heat Producing Elements
▶ Incompatible Elements
▶ Large Ion Lithophile Elements
▶ Lead Isotopes
▶ Oklo Nuclear Reactor
▶ Solubility
▶ Stable Isotopes
▶ Thorium
▶ Trace Elements
▶ Uranium Decay Series
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