Th are still cationic, while in 8 M HNO; or in the strong carbonate solutions,
both cations would form negatively-charged complexes which do not readily
adsorb, The extraction conditions can change the Pu oxidation state present
and therefore, these results only support the plant uptake data which indicated
that Pu and Th are likely present in similar forms,

TABLE 5.

EXTRACTION OF U, Th, AND Pu FROM FLOODPLAIN SOIL
USING MILD EXTRACTANTS

U
Extractant

Th

Pu

While neptunium has not been studied extensively, pliant uptake (Price 1973)
and soil adsorption (Routson et al,, 1975) studfes have indicated higher
mobility relative to the rest of the actinides.
Bonditetti (1976) noted evidence
for reduction of Np(V) to Np(IV) in an acid soil. Thus, while Np may be very
available to plants if it remains oxidized (Np(V)), if Fe? or other reductants
are present, Np(IV) may be stabilized to some extent. Tetravalent Np would be
expected to behave like Pu(I¥) (low plant uptake) and attention should be paid
to instances where Np uptake is similar to Pu since this may indicate that
Np(IV) is being stabilized.

a*
SUMMARY

1 M HNO,

73

10% NaC0, - 5% NaHCO,

71

7.9
4s

7.7
54

*Z of & M HNO, extractable U (8.18 ug/g), Th (16.8 ug/g} and
Pu (144 dpm/g).

The question of which Pu oxidation states dominate in the environment has been
discussed, using thermodynamic approaches and environmental measurements to
illustrate the complexity of the problem, When thermochemical calculations
are considered, trivalent Pu appears to be a likely soluble state, particularly
under reducing conditions, Penta- and hexavalent states have also been calculated to be important. The oxidation states of Pu in White Oak Lake water
appear to be III or IV.
While Pu(II1) might be present (based on thermodynamic
considerations), the observed concentrations are consistent with the presence
of Pu(IV). Observed concentrations of soluble Pu in various natural waters do
not remotely approach current permissible limits.
Concentrations of soluble Pu exceeding predicted solubilities have been observed
in Pu0. dissolution studies.
This phenomenon appears related to complex
oxidation state changes as the result of radiolysis; however, the absolute
dissolution rate of Pu. is very small and some evidence is available to raise
the question of the relative importance of chemical solubility vs. physical
fragmentation as the important "dissolution" mechanism.
The relative availability of transuranium elements to plants appears related
to the oxidation state present in the soil.
From the limited data available,
the pentavalent oxidation state appears to be more available than the other
valences. Plutonium uptake by plants appears to be less than reported for Am,
Cm, or U.
In one case, the behavior of Pu and Th appeared similar.
This
would suggest that plant assimilation of these elements should follow the
valence order 5 > 6 = 3 > 4.
This order is the inverse of the relative tendency
of adsorption to soil.
The information presented exemplifies the complexities of evaluating Pu behavior
in natural solutions and identifies how further research should be structured
to answer important questions of environmental mobility and biogeochemistry of

471

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