Hydrolysis is an important property that needs to be considered, since the
state of hydrolysis of hydrolyzable ions is one of the controlling factors on
their adsorption and desorption. For example, Matijevié et al. (1961) studying
the Th adsorption of AgI sols found that the hydrolyzed species of Th are more
strongly adsorbed than the simple hydrated fon. According to the ion adsorption
model of James and Healy (1972), hydrolysis could bring about conditions
favorable to the adsorption of lower charged species that are formed ag it
progresses. This is explained by the fact that as hydrolysis proceeds, the
solvation energy term in their model changes in magnitude much more than the
coulombic energy term, The hydrolysis of microamounts of Am depends on its
concentration and on the chemical environment such as the kind and the concentration of the acid or base electrolyte (Korotkin, 1973b, 1974). At present, the
effect of an electrolyte Is attributed to the change of the activity of the
dons due to the change of their state of hydration. Samartseva (1969), using
the technique of sorption on Pt, determined the beginning of hydrolysis of

241am (10

1° 4) to be at pH = 2.0-2.5.

Shalinets and Stapanov (1972), by

electromigration technique, found the beginning to be in the similar pH range

for Am at 10 > M concentration.

Korotkin (1973a, 1973b, 1974), using distribu-

tion chromatography and electromigration techniques, determined it to be at

pH = 0.5-1.0 for 2"!Am concentration range of 10 '¥-10 § M.

Obviously, there

are some discrepancies, part of which may be due to experimental conditions.
In any case, it would be helpful to know the state of hydrolysis of Am ab a
function of pH in a complex system as a soil.

Along with hydrolysis, the degree of polymerization under various conditions
The beginning pH for the polymerization of Am in
needs to be considered also.
Some
a complex system such as a soil does not appear to have been defined.
An investiexperiments with simple aqueous solutions, however, have been done.

gation by Samartseva (1969) on the sorption and desorption of 241am from Pt

showed that up to pH = 4.0-4.5, the sorption procegs was reversible, indicating
that 2"lam was fonically dispersed, whereas at pH = 5, irreversibility of

Resident Am in a soil collected beneath a waste storage crib was leached by
groundwater and by 1 N NaNO3 to a considerably greater extent than the resident
Pu (Hajek, 1966).
In the chemical extraction of soil, collected in the Pucontaminated area at the Rocky Flats Plant and assumed to be contaminated by
Am and Pu in the dioxide form, the Am extraction coefficients were generally
higher than the values for Pu by one or two orders of magnitude (Cleveland and
Rees, 1976). Also, plant uptake studies have shown strong indication that Am
is more readily taken up by the plant than is Pu (Cline, 1968; Price, 1972;
Romey et at., 1975; Adams et al., 1975). The comparative environmental
behavior of Pu and other transuranium elements have been discussed in an

excellent review by Dahlman, Bondietti, and Eyman (1976).

Few experiments that relate to the desorption of *"/Am in soils have been

done. Hajek (1966) found that 7.5% of the resident Am in a soil collected
under a waste storage crib was leached by 1 N NaNOq. Knoll (1969) in a soil
column experiment found that the soil had little or no effect on removing the
Am from any of the tagged organic compounds applied, and certain untagged
organic compounds (di-(2-ethylhexy1} phosphoric acid and hydroxyacetic acid)
completely leached the 7"!Am from the tagged soil. Wallace (1972a) reported
that 100% of 2" am applied to a loam soil was extracted by DTPA, but not by
EDDHA (ethylenediamine di-ortho-hydroxyphenol acetic acid).
Apparently,
certain chelates are more stable to exchange in the soil than others. Cline
(1968) showed a soil type effect.
In soil columns leached with 100 inches
(254 cm) of irrigation water, in excess of 9B% of the Am was retained in the
top 1 cm of the acid sotl, whereas only 76% was retained in the top of the
alkaline soil.

MATERIALS AND METHODS

24am sorption, which is a characteristic of the colloidal state, occurred.

Sorption studies on Am in soils is still
Sorption and Desorption in Soils.
Routsen, Jansen, and Robinson (1975) determined the distribution
limited,
coefficients (K, values) of 24lam in subsoils of two different soils, one from
the arid western United States and the other from the humid southeastern
United States. The first soil, which was of neutral reaction and higher in
CaCO3 content and cation exchange capacity, showed considerably higher K
values (> 1,200) than the second soil, which was acidic and higher in clay
content.

Few comparisons of sorption with respect to other transurantum elements have

been made. Routsen, Jansen, and Robinson (1975) showed that 7*!am (III) was
adsorbed to soil stronger than 237Np (V). By inference from the quantitative

difference of behavior between Am and Pu, it appears that in general Am may be
less strongly sorbed to soils than Pu. For example, measurements of the
vertical distribution of ?“!am and 239*240p,, in NTS soil profiles have found
, that in some profiles, a decrease in the 2399240py/241am ratio with depth

occurred, indicating greater vertical movement of 2*1!Am relative to 239*?4°py
(Fowler and Essington, 1974; Gilbert et al., 1975; Essington et al., 1976).

80

The soil used for this study was Aiken clay loam (Ultisol) and its chemically
treated forms. The chemical properties of these soil materials are shown in
Table 1.
The influences of the various soil components on the extractability of 21am
were determined indirectly by chemically removing selected components and
determining the effect of their removal. Except for free alumina, silica, and
amorphous alumino-silicate, the procedures for the removal of the various
components have been reported previously (Nishita, 1976}.
In essence, treatment I was the CaClo treatment of the virgin soil, This treatment removed the
water-soluble salts and organic matter, reduced the amount of exchangeable Na,
K, and Mg, and retained Ca as the major (> 50% saturation of the cation
exchange complex) exchangeable cation. Treatments IE through V were done in
sequential manner. Treatment II was the digestion of the virgin soil with
dilute HCL. This treatment removed the HCl-soluble organic matter and salts
and carbonates, if present. Treatment IIT, which was the digestion of the
samples in 30% H202, brought about the decomposition of organic matter, the
dissolution of Mn oxides, and some residual carbonates, if present.
Treatment IV

81

Select target paragraph3