In batch equilibration studies (Bondie
tti, 1974}, Ca-saturated humates
removed greater than 94% of the Pu(iV)
from pH 6.5 aqueous solutions |
(compositions not given).
It is unclear whecher the humates repres
ented
surface for precipitation of hydrol
yzed species or were Iinvelved in
‘
complexation of Pu.
However, in studies of Pu desorption
from humates and
reference clays, cttrate removed 10-302
of sorbed Pu from the clays but
less than 1% from the humic acids.
Ligands forming stronger complexes
with Pu (DTPA and EDTA) were required
to remove significant quantities (
to 30%) of the Pu from the humate complex
.
mp
Although humic and fulvic acids likely
account for most of the metal
immobilization attributed to the soil organic
matter, (e.g., Hodgson
1963; Stevenson & Ardakani, 1972), they have
the potential for Formation
of soluble complexes with metals, particu
larly in dilute solutions.
Smatlh
quantities of metal fulvates, thought to
be of lower molecular weight than
the humates, may be present in soil solutio
n.
A nondialyzable material
with infrared absorption spectra and element
al analyses similar to fulvie
acids
was

isolated

from a dilute salt

(0.01 M KBr)

extract of a mineral

soil by Geering and Hodgson (1969).
The material exhibited a concentration
equivalent to 2.5% of a dialyzable fractio
n but was more effective in
complexing Cu and 2n,
Nonhumic Substances With Potential For Metal
Complexation.
Lower molecular
weight biochemicals of recent origin have
been implicated in metal complexation and solubilization in soil.
These materials represent (1) components
of living cells of microorganisms and plant roots
and their exudates and :
(2) the entire Spectrum of degradation products
which ultimately serve as
the building units of the soil humic fraction
.
The quantity and composition of these materials will vary with soil,
vegetation, and environmental
conditions (Alexander, 1961, 1971).
Readily decomposable wastes disposed to
soil under conditions appropriate for microbta
l growth may, for example
result in immediate and marked increases in organic
materials identified
in

category (1) and longer term increases of materials
in category (2).

Conversely, toxic materials may have the opposite
effects.
The specific
compounds produced will be dependent upon the
properties of the waste and
soil environmental conditions after disposal (Routson
and Wildung, 1969).

Although the concentration of the transuranics
and other metals soluble in
the soil solution or in mild extractants is low,
often near minimum detect—able levels, the major portion of Cu and Zn have been
shown to be associared
with low molecular weight components. Most of the
titratable acidity of
this fraction has been attributed (Geering & Hodgson,
1969) to aliphatic
acids (< pH 7.0) and amino acids (> pH 7.0).
The production, distribution, and action of organic
acids in soil has been
reviewed by Stevenson (1967).
A wide range of organic acids are produced
by microorganisms known to be present in soil.
These include (1) simple
acids such as acetic, propionic, and butyric, produced
in largest quantities
by bacteria under anaerobic conditions, (2) carboxyli
c acids derived from
monosaccharides, such as gluconic, slucuronic, and
a-ketoglucenic acids
produced by both bacteria and fungi, (3) products of the
citric acid cycle
such as succinic, fumaric, malic, and citric acid,
which are common

142

metabolic excretory products of fungi, and (4) aromatic acids such as
p-hydroxybenzoic, vanillic, and syringic acids thought to be fungal
decomposition products of plant lignins.
A variety of organic acids have
also been reported in root exudates.
The other important group of compounds identified in significant quantities
in the soil solution by Geering and Hodgson (1969) which may be expected
to exhibit strong affinity for metals are the amino acids. The qualitative
and quantitative aspects of amino acida and other nitrogenous components
in soils have been reviewed by Bremmer (1967).
It was concluded that soil
acid hydrolysates do not differ greatly in amino acid composition but
quantitative differences may occur with differences in soil, climatic, and
cultural practices. A number of acidic and basic amino acids have been
reported in soil. However, it appears that the major portion of amino

acid-N that is present in hydrolysates is in (1) the neutral amino acids

glycine, alanine, serine, threonine, valine, leucine, isoleucine and
proline, (2) the acidic amino acids, aspartic acid and glutamic acid, and
(3) the basic amino acids, lysine and arginine. Most of the amino acids
detected in soil hydrolysates have also been shown to exist free in smail
quantities in scils with levels seldom exceeding 2 ywe/g.
In the soil
solution (Geering & Hodgson, 1969), neutral amino acids also appeared to
predominate,
Basic amino acids were not detected although two acidic
amino acids (aspartic and glutamic acids) were present.
Stevenson and Ardakani (1972) concluded that organic acids and amino
acids, while present only in small quantities in soil, were present in
sufficient quantities in water-soluble forms to play a significant role in
solubilization of mineral matter in soil.
Small quantities of a number of
other complexing agents, such as nucleotide phosphates, polyphenols,
phytic acid, porphyrins, and auxina, also exist in soil (pertinent references
have been summarized by Mortensen, 1963).
However, it is unclear at
present, whether these materials would be present in sufficient quantities
in the soil solution under most soil conditions to affect tranguranic
solubility over the long-term.
MICROBIAL TRANSFORMATION OF THE TRANSURANIC ELEMENTS IN SOIL
Potential Mechanisms of Transformation
From the results of limited atudies of soil chemistry, microbiology and
plant availability of transuranics in soils, and by inference from studies
ef complexation of other trace metals in soils (as discussed above) it may
be concluded that the soil microflora will play a significant role in
transformations governing the form, and ultimately, the long-term solubility
and behavior of transuranic elements in soil. There are four general
mechanisms whereby microorganisms may alter the form of trace metale in
soil (Alexander, 1961; Wood, 1974}. These include (1) indirect mechanisms
resulting from metal interactions with microbial metabolites, or changes
in pH and Eh, (2) direct transformations such as alkylation and alteration
of the valence state through microbial oxidation (use of the metal as an
energy source) or microbial reduction (use of the metal as an electron
acceptor in the absence of oxygen), (3) immobilization by incorporation

143

Select target paragraph3