Journal of Geochemical Exploration 88 (2006) 246 – 248

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Modeling humic acids transport in a bauxite profile:

Los Pijiguaos, Venezuela
T. Tosiani *, W. Meléndez, F. Vivas
Instituto de Ciencias de la Tierra. Universidad Central de Venezuela, Aptdo. 3895, Caracas 1010-A, Venezuela
Received 11 March 2005; accepted 19 August 2005
Available online 2 November 2005

Abstract

Los Pijiguaos bauxite deposit is located in Southern Venezuela, in a tropical rain forest environment. Among the various
impurities during the bauxite processing (Bayer process), organic matter compounds present in Bayer liquor can slow the rate of
alumina precipitation, and reduce product yield and quality. Soil samples were taken from a 37-m-deep core and the distribution of
organic carbon (OC) was investigated as well as its relationship with major oxides Al2O3, Fe2O3, SiO2 and with the mineral phases
gibbsite, hematite, kaolinite and quartz. Each sample was subjected to an adsorption process of humic acids by interaction with
solutions of known concentrations. Maximum adsorption capacity was also studied in each mineral separately, which allowed
calculation of the theoretical adsorption capacity of each soil sample. Even if concentrations of OC were higher in the first 5 m of
the profile (0.2–0.5%), samples exhibited a low adsorption capacity (0.02%), while at depth between 10 and 37 m, samples showed
lower OC concentrations (0.03–0.05%), and a larger OC adsorption capacity (0.08%). The model for the adsorption capacity only
works between 10 and 30 m of depth, since in the first 10 m the bauxitic profile seems to be saturated in OC, because the
concentration of OC is higher than the maximum predicted by adsorption experiments.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Humic acid; Bauxite; Laterite; Adsorption; Pijiguaos

1. Introduction Several studies have been conducted on the origin

Los Pijiguaos bauxite deposit, located at the north-
western end of the Guayana Shield in Venezuela, 500
km South of Caracas, is developed on a Precambrian
Rapakivi Granite Batholith, the Parguaza Granite. This
deposit is situated on a planation surface between 600
and 700 m a.s.l.; it is believed to have originated from
an erosional event that took place during Late Creta-
ceous–Early Tertiary times. The vegetation of this
zone is typical of high pluviosity tropical forests.
* Corresponding author. Tel.: +58 212 6051201; fax: +58 212
6051152.
E-mail address: tosiani@cantv.net (T. Tosiani).
0375-6742/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2005.08.049
and distribution of some elements and minerals in
weathered profiles of this deposit (Tosiani et al.,
1990; Lo Mónaco and Yánes, 1990). The Al2O3,
SiO2 and Fe2O3 species make up more than 95% of
the chemical composition, with gibbsite, kaolinite,
hematite and quartz as the dominant mineral phases.
Gibbsite is the most abundant mineral in the econom-
ic-grade bauxite horizon. Kaolinite is not present in
the bauxite zone, but in the lower saprolite zone,
kaolinite can be more than 5 wt.%. Hematite is com-
monly more abundant than goethite. In the bauxite
horizon, however, the goethite/hematite ratio is greater
than 1 (Meyer et al., 2002); but according to Soler and
Lasaga (2000), the hematite is the iron oxide predom-
 T. Tosiani et al. / Journal of Geochemical Exploration 88 (2006) 246–248
Fig. 1. Distribution of TiO2, Fe2O3, SiO2 and Al2O3 in soil samples
from weathered profiles of Los Pijiguaos bauxite deposit in the
Guayana Shield, Venezuela.
inant in bauxite horizon, and the bauxitization process
is still active. Transport of various elements through
the bauxitic profiles is attributed to the complex-form-
ing capacity of the organic matter (humic and fulvic
acids) in solution (Covelo et al., 2004; Tombácz et al.,
2004). Rain water interacts with the organic matter in
the topsoil, producing enriched solutions in humic and
fulvic acids that percolate and adsorb onto the miner-
als that are present. Among the various impurities
during the bauxite processing (Bayer process), organic
carbon (OC) is the most prominent one that affects the
rate of alumina precipitation, reducing product yield
and quality. In this work, we investigate the correla-
Fig. 2. Percentage of minerals present in each soil sample from weathered profiles of Los Pijiguaos bauxite deposit in the Guayana Shield,
Venezuela, estimated from concentrations of major elements.
247
tion between OC and mineral phases, and a series of
sorption experiments of humic acid were carried out
on soil samples collected from a 37-m-deep drill core,
in order to develop a quantitative model for the sorp-
tion and transport phenomena.
2. Material and method
Samples were taken from a 37-m-deep-drill core,
where along each meter the sample was mixed and an
aliquot was collected for a total of 37 samples. Solu-
tions of humic acid were prepared from a commer-
cially available humic acid sodium salt, technical
grade that was obtained from Aldrich Chemical (Mil-
waukee, WI, USA). All experiments were performed
at pH = 5 and ionic strength adjusted to 0.001 N NaCl.
Measurements of dissolved organic carbon (DOC)
were performed by UV spectroscopy in solutions
and total organic carbon (TOC) with a LECO element
analyzer in solid samples. Oxides concentration
(Fe2O3, Al2O3, SiO2 and TiO2) was measured by X-
ray fluorescence, and phase minerals were identified
by X-ray diffraction.
3. Results
Five hours were necessary to reach equilibrium be-
tween bauxite and the solution of humic acid. Fig. 1
shows the distribution for major elements expressed in
% oxides: the first 4–5 m are enriched with Fe2O3 (10–
18%) and Al2O3 (42–46%) making up the richest part
the deposit. The maximum adsorption capacity was
measured on quartz, kaolinite, gibbsite and hematite
minerals sampled in some sections of the same deposit
and, amounted to 0%, 0.099%, 0.125% and 0.191%
DW, respectively. The percentage of each mineral phase
in each sample was also calculated from the concentra-
tions of the major elements (Fig. 2). These results and
the fraction of each mineral ( F) allowed the calculation
248 T. Tosiani et al. / Journal of Geochemical Exploration 88 (2006) 246–248
Fig. 3. (A) Organic carbon distribution estimated from the adsorption
!
capacity of quartz, hematite, gibbsite, and kaolinite ( ); organic
carbon distribution resulting from adsorption experiments (E). (B)
Original organic carbon distribution as measured in samples previous
to the adsorption process (x); sum of the original organic carbon + or-
ganic carbon adsorbed in the experiments performed ( ).
! concentration that can be reached; the fact that in the
of the expected sorption capacity for OC (Eq. (1)).
Results are shown in Fig. 3A ( ).


! rest of small dry roots. We think that there is no other
%Cmax ¼ Fquartz  0 þ ðFkaolinite  0:099Þ

of OC.
þ Fgibbsite  0:125
þ ðFhematite  0:191Þ ð1Þ
The maximum adsorption capacity obtained experi-
mentally for each sample is presented in Fig. 3A (E);
in the first 10 m, it barely reaches 0.05%; more pre-
cisely, in the first meter, the adsorption capacity is the
lowest while this layer is the richest in hematite. Fig. 3B
shows the distribution of OC before (x) and after the
!
adsorption ( ). In the first meter of the profile, the
initial OC concentration (0.5%) is three times the aver-
age value and higher than the maximum adsorption
capacity found for pure hematite. At that depth there
may be a possible influence of roots that increment the
% OC value; but those high values coincide with the
highest Fe2O3 concentration (18%) (Fig. 1). In the first
10 m, experimental values are quite lower as compared
to theoretical (expected) values, even if there is a
considerable increment of the adsorbent phases (hema-
tite and gibbsite); these results and the lower adsorption
capacity measured in the first meter of the profile (rich
in organic carbon and hematite) suggest that these
mineral phases may be nearly saturated with organic
carbon.
4. Conclusions
In tropical rain forests, rain waters flow through
layers of decomposing leaves, getting enriched in
humic and fulvic acids that interact with minerals.
Even if in the first meters, hematite and gibbsite prevail
– mineral phases of highest adsorption capacity for OC
– the lowest adsorption values are obtained. As depth
increases, concentration of the adsorbent phases
decreases between 10 and 37 m, and a larger OC
adsorption capacity is observed. According to the sorp-
tion experiments, 0.19% OC should be the maximum
first 5 m the OC concentration is higher can be attrib-
uted to the contribution of non humic substances like
mineral phase that could contribute to a high adsorption
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