Geoderma 154 (2010) 518–528

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Geoderma
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / g e o d e r m a

Soil mineral genesis and distribution in a saline lake landscape of the Pantanal
Wetland, Brazil
S.A.C. Furquim a,⁎, R.C. Graham b, L. Barbiero c, J.P. Queiroz Neto a, P. Vidal-Torrado d
a
Departamento de Geografia, Universidade de São Paulo, São Paulo, Brazil
b
Soil & Water Sciences Program, Department of Environmental Sciences, University of California, Riverside, USA
c
Laboratoire de Mécanisms et Transferts en Géologie, UMR 5563 CNRS-IRD-UPS-OMP, Toulouse, France
d
Departamento de Ciência do Solo, Universidade de São Paulo, Piracicaba, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The origin of the saline lakes in the Pantanal wetland has been classically attributed to processes occurring in
Received 20 August 2008 past periods. However, recent studies have suggested that saline water is currently forming from evaporative
Received in revised form 6 January 2009 concentration of fresh water, which is provided annually by seasonal floods. Major elements (Ca, Mg, K) and
Accepted 20 March 2009
alkalinity appear to be geochemically controlled during the concentration of waters and may be involved in
Available online 23 April 2009
the formation of carbonates and clay minerals around the saline lakes. The mineralogy of soils associated
with a representative saline lake was investigated using XRD, TEM-EDS, and ICP-MS in order to identify the
Keywords:
Nhecolândia
composition and genesis of the secondary minerals suspected to be involved in the control of major
Salinity elements. The results showed that Ca, Mg, and K effectively undergo oversaturation and precipitation as the
Mineral neoformation waters become more saline. These elements are incorporated in the authigenically formed carbonates,
Carbonates smectites, and micas surrounding the saline lake. The control of Ca occurs by precipitation of calcite and
Mg-smectite dolomite in nodules while Mg and K are mainly involved in the neoformation of Mg-smectites (stevensitic
Fe-mica and saponitic minerals) and, probably, iron-enriched micas (ferric–illite) in surface and subsurface horizons.
Therefore, our study confirms that the salinity of Pantanal, historically attributed to inheritance from former
regimes, has a contribution of current processes.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction The Nhecolândia sub-region (27,000 km2), located in the central-

The Pantanal wetland, located in the central area of South America
(16°–20°S and 58°–50°W), is the largest complex of continental
wetlands in the world, with an area of about 200,000 km2 (Por, 1995)
(Fig. 1A). Characterized by low altitudes (b200 m) and extremely low
gradients (0.02 to 0.03°), the wetland is a still active alluvial plain,
partially covered by seasonal flooding mainly in the summer
(November to March) (Silva, 1986; Scott, 1991). The Quaternary sedi-
ments underlying the plain are mainly sandy alluvial deposits of the
Paraguai River and tributaries. Most of the flooding water and the
deposited sediments are carried from surrounding highlands (200 to
900 m), which are formed by Precambrian crystalline and Mesozoic
sedimentary rocks (Del'Arco et al., 1982; Alvarenga et al., 1984; Godoi
Filho, 1986; Por, 1995). In spite of the recurrent presence of water, the
wetland presents an annual hydrological deficit of 300 mm, resulting
from a mean annual rainfall of 1100 mm and a mean annual
evapotranspiration around 1400 mm (Alvarenga et al., 1984; Por,
1995).
⁎ Corresponding author. Tel./fax: +55 11 30913794.
E-mail address: sfurquim@usp.br (S.A.C. Furquim).
southern portion of the Pantanal, is distinguished by the existence of
about 7000 fresh water lakes (“baías”) and 1500 alkaline–saline lakes
(“salinas”), generally associated with temporary channels (“vazantes”)
and sand hills (“cordilheiras”) (Fig. 1) (Cunha, 1943; Brum and Sousa,
1985; Mourão et al., 1988; Fernandes, 2007). The fresh water lakes are
temporary or permanent water bodies with different forms and
dimensions and up to 2 m deep. Coalescence of fresh water lakes during
the flooding periods forms the temporary channels, which are several
kilometers long and up to 30 m wide. The alkaline–saline lakes are round
depressions with permanent salty water, generally 500 to 1000 m in
diameter and 2 to 3 m in depth. They are located inside the sand hills,
which are narrow (200–300 m wide) and elongated stripes of dryland, 2
to 3 m higher than other landscape features and covered by savanna
vegetation.
Different hypotheses have been addressed to explain the origin of
these Nhecolândia landforms and the subject is still a matter of
debate. A set of explanations invokes eolian processes occurring in the
last arid phase (Late Pleistocene) as being the responsible for the
formation of sand hills and lakes. In this view, sand hills are seen as
paleo-longitudinal dunes (Klammer, 1982) and fresh water and/or
saline lakes are wind deflation depressions (Almeida and Lima, 1956;
Tricart, 1982; Soares et al., 2003; Assine and Soares, 2004). Saline lakes

0016-7061/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.geoderma.2009.03.014
 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528
were specifically defined by Tricart (1982) as old sebkhas, where the
eolian deflation was facilitated due to aggregation of fine particles by
salts accumulated on the soil surface. Another hypothesis attributes
the origin of sand hills and lakes to the shifting of river courses, which
occurred during and after the more humid climate prevailing during
deglaciation (Early Holocene). In this context, lakes would be inun-
dated depressions located inside cutoff meander banks or isolated by
embankments while sand hills would develop through transformation
of shortcut meanders banks into elongated sand ribbons. The distinc-
tion between fresh water and saline lakes would depend on the
recurrent input of fresh water from seasonal floodings (Wilhelmy,
1958; Ab'Saber, 1988). Eiten (1983) provided a different interpreta-
tion, attributing lake genesis to relict karstic or pseudo-karstic sys-
tems. Although these studies referred to different processes, they
all agree with a past origin of the saline lakes and other typical
Nhecolândia landforms.
However, recent geochemical studies involving surface and
subsurface waters of Nhecolândia suggested that saline water has
currently arisen from evaporative concentration of subsurface fresh
water (Barbiero et al., 2002, 2007). The water concentration seems to
be triggered by the presence of a subsurface impervious green horizon
surrounding the saline lakes, which prevents the groundwater
outflow through the sand hill during the dry season, thereby retaining
the water so it is concentrated by evaporation. The authors show that
fresh and saline waters belong to the same chemical family and
suggest that most of the chemical compositional changes in the
system are related to precipitation of some elements (mainly Ca, Mg,
K) as solutions become more saline. The chemical elements controlled
in this way are suspected to be involved in present-day authigenic
formation of carbonates (calcite or Mg-calcite) and silicates (steven-
site, sepiolite, Mg-montmorillonite, or amorphous) in the soils
surrounding the saline lakes. The identification of the minerals
supposed to be responsible for the control of chemical elements
Fig. 1. A — Location of Pantanal wetland and Nhecolândia sub-region; B — Aerial picture showing the main landscape features of Nhecolândia, the studied toposequence (T1), and the
water survey transect.
519
during water concentration should provide insight into the role of
current processes in the origin of salt waters in Nhecolândia.
A detailed mineralogical investigation of the soils surrounding a
representative alkaline–saline lake (Salina do Meio, Fig. 1B) was carried
out by our research team, the results of which are beginning to be
disseminated (e.g. Furquim et al., 2008). In spite of the extensive number
of saline lakes in the Nhecolândia, our studies represent a pioneering
effort in understanding the silt and clay mineralogy in these landscapes.
In this paper, we further elucidate the linkages between soil mineralogy,
geomorphology, and geochemistry of these lakes by providing a com-
prehensive view of the composition and genesis of the fine-grained
minerals in the Salina do Meio landscape.
2. Study area
Soils were sampled along a toposequence (T1) extending from
the border of the local sand hill to the surface level of Salina do Meio
(Figs. 1B and 2B). The surface water level of the saline lake varies
throughout the year according to the watertable dynamics (Fig. 2B):
from November to March, the level is high and the water is close to the
border of the sand hill; from April to October, the level goes down,
exposing most of the lake shore. Thus, the field work was done at the
peak of the dry season, when the soils were at maximum exposure.
The morphological and analytical properties of the soil cover along
T1 (Fig. 2B) are summarized below and more fully discussed by
Furquim et al. (2008). The soil consists of a pale brown (10YR 6/3),
single grain, sand surface material (horizon 1), which is laterally
replaced toward the lake by a dark gray (10YR 4/1), mostly prismatic,
loamy sand, surface material, rich in decomposed algae (horizon 2).
Beneath this, there is an organic-enriched, grayish brown (10YR 4/2),
massive horizon with a sand texture (horizon 3). This, in turn, overlies a
light brownish gray (2.5Y 6/2), single grain horizon, with a sand texture
and abundant vertical organic-rich volumes (horizon 4). The deepest
520 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528
Fig. 2. A — Location of piezometers (Pz) and watertable samplers (G) in the water survey transect (Barbiero et al., 2007); B — Soil horizons and pH values along toposequence 1 (T1).
horizons consist of a gray (2.5Y 5/1), massive, loamy sand material,
with common presence of millimeter- to centimeter-diameter
nodules (horizon 5), and a greenish (5Y 5/2), massive, sandy loam
material, which has rare to common presence of nodules and is
indurated by amorphous silica (horizon 6). The amounts of clay in
the soil range from 3 to 20% and are mainly concentrated in horizons
2 (8.5%) and 6 (10 to 18%). Soil pH varies from 5.4 to 11 along the
toposequence, but 70% of the measurements are higher than 10. Gray
and greenish horizons (5 and 6) are generally the most alkaline, with
pH values up to 11 (Fig. 2B). Electrical conductivity (EC) values
display a wide range (0.3 to 43 dS m− 1), but are higher toward the
saline lake. Na is the main cation on exchange sites in all horizons,
ranging from 3 to 190 cmolc/kg.
Preliminary soil morphology surveying in different places of
Nhecolândia showed that soil organization of T1 is representative of
the saline lakes. The sand surface horizon (1) and the subsurface gray
(5) and green (6) horizons were identified around all the surveyed
saline lakes (Sakamoto, 1997; Barbiero et al., 2000; Fernandes, 2000;
Silva and Sakamoto, 2003; Silva et al., 2004) while the dark surface
horizon (2) and the light sand subsurface horizon with vertical
organic volumes (4) were found in most of the studied saline lakes
(Sakamoto, 1997; Silva and Sakamoto, 2003; Silva et al., 2004). It is
important to highlight that the green and indurated horizon typically
associated with saline lakes is the feature pointed out by Barbiero et al.
(2007) as being responsible for the isolation of groundwater around
saline lakes during the dry season, allowing the evaporative
concentration of waters.
The geochemistry study of surface and subsurface waters of a
transect involving T1, the adjacent sand hill, and a neighboring fresh
water lake (Figs. 1B and 2A) was carried out by Barbiero et al. (2007).
The results showed that fresh waters (piezometers Pz5 to Pz15 and
samplers G7 to G15, Fig. 2A) were of Na–K–HCO3 + CO3 type, whereas
saline waters (Pz2, Pz3, G0 to G6, and lake, Fig. 2A) were of Na–HCO3 +
CO3 type. Similar to the regional water conditions measured by
Barbiero et al. (2002), the geochemical control of Ca, Mg, and K in the
more saline waters of the transect suggested the involvement of
these elements in the formation of minerals around Salina do Meio
(Fig. 3; A, B, and C). Equilibrium diagrams show that saline waters
of the transect are at equilibrium or slightly oversaturated with
respect to Mg-silicates (saponite, stevensite, and sepiolite) (Fig. 3; D
and E), attesting that those minerals could originate from these
waters. The chemical characteristics of water samples collected
specifically along T1 (Pz2, G0, and G1) are listed in Table 1. These
results include alkaline pH, high EC (mainly G0 and lake), high K
 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528 521

Fig. 3. A, B, and C— Concentration diagrams showing the evolution of Ca, Mg, and K during the concentration of waters in the transect involving Salina do Meio. Na amounts represent
the concentration factor. The solid line denotes the simulation of evaporation with precipitation of Mg-calcite and a Mg-silicate (sepiolite). D and E — Diagrams showing equilibrium
conditions in solution for different minerals (Barbiero et al., 2007).

content (mainly G0 and lake), and low contents of Al. Silica
concentrations are lower than 100 mg/L, but increase toward the
saline lake.
3. Mineralogical methods
Twenty whole soil samples and 17 nodules were collected along T1
from horizons of 5 pedons (P1 to P5) exposed by trenches (Fig. 2B).
Soil samples and nodules were crushed with a mortar and pestle
and passed through a 100-mesh sieve. These powdered materials
were randomly packed in an aluminum sample holder and submitted
to X-ray diffraction (XRD) for identification of carbonate minerals and
measurement of d060 values of phyllosilicates. Calcium carbonate
equivalent of the ground samples was determined by a manometric
method (Nelson, 1982) and total C was determined by dry combustion
(Nelson and Sommers, 2001). Organic C was calculated by the
difference between total C and inorganic C, the last derived from
calcium carbonate equivalent values.
Fine silt (2–20 μm), coarse clay (0.2–2 μm), and fine clay (b0.2 μm)
fractions of the 20 collected soil samples were separated by
centrifugation and sedimentation following destruction of organic
matter with NaOCl (pH 9.5) (Anderson, 1963). These fractionated
samples were used in the following analyses.
XRD was carried out for the 3 fractions of all the 20 samples. Silt
and clays underwent 5 treatments: Mg saturation (52% relative
humidity), ethylene glycol (EG) solvation of Mg-saturated clays, air
dry K saturation, and heating of the K-saturated samples at 350 °C and
550 °C (Jackson, 1979). Glass slides of oriented specimens were

Table 1
Characteristics of waters from Salina do Meio and surrounding watertable (cations with 2 repetitions).

Pz2 G1 G0 Salina do Meio

pH – 7.66 8.66 9.25 9.64
EC dS/m 6.19 8.76 19.18 12.74
Eh – − 25.2 − 217.0 − 364.5 − 125.0
Temp. °C 31.1 31.2 34.2 40.2
HCO3 + CO3 mEq/L 29.73 26.49 194.08 67.62
Cl− mmol/L 21.58 15.78 76.17 66.64
Si(OH)4 3.2098 3.5155 36.9463 38.6839 51.4686 52.3721 97.6426 89.5579
Al3+ 0.0007 0.0007 0.0196 0.0594 0.0039 0.0040 0.0514 0.0272
Mg2+ mg/L 1.0813 1.1843 0.0356 0.0372 0.2202 0.2241 2.2365 2.0513
Ca2+ 6.2313 6.8249 1.4463 1.4720 4.2313 4.3056 8.5382 7.8313
Fe 0.0826 0.4466 0.0319 0.0439 0.0120 0.0342 0.0553 0.0880
Na+ – – 982.2820 1028.479 5827.8413 5930.1401 – –
K+ 34.6911 37.9959 230.1342 240.9576 1094.8175 1114.0353 945.9906 867.66

EC: electrical conductivity; Temp.: temperature; Pz.: piezometer; G: watertable samplers.

522 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528
prepared by smearing a paste of clay or dropping a water–silt slurry on
the slide (Theisen and Harward, 1962). All the XRD analyses were
performed in a Siemens D-500 diffractometer (CuK radiation with
graphite crystal monochromator), employing a step size of a 0.02° 2θ
and a count time of 1.0 s per step. The XRD peak intensities from the
EG- and Mg-treated clays were used to calculate the semi-quantitative
amount (%) of each mineral in the assemblages (Biscaye, 1965), and to
estimate the relative content of iron in the mica structure, using the
formula I(001) / I(002), where I(001) and I(002) represent, respec-
tively, the intensity of the d001 and d002 mica peaks (Brown and
Brindley, 1980; Huggett et al., 2001). Results higher than 2 indicate a
relatively large Fe-content in the octahedral sheet (Brown and
Brindley, 1980; Deconinck et al., 1988).
Quantitative analyses of major elements (Si, Al, Fe, Mg, Ca, Na, K)
and rare earth elements-REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu, and Y) were carried out on the fine-clay fraction of 18
samples by inductively coupled plasma-mass spectrometry (ICP-MS),
using a Perkin-Elmer equipment, model Elan 6000.
The fine-clay fraction of 5 selected samples was analyzed using a FEI-
CM300 transmission electron microscope (TEM) linked with a Phoenix
energy-dispersive X-ray microanalyser (EDS). Six crystals of kaolinite
(P1—horizon 6, P5—horizon 6), 6 crystals of smectite (P1—horizon 6;
P4—horizon 2; P5—horizon 2), and 1 crystal of mica (P3—horizon 6)
were examined. For analysis, a dilute suspension containing the fine
clay was dropped on a standard Cu grid with carbon film. The
chemical composition of individual crystals was determined by EDS
for each sample. The collected data were used to calculate the
chemical formulas of the individual crystals.
4. Carbonates
The studied soil samples generally have very low contents of calcium
carbonate equivalent, with values ranging between 0.2 and 3.2%. The
greatest values (1.2 and 3.2%) occur in the surface horizon 2 of P4 and P5.
Consistent with this, XRD analysis revealed the presence of calcite
(CaCO3) in the fine silt of the surface horizons of P3, P4 and P5 (Fig. 4).
Most of the analyzed nodules have much higher calcium carbonate
equivalents than the whole soil samples. Values vary from 0.2 to 44%,
but 65% of the nodules have CaCO3eq amounts greater than 6%. XRD
Fig. 4. XDR patterns showing the presence of carbonates in fine silt samples (air dry K-saturated peaks) and nodules (b 100-mesh powder). Identified minerals: Q — quartz; M —
microcline; C — calcite; D — dolomite; N — nahcolite.
patterns of these carbonate-enriched nodules show 3 carbonate
minerals: calcite (CaCO3), dolomite (CaMg(CO3)2) and/or nahcolite
(NaHCO3) (Fig. 4).
Carbonate precipitation has been observed in soils that are fre-
quently subjected to evaporative concentration of solutions (Fehren-
bacher et al., 1963; Mahjoory, 1979; Kohut and Dudas, 1995). Alkaline
earth carbonates, such as calcite and dolomite, are generally the first
minerals to precipitate in the concentration process. Calcite generally
contains less than 5%mol of Mg(CO3) because it usually precipitates
from more diluted solutions, which typically have low Mg/Ca ratios
(b1). However, this ratio increases as calcite formation continues,
allowing the subsequent precipitation of Mg-carbonates such as mag-
nesite and dolomite (Eugster and Hardie, 1978; Boettinger and
Richardson, 2001).
As already stated, the concentration diagrams displayed in Fig. 3
(A and B) show a trend of decreasing concentration of Ca and Mg in
more saline waters of the transect involving Salina do Meio (Barbiero
et al., 2007), which is in agreement with the regional results obtained
by Barbiero et al. (2002). The geochemical control of these elements in
more saline waters suggests their involvement in the precipitation of
Ca- and Mg-carbonates in the soils associated with Salina do Meio,
inasmuch as the solubility limits of these minerals are the first to be
exceeded in the concentration process. The presence of calcite in the
surface horizons within the area of seasonal lake-level variation (P3
to P5) and the occurrence of calcite- and dolomite-enriched nodules
confirm the prediction made by water analyses and support the
neoformation of these carbonate minerals around the saline lake.
5. Clay minerals
X-ray diffraction patterns indicate an overwhelming dominance of
quartz and kaolinite in the coarse clay, and the presence of smectite,
mica, kaolinite, and quartz in the fine clay. The composition and
genesis of the 3 detected clay minerals are presented below.
5.1. Kaolinite
Kaolinite occurs in all the analyzed horizons of the toposequence
in both coarse and fine-clay fractions. Semi-quantitative calculations
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Fig. 5. Percentages of clay minerals in coarse and/or fine-clay assemblages along T1.

523
524 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528

estimate 3 to 77% of kaolinite in coarse clay assemblages, with no Maracaju”, where soils are acid, leached Psamments (Orioli et al.,
trend of vertical or lateral distribution along the toposequence (Fig. 5). 1982), ideal for kaolinite formation. Iron-rich kaolinites are very
Fine-clay assemblages contain 4 to 53% of kaolinite, with a general commonly formed in tropical soils (Herbillon, 1976; Newman and
decrease toward the saline lake (P5) (Fig. 5). Brown, 1987) and this may be the case in “Planalto de Maracaju”.
TEM/EDS results were used to calculate structural formulas of 6 Experiments of kaolinite dissolution under room temperature and
individual kaolinite crystals. One representative formula is listed in Table 2 pressure show very high concentrations of dissolved Si(OH)4 and Al in
(number 1). In all the analyzed specimens, tetrahedral sheet is formed by strongly acid (≤ 3) and strongly alkaline conditions (≥10) (Huertas
Si, with no Al substitution, and octahedral sheet is formed by Al and Fe3+. et al., 1999). Because most of the soil and water pH values are strongly
Aluminum ranges from 1.43 to 1.81 atoms per unit formula on the basis of alkaline in the Salina do Meio toposequence, kaolinite is probably
14 negative charges (apuf/14) and Fe3+ varies from 0.08 to 0.25 apuf/14, undergoing dissolution and releasing Si, Al, and Fe into solution. The
but the values are ≥0.13 in 5 of the 6 crystals. Iron substitution of pseudo-hexagonal crystals of kaolinite with subangular vertices and
octahedral Al in kaolinites is commonly less than 0.04 apuf/14 (Newman rough surfaces are probably evidences of this weathering process.
and Brown, 1987), which qualifies the studied specimens as iron-rich
kaolinites. The octahedral sum is slightly lower than 2.00 apuf/14 in all 5.2. Smectites
formulas probably because of the absence of Na in the results, which is
due to an interference of Cu from the Cu grid of the TEM samples holder Smectites in the Salina do Meio toposequence have been thor-
(Hover et al., 1999). TEM images show that the analyzed kaolinite crystals oughly studied by Furquim et al. (2008) and the most relevant aspects
are hexagonal or pseudo-hexagonal shaped, with angular or subangular are presented here. Based on semi-quantitative estimates for the fine-
vertices and smooth to rough surfaces (Fig. 6; A and B). clay fraction, substantial percentages of smectite are present in two
Some evidence suggests that kaolinite is allochthonous in the zones of the toposequence (Fig. 5): an upper zone, formed by all
study area. First, stability diagrams available in the literature showed horizons of P1 and P2; and a lower zone, formed by surface horizons 1
that kaolinites are stable under low values of pH–pK and pSi(OH)4 at and 2 of P3, P4, and P5. The results indicate the occurrence of different
room pressure and temperature, typical conditions of acid, well- smectite minerals and mechanisms of genesis in these zones.
drained, and leached soils (Tardy et al., 1973; Bohn et al., 1985; Velde,
1995). Soils associated with Salina do Meio are strongly alkaline, 5.2.1. Smectites from the upper zone
poorly drained, and have high base saturations, the opposite In this zone, XRD 00l patterns show a random interstratification of
conditions for the ideal formation of this mineral. Second, neoformed smectite with mica and vermiculite (Fig. 7) while 060 XRD peaks (0.149–
clays tend to concentrate in the fine-clay size and kaolinites of the 0.150 nm) indicate a dioctahedral domain in the fine-clay samples. Si, Al,
study area are abundant in both coarse and fine-clay fractions. and Fe3+ are the most abundant major elements of these samples, as
Therefore, the studied kaolinites were probably transported by the indicated by ICP-MS analysis, with amounts varying from 49 to 63% for
tributaries of the Paraguai River and deposited in the alluvial plain Si, 15 to 23% for Al (Fig. 8), and 5 to 10% for Fe3+. Results from TEM-EDS
along with the dominant sand particles. The source area of analysis of a single flake-shaped smectite crystal from P1—horizon 6
Nhecolândia sediments is a tropical highland known as “Planalto de (Table 2, number 2) agree with the ICP-MS analysis in that they yielded a
structural formula with high tetrahedral Al (0.8 apuf/22) and dominance
of Al (1.7 apuf/22) and Fe3+ (0.5 apuf/22) in the octahedral sheet. These
Table 2
characteristics qualify the analyzed specimen as a ferribeidellite (Güven,
Oxides and structural formulas of clay minerals and amorphous specimen.
1988; Reid-Soukup and Ulery, 2002). This crystal probably has some
1 2 3 4 5 6 hydroxyl-Al, -Fe in the interlayer position, raising the octahedral sum
Upper zonea Lower zonea above 2.00 apuf/22 (Weaver and Pollard, 1973).
P5-hor 6 P1-hor 6 P4-hor.2 P5-hor. 2 P3-hor.6 P3-hor. 6 The following characteristics suggest that these dioctahedral
SiO2 53.8 52.3 62.0 60.7 54.3 73.8 smectites originated from transformation of micas: 1) interstratifica-
Al2O3 39.7 35.0 7.0 10.7 27.7 10.2 tion with mica, as showed by 00l XRD patterns (Fig. 7); 2) high Al
Fe2O3 5.1 10.0 6.3 4.2 8.2 9.1
tetrahedral substitution in the structural formula (Table 2, number 2),
MgO 0.0 1.3 17.7 17.1 2.9 2.8
CaO 0.0 0.8 1.2 1.3 0.0 0.0 as expected for smectites transformed from micas (Borchardt, 1989);
MnO 0.0 0.0 0.0 0.0 0.0 0.9 3) dominance of iron-rich micas in the studied toposequence, as
K2O 1.5 0.6 1.6 0.9 4.8 4.1 discussed in the section on micas (Section 5.3); and 4) interstratifica-
Cl− 0.0 0.0 1.3 2.4 0.0 0.0 tion with vermiculite (Fig. 7), which is commonly an intermediate
Si4+ 2.04 3.18 3.96 3.87 3.43 –
phase in the transformation of mica toward smectite in soils
Al3+ 0.00 0.82 0.04 0.13 0.57 – (Crawford et al., 1983; Badraoui et al., 1987; Ransom et al., 1988).
∑Tetrahedral 2.04 4.00 4.00 4.00 4.00 –
5.2.2. Smectites from the lower zone
Al3+ 1.78 1.69 0.49 0.67 1.49 –
In this zone, all 060 XRD patterns display a strong peak of
Fe3+ 0.15 0.46 0.30 0.20 0.39 –
Mg2+ 0.00 0.04 1.69 1.63 0.12 – 0.152 nm, revealing a trioctahedral domain in the fine-clay samples.
∑Octahedral 1.93 2.19 2.48 2.50 2.00 – ICP-MS results show dominance of Si (44–51%) and Mg (13–15%)
among major elements (Fig. 8) and indicate much lower amounts
K+ 0.07 0.05 0.13 0.07 0.39 – of REE than samples from the upper zone (Fig. 9). Major element
Ca2+ 0.00 0.05 0.08 0.09 0.00 –
contents are corroborated by the calculated structural formulas of
Mg2+ 0.00 0.08 0.00 0.00 0.15 –
5 flake-shaped smectite crystals. Two of these formulas are listed
Anions O5 O10 O10 O10 O10 – in Table 2 (numbers 3 and 4) and a representative picture of one
OH− 4.00 2.00 1.86 1.74 2.00 – crystal is displayed in Fig. 6 (C). In all formulas, tetrahedral Al is low
Cl− 0.00 0.00 0.14 0.26 0.00 –
(0–0.14 apuf/22) and Mg is the main cation in the octahedral sheet
Tetrahedral charge 0.16 − 0.82 − 0.04 − 0.13 − 0.57 –
Octahedral charge − 0.24 0.51 − 0.25 − 0.12 − 0.12 – (1.49 to 2.30 apuf/22). Substitution of Al for Si in the tetrahedral
Total charge − 0.08 − 0.31 − 0.29 − 0.25 − 0.69 – sheet is zero or near zero in two crystals (e.g. Table 2, number 3) and
Interlayer charge 0.07 0.31 0.29 0.25 0.69 – between 0.12 and 0.14 apuf/22 in the other 3 crystals (e.g. Table 2,
Hor.: horizon. number 4). These are typical characteristics of the Mg-rich end-
a
Zones of smectite concentration. members stevensite, which has near-zero Al substitution, and
 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528 525

Fig. 6. TEM pictures of: A— Kaolinite crystal with angular vertices and smooth surfaces; B— Kaolinite crystals with subangular vertices and smooth to rough surfaces; C: Smectite
crystal with flake shape; D: Mica crystal with lath shape; E: Amorphous silica-rich phase with mineral crystallization.

saponite, which presents slightly higher Al substitution (Weaver and
Pollard, 1973). However, because of the presence of certain proper-
ties not found in stevensite and saponite, such as very low octahedral
sum and Cl substitution for OH, the studied specimens are designated
as stevensitic and saponitic minerals. The considerably lower
octahedral sum is mainly attributed to the presence of a dioctahedral
component in the crystals and, to a lesser degree, to the absence of Na
in the analysis due to an interference of Cu grids of TEM samples
holder (Hover et al., 1999).
Some lines of evidences show that stevensitic and saponitic
minerals originate by direct precipitation from the saline lake: 1)
minerals formed by chemical precipitation from waters have much
lower REE values than inherited or transformed minerals (Torrez Ruiz
et al., 1994; Jamoussi et al., 2003), and this is true of the Mg-smectites
of the studied area (Fig. 9); 2) the concentration diagram displayed in
Fig. 3(B) shows that Mg precipitates during the concentration process,
potentially as Mg-smectites; 3) equilibrium diagrams reveal that
saline waters of the transect at Salina do Meio are at equilibrium or
oversaturated with respect to Mg-silicates (saponite, stevensite, and
sepiolite) (Fig. 3; D and E), attesting that these minerals can
precipitate from the saline waters; and 4) horizons having Mg-
smectites occur only on the surface and exactly within the area of
seasonal lake-level variation (Fig. 5), indicating that these minerals
are directly associated with the lake dynamics.
5.3. Micas
XRD patterns from oriented clays show that mica is present in all
horizons analyzed for the toposequence. The higher percentages (67
to 84%) clearly occur in the gray (5) and green (6) horizons of the
pedons nearest to the saline lake (P3, P4, and P5) (Fig. 5).
526 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528
Fig. 7. Example of smectite peaks behavior under different treatments. Mixed-layer mica
smectite is identified in the upper zone (P1, horizons 1, 3, 5, and 6; P2, horizons 1, 5, and
6) by the partial coalescence of the d001 mica and smectite peaks in K (22 °C) and/or Mg
patterns and a clear separation of these peaks in the EG patterns. Mixed-layer
vermiculite–smectite is recognized in this zone by total or partial collapse of smectite
peaks to 10.0 Å in K-saturated samples (22 °C) (P1 and P2, horizons 1 and 6).
XRD 001 diffraction peaks suggest an interstratification of mica
with smectite layers in all samples. This interpretation is based on
very broad and asymmetrical mica peaks from Mg- and/or K-saturated
clays and a decrease of width and asymmetry of mica peaks
accompanied by a better definition of smectite peaks upon EG-
solvation of the Mg-clays (Fig. 10). Results of the I(001) / I(002) index
shows values higher than 2, suggesting that all fine-clay samples
contain Fe-rich micas.
TEM-EDS analysis of one lath-shaped mica crystal from P3—
horizon 6 (Fig. 6D; Table 2, number 5) confirms the trend pointed out
by the I(001) / I(002) index. The calculated structural formula of this
crystal defines Al (1.5 apuf/22) and Fe3+ (0.4 apuf/22) as the main
Fig. 8. Relationship between Si%–Al% and Si%–Mg% in the upper and lower zone samples.
Fig. 9. Sum of REEs in upper and lower zone samples.
cations of the octahedral sheet. This amount of octahedral Fe3+,
intermediate between illite and glauconite minerals, qualifies the
studied specimen as a ferric–illite (Fe-illite) (Porrenga, 1968; Baker,
1997; Hugget et al., 2001). Abundant crystallites associated with Si-
rich amorphous materials were also detected in the analyzed sample
(Fig. 6E; Table 2, number 6).
Although research about this mica is still underway, the following
water chemistry (Barbiero et al., 2007) and mineralogy data suggest
an authigenic formation: 1) geochemical control of K in the more
saline waters of the transect involving Salina do Meio (Fig. 3C) shows
that the involvement of this element in the precipitation of micas is
possible; 2) synthesis experiments under room conditions carried out
by Harder (1974) verified neoformation of mixed-layer illite–smectite
from waters that had similar chemical characteristics to those of the
study area, such as alkaline pH, Si(OH)4 concentration lower than
100 mg/L, and high K concentration; 3) the mechanism of neoforma-
tion observed by Harder (1974) involved initial precipitation of
amorphous hydroxides from solutions, followed by mineral crystal-
lization after aging. The presence of amorphous materials associated
with mica crystals in the sample investigated by TEM-EDS might be
evidence of the same mechanism of mica neoformation in the study
area. Further investigation will probably give more consistent
information about genesis of mica around Salina do Meio.
6. Conclusions
The current evaporative concentration of waters is promoting
precipitation of Ca, Mg, and K from the more saline solutions and their
consequent participation in authigenic mineral phases (carbonates,
smectites, and probably micas) around Salina do Meio. The
 S.A.C. Furquim et al. / Geoderma 154 (2010) 518–528
Fig. 10. Example of mica peaks behavior under different treatments: broad and
asymmetrical mica peaks on Mg- and/or K-saturated patterns, decrease of width and
asymmetry of mica peaks and better definition of smectite peaks on EG patterns.
involvement of Ca and part of the Mg in the precipitation of
carbonates is confirmed by nodules containing up to 44% of CaCO3eq,
consisting of calcite (CaCO3) and dolomite (CaMg(CO3)2). The major
control of Mg, however, occurs by precipitation of Mg-smectites
(stevensitic and saponitic minerals) within surface horizons (1 and 2)
of the area of seasonal lake-level variation (P3 to P5). Potassium
probably participates in the neoformation of Fe-micas in the deepest
horizons (5 and 6). The dissolution of kaolinites, which are
allochthonous in the study area, probably increases the supply of Si,
Al, and Fe of the solutions, contributing to the neoformation of the
other clays.
The identification of these mineralogical processes within the soils
surrounding the studied alkaline–saline lake corroborates the hypoth-
esis formulated by Barbiero et al. (2002, 2007) that chemical variation
between fresh and saline waters of Nhecolândia is related to mecha-
nisms triggered by present-day evaporative concentration of fresh
waters. Therefore, our study confirms that the salinity of Pantanal,
527
historically attributed to inheritance from former regimes, has a con-
tribution of current processes.
Acknowledgments
The authors wish to thank Capes for the doctoral fellowship to
S.A.C.F. and for the financial support to the research through a Capes-
Cofecub cooperation (412/03); Dr. Arnaldo Sakamoto, Dr. Rosely
Pacheco Dias Ferreira, Dr. Sônia Furian, Dr. Nádia Nascimento, MS Ary
Tavares, undergraduate and graduate students of the University of
Mato Grosso do Sul (UFMS), and employees of the Nhumirim Farm
for their assistance in the field; Paul Sternberg, Marcos Pinheiro, and
Luís Silva for general help with the laboratory work; and Dr.
Krassimir Bozhilov for TEM assistance.
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