Journal of South American Earth Sciences 112 (2021) 103634

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Journal of South American Earth Sciences

journal homepage: www.elsevier.com/locate/jsames

Chemical and mineralogical changes in the textural fractions of

quartzite-derived tropical soils, along weathering, assessed by portable
X-ray fluorescence spectrometry and X-ray diffraction
Fernanda Magno Silva a, Sérgio Henrique Godinho Silva a, Salvador Francisco Acuña-Guzman a, b,
Elen Alvarenga Silva a, Bruno Teixeira Ribeiro a, Tatiele Fruett c, Alberto Vasconcellos Inda c,
Anita Fernanda dos Santos Teixeira a, Marcelo Mancini a, Luiz Roberto Guimarães Guilherme a,
Nilton Curi a, *
a
Federal University of Lavras, Soil Science Department, P.O. Box 3037, Zip Code 37200-000, Lavras, MG, Brazil
b
Department of Agricultural and Biosystems Engineering, University of Puerto Rico, Mayagüez Campus, P.O. Box 9000, Mayagüez, Puerto Rico, USA, 00681
c
Soil Science Department, Federal University of Rio Grande do Sul, Porto Alegre, Rio Grande do Sul, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: The variability of mineralogical and chemical characteristics of soils reflects their parent material, the different
Parent material weathering degrees and soil formation processes. Through the association of portable X-ray fluorescence (pXRF)
Soil mineralogy spectrometry and X-ray diffraction (XRD), this work aimed to evaluate the concentration of major and minor
Proximal sensors
elements and their relationship with the mineralogy of the sand, silt and clay fractions in a catena of soils derived
Weathering
from quartzite with different weathering degrees in Southern Minas Gerais State, Brazil. Five soil profiles were
described and sampled: Lithic Ustorthent, Typic Ustorthent, Typic Dystrustept, Xanthic Haplustox, and Typic
Ustifolist. Sand, silt and clay fractions were separated and analyzed with pXRF and XRD for characterization of
elemental contents and mineralogy, respectively. For all soils, Si content was higher in the sand fraction, cor­
responding to quartz, confirmed by XRD, a predominant mineral in quartzite and in the sand fraction of tropical
soils. Al content was always higher in the clay fraction, reflecting the presence of kaolinite, gibbsite and mica.
Quartz, mica and kaolinite were the dominant minerals in the silt fraction. Si in the sand fraction showed a strong
and negative correlation with K and Ca, while Al in the sand fraction showed high and positive correlations with
Ca and Fe. Fe, K, Ca and Al were released from the most weathered soils, while Si remained almost constant due
to its large presence in quartz. The pXRF in tandem with XRD provided in-depth clarifications on the chemical
and mineralogical differentiation of the sand, silt and clay fractions of soils along weathering.

1. Introduction organisms, parent material, relief, and time (Jenny, 1941; Buol et al.,
2003; Schaetzl and Anderson, 2005). Parent materials have a relevant
Variability among soils is the result of complex and ongoing influence on soil attributes. Early pedologists based their concepts
biogeochemical processes due to formation factors such as: climate, heavily on soil’s parent material. Nowadays – with a more holistic

Abbreviations: pXRF, portable X-ray fluorescence; XRD, X-ray diffraction; ADFE, Air-dried fine earth; NIST, National Institute of Standards and Technology; CEC,
cation exchange capacity; LU, Lithic Ustorthent; TU1, Typic Ustorthent; TD, Typic Dystrustept; XH, Xanthic Haplustox; TU2, Typic Ustifolist; SDD, silicon drift
detector; TFx, transfer factor; TFx/Ti, transfer factor from parent material into the soil; AFx, accumulation factor; PSx, elemental concentration in the corresponding
particle size fraction; EWPM, easily-weatherable primary minerals; HA, A horizon; HB, B horizon; HC, C horizon; HH, Histic horizon; Mc, mica; Kt, kaolinite; Qz,
quartz; Ru, rutile; Mn, magnetite; Gb, gibbsite; Hm, hematite.
* Corresponding author.
E-mail addresses: fernanda_magno@yahoo.com.br (F.M. Silva), sergio.silva@ufla.br (S.H.G. Silva), salvador.acuna@upr.edu, sacuna@posgrado.cidesi.edu.mx
(S.F. Acuña-Guzman), elenalvarenga@yahoo.com.br (E.A. Silva), brunoribeiro@ufla.br (B.T. Ribeiro), tatielefruett@yahoo.com.br (T. Fruett), alberto.inda@ufrgs.
br (A.V. Inda), teixeira.afs@hotmail.com (A.F.S. Teixeira), mrcl.mancini@gmail.com (M. Mancini), guilherm@ufla.br (L.R.G. Guilherme), niltcuri@ufla.br,
niltcuri@dcs.ufla.br (N. Curi).

https://doi.org/10.1016/j.jsames.2021.103634
Received 27 August 2021; Received in revised form 8 November 2021; Accepted 10 November 2021
Available online 19 November 2021
0895-9811/© 2021 Elsevier Ltd. All rights reserved.
F.M. Silva et al.
perspective – we still consider geologic factors rather important to
achieve a complete understating of physical, chemical and mineralog­
ical properties of soils (Resende et al., 2011, 2014; Schaetzl and
Anderson, 2005). For instance, Heckman and Rasmussen (2011)
demonstrated that lithology controls pedogenic processes and soil
physicochemical characteristics in a lithosequence of four parent ma­
terials in cool, semiarid forested ecosystems. Similarly, Acosta et al.
(2011) analyzed major and trace elements of 21 soils derived from
different parent materials and observed significant correlations between
soil elemental contents and the underlying rock types. The same can be
said about soils that formed under tropical conditions in Brazil. Araujo
et al. (2014) studied eight soils over different lithologies in Southern
Minas Gerais, Brazil, to learn about parent material influence on soil
mineralogy. They found that a quartzite-derived Inceptisol presented
acidic pH (4.6–4.9, H2O), low cation exchange capacity (CEC), and low
natural fertility. Soil SiO2 content (approx. 60%) was driven by parent
material SiO2 content (>90%). Bulk-rock K2O content of 1.85% indi­
cated mica presence in the quartzite. The authors found that these
properties were deeply related to mineralogy, which was kaolinitic with
little 2:1 clay minerals, mainly illite and hydroxy-Al-interlayered
vermiculite (Araujo et al., 2014).
Pursuing a more detailed approach in soil science, however, is not an
easy task. It implies the need for more samples and complex analyses,
which consequently increases cost and time. To overcome such con­
straints, new technologies have been adopted in tandem with the well-
known traditional methods. An example of this novel trend is the
portable X-ray fluorescence (pXRF) spectrometer. Recently, this prox­
imal sensor has proved to be a reliable, non-destructive, low-cost, and
environmentally friendly technology for soil characterization (Weindorf
et al., 2014; Weindorf and Chakraborty, 2016). Sharma et al. (2014),
recommended the use of pXRF for the fast and simple pH assessment of
soils, since pXRF analysis is non-destructive and preserves the samples.
Silva et al. (2020) proposed the use of pXRF to obtain the contents of Al,
Fe, Si, P and Ti instead of sulfuric acid digestion analyses, which are
expensive, time-consuming and generate a large amount of chemical
waste.
A variety of materials – relevant to earth sciences and the environ­
ment – have been analyzed using pXRF. As reported in recent years, this
equipment is able to identify and quantify chemical elements in soils,
living plants, and liquid samples (Shand and Wendler, 2014; Ribeiro
et al., 2017; Chakraborty et al., 2017; McGladdery et al., 2018; Pearson
et al., 2017, 2018; Ravansari and Lemke, 2018; Silva et al., 2018a,
2021). Likewise, pXRF is also capable of assessing information related to
soil mineralogy and parent material, as reported by Stockmann et al.
(2016) and Mancini et al. (2019a, 2019b) in Australia and Brazil,
respectively.
One of the standard ways to study soil mineralogy is via X-ray
diffraction (XRD). Soil mineralogy characterization has largely relied for
decades on different techniques of XRD analysis (Jackson, 1956; Brown
and Brindley, 1980; Whittig and Allardice, 1986; Moore and Reynolds,
1989). Pedologists have used this knowledge to better understand
pedogenesis processes, soil physicochemical properties, and soil overall
behavior. Although some studies have evaluated the capabilities of
coupling XRD and X-ray fluorescence for archaeometry research (Cuevas
and Gravie, 2011; Beck et al., 2014), little work has been done to
advance soil science utilizing both techniques concomitantly for a ho­
listic understanding of soil mineralogy and elemental content distribu­
tion in soil particle size fractions, especially evaluating soils derived
from the same parent material, but with different degrees of weathering.
This approach may provide insights on soil chemical development and
mineralogical changes over time.
Hence, the objective of this study was to use pXRF measurements and
XRD analyses to characterize the mineralogy and examine the pedoge­
netic processes of a catena of soils – sequence of soils from the top to the
base of a hillslope (Milne, 1935) – derived from quartzite with soils
presenting different degrees of weathering (from Entisols to Oxisols).
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Journal of South American Earth Sciences 112 (2021) 103634
XRD and pXRF were used in tandem to determine the elemental
composition and mineralogical characteristics of particle size fractions
of the studied soils, aiming to correlate mineralogical (XRD) and
chemical (pXRF) information with the pedological and environmental
processes that led to their formation. We hypothesized that the quanti­
fication of chemical elements via pXRF associated with soil mineralogy
identified by XRD will successfully offer reliable information about the
degree of soil weathering and, mainly, how chemical/mineralogical
properties change along weathering among the soil particle size frac­
tions, horizons and soil classes.
2. Material and methods
2.1. Site description
The study area is located at the Bocaina Mountain Range, in Southern
Minas Gerais, Brazil (Fig. 1). The dominant lithology is quartzite and the
geological formation belongs to the Andrelândia Megassequence of
Neoproterozoic age (Curi et al., 1990). This area has been used as native
pasture, although also containing scarce small trees. According to
Köppen, the climate is classified as humid subtropical with dry winter
and hot summer (Cwa). The annual average temperature is 20.4 ◦ C, and
the annual rainfall is 1460 mm. The wet season occurs from October to
April, mainly during spring and summer (Dantas et al., 2007; Alvares
et al., 2013). The altitude of this catena of soils ranges from 1040 to 960
m.
2.2. Soil sampling and particle size fractionation
Five soil profiles were described along this catena and classified
according to US Soil Taxonomy (Soil Survey Staff, 2014) as Lithic
Ustorthent, Typic Ustorthent, Typic Dystrustept, Xanthic Haplustox,
Typic Ustifolist. Although the latter soil did not derive directly from
quartzite, the sediments into which organic matter was deposited orig­
inated from rock fragments and sediments resultant from the weathering
of soils indeed derived from quartzite. Consequently, this soil profile at
the lowest landscape position was identified as relevant to be included in
the chosen catena for the holistic comprehension of pedogenic processes
in the region.
Soil samples were taken from each horizon of the soil profiles, taking
into consideration each horizon depth as follows: Lithic Ustorthent (A
horizon: 0–5 cm; C horizon: 5–15 cm); Typic Ustorthent (A horizon:
0–20 cm; C horizon: 20–40 cm); Typic Dystrustept (A horizon: 0–18 cm;
Bw horizon: 18–40 cm; C horizon: 77 cm+); Xanthic Haplustox (A ho­
rizon: 0–10 cm; Bo horizon: 20–80 cm; C horizon: 100 cm+); and Typic
Ustifolist (A horizon: 0–18 cm; H horizon: 23–80 cm).
The soil samples were air-dried and passed through a 2-mm (air-
dried fine earth – ADFE) sieve for soil particle size distribution analysis
by pipette method, and separation of sand, silt and clay fractions (Gee
and Bauder, 1986). Clay dispersion was performed with 50 g of sieved
and air-dried soil, using 100 mL 0.1 mol mol− 1 of sodium hydroxide. The
soil in solution was shaken on an orbital table for 3 h. After shaking, the
suspension was passed through a 53-μm sieve. The sand fraction was
retained, while the sieved material (silt + clay fractions) was separated
by sedimentation of the silt fraction according to Stokes’s law (Gee and
Bauder, 1986).
2.3. pXRF chemical analyses
Chemical elemental contents were determined for ADFE, sand, silt
and clay fractions of each horizon of the five soil profiles using pXRF
under laboratory conditions according to Weindorf and Chakraborty
(2016). Measurements were made in triplicate in Trace (dual soil) mode
with a dwell time of 60 s per scan. The ADFE and soil fractions of each
horizon were analyzed using a pXRF Bruker® (S1 Titan LE model)
containing a Rhodium (Rh) thin window X-ray tube; X-ray generator of
F.M. Silva et al. Journal of South American Earth Sciences 112 (2021) 103634

Fig. 1. Location of the selected catena of tropical soils derived from quartzite at the Bocaina Mountain Range, Minas Gerais, Brazil. Sampling sites for each soil are
referred as follows: LU = Lithic Ustorthent, TU1 = Typic Ustorthent, TD = Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist.

15–50 kV with 5–100 μA, maximum of 4 W output; and a silicon drift
detector (SDD) with typical resolution <145 eV. In order to evaluate
pXRF elemental determinations, two standard reference materials
certified by the National Institute of Standards and Technology (NIST
2710a and 2711a), and a check-sample (CS) from Bruker® were used to
obtain the recovery values (elemental content determined via
pXRF/certified elemental content) (Table 1) of the elements used in this
study: Al, Ca, Cu, Fe, K, Rb, Si, Sr, Ti, Y, Zn and Zr. Zero values indicate
that either the element was not detected by pXRF or the reference
material did not provide a value for the element. These elements were
detected by pXRF for most soil samples, allowing comparisons of their
content between both horizons and soil profiles.
2.4. XRD mineralogical characterization
Mineralogy was determined for sand, silt and clay fractions of each
horizon of the five soil profiles based on X-ray diffraction (XRD) ana­
lyses. Non-oriented soil fraction samples were analyzed on a Bruker D2

Table 1
Recovery values (elemental content determined via pXRF/certified elemental content, %) of the elements determined via portable X-ray fluorescence (pXRF) spec­
trometry for three certified reference materials.
Material Al Ca Cu Fe K Rb Si Sr Ti Y Zn Zr

CSa 84 0 93 92 88 0 91 0 0 0 0 0
2710a 76 45 82 77 61 94 68 86 78 0 92 112
2711a 112 43 71 64 47 97 62 102 81 0 83 0
a
Check sample.

3
F.M. Silva et al. Journal of South American Earth Sciences 112 (2021) 103634

PHASER diffractometer, equipped with a LYNXEYE™ fast linear module
and operated with Diffract Suite™ software. Analyses were performed
by using CuKα radiation (λ = 1.541838 Å), Ni filter, and X-ray generator
of 30 kV with 10 mA. The samples were irradiated from 4 to 50◦ 2θ at a
step size of 0.02◦ 2θ and step time of 0.5 s− 1. The referred software
generated the X-ray patterns, which were later interpreted with the aid
of tables reported by Brindley and Brown (1980). The weight of the
samples varied between the sand, silt and clay fractions. However, for
comparison purposes, the samples of each fraction were standardized for
the same weight.
2.5. Element transfer from parent material to soil and accumulation into
soil fractions
We calculated the transfer factor (TFx) of each compound or element
using Equations (1) and (2), based on the methodology presented by
Acosta et al. (2009, 2011). TFx was calculated as the concentration of an
element transferred from parent material into the soil (Eq. (1)). Equation
(2) considered a Ti transfer factor as an indicator of the degree of
weathering, while estimating the transfer factor from parent material
into the soil (TFx/Ti).
TFx = Cx /Yx (Eq. 1)

Fig. 2. Major elemental compositions in sand (green), silt (blue) and clay (red) fractions – using portable X-ray fluorescence (pXRF) spectrometry – of five soil
profiles derived from quartzite at the Bocaina Mountain Range, Minas Gerais, Brazil.

4
F.M. Silva et al.
where: Cx is the elemental concentration in bulk soil, and Yx is the
elemental concentration in parent material, meanwhile:
TFx / Ti = (Cx / CTi )/(Yx / YTi ) (Eq. 2)
where: CTi is the concentration of Ti in bulk soil, and YTi is the con­
centration of Ti in parent material.
Values of TFx/Ti > 1.0 indicate compound or elemental accumulation
in soils due to soil forming processes, while values of TFx/Ti<=1.0
suggest transfer of compound or element was not detectable, or that loss
of compound or element may have occurred due to pedogenic processes.
Although soils in this catena are very little influenced by anthropogenic
activities, elevated transfer factors (TFx > 2.0) could indicate differently.
The accumulation factor of a compound or element (AFx) in a par­
ticle size fraction with respect to the bulk soil horizon was calculated
using Equation (3) (Acosta et al., 2009, 2011).
AFx = PSx /Cx (Eq. 3)
Fig. 3. Trace elemental compositions in sand (green), silt (blue) and clay (red) fractions – using portable X-ray fluorescence (pXRF) spectrometry of five soil profiles
derived from quartzite at the Bocaina Mountain Range, Minas Gerais, Brazil.
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Journal of South American Earth Sciences 112 (2021) 103634
where: PSx is the elemental concentration in the corresponding particle
size fraction. Values of AFx>1.0 indicate greater compound or elemental
concentration in the soil fraction, while values of AFx<1.0 suggest
compound or element loss due to pedogenic processes.
2.6. Statistical analyses
Descriptive statistics (mean, standard deviation, maximum and
minimum values) of elemental concentrations were computed. The
concentrations of compounds and elements – in each soil fraction as
quantified by pXRF – were graphically portrayed in the form of histo­
grams and boxplots. Pearson correlation analyses were performed be­
tween the concentrations of compounds and elements, and depicted as
dot charts. Statistical analyses were compiled and executed with soft­
ware R (R Core Team, 2018). Graphic representations were generated
with the R package GGally (Schloerke et al., 2018) also in software R.
F.M. Silva et al. Journal of South American Earth Sciences 112 (2021) 103634

3. Results of Lithic Ustorthent increased with depth, while Y and Zr presented

similar concentration trends in more developed soils.
3.1. Analyses of the sand, silt and clay fractions via pXRF By analyzing all the data points of pXRF elemental contents in soil
fractions, it can be observed that most of Si is concentrated in the sand
According to pXRF-measured contents of major elements in gran­ and silt fractions (Fig. 4). Conversely, the highest contents of Ca, K, Al
ulometric fractions (Fig. 2), Si content was the highest in the sand and Fe were largely concentrated in the clay fraction. Si in the sand
fraction and the lowest in the clay fraction for every soil. As soil depth fraction showed a strong negative correlation with Al (r = -0.89), K (r =
increased, a proportional increase in total Si content for the Typic -0.87), Ca (r = -0.89), and Fe (r = -0.82). Similarly, Si showed a negative
Ustorthent was observed; conversely, total soil Si content decreased for correlation with Al in the silt fraction (r = -0.75). Positive correlations,
the Lithic Ustorthent and Typic Ustifolist as soil depth increased. in the sand fraction, were observed for Al with Ca (r = 0.94), and Fe (r =
The Al contents were the lowest in the sand fraction and the highest 0.9). Likewise, Al was positively correlated to K in the sand (r = 0.91)
in the clay fraction for every soil. This is associated to the presence of and silt (r = 0.76) fractions.
kaolinite, gibbsite and mica in the clay fraction, as confirmed by XRD
(later discussed in Fig. 6). Fe contents were always the highest in the clay
3.2. X-ray diffractometry of the sand, silt and clay fractions
fraction. Contents ranged from 3% in the sand and silt fractions of every
soil up to 8% in the A horizon of the Typic Ustorthent (Fig. 2). Low
Quartz is the predominant mineral in the sand fraction for every soil
contents of Fe and Al in the C horizons indicate little presence of these
(sharp diffraction peaks), followed by mica (smaller diffraction peaks) as
elements in the parent material.
observed by the XRD patterns in Fig. 5. The greatest diffraction peaks for
The K contents were the highest in the silt fraction of less developed
mica (Fig. 5), a potential source of K, were observed in the sand fraction
soil profiles (Lithic Ustorthent and Typic Ustorthent). Conversely, for
of the C horizon of the Lithic Ustorthent, and in the A horizon of the
more weathered soils (Typic Dystrustept and Xanthic Haplustox), K
Typic Ustorthent. For the latter, mica may have come as part of depos­
contents are the highest in the clay fraction. This same pattern was
ited material eroded from adjacent upper areas.
observed for Ca contents. The Ca and K concentrations increased with
In the silt fraction, the dominant minerals were quartz, mica and
depth for coarse fractions of the least developed soil (Lithic Ustorthent).
kaolinite (Fig. 6). The intensity of the peaks indicates more mica and
Measurements of trace elements in soil fractions also provided some
kaolinite are present in this fraction, as compared to diffraction peaks of
insight regarding the degree of weathering of each soil profile. For
these minerals in the sand fraction (Fig. 5).
instance, Cl presence was detected mainly in the clay fraction of every
The most intense peaks for mica were observed in the silt fractions of
soil (Fig. 3). Cu content was the highest in the clay fraction of Typic
the Lithic Ustorthent (A and C horizons), while the largest kaolinite ones
Ustorthent, Xanthic Haplustox, and Typic Ustifolist. Zn, Rb, and Sr
corresponded to the Typic Ustorthent (A and C horizons). These results
contents were the highest in the clay fractions. However, for the least
are in agreement with the mineralogical differences expected for these
developed soil (Lithic Ustorthent), the highest levels of Y and Zr were
two Entisols. Since the Typic Ustorthent is a relatively more developed
measured in the silt and sand fractions. Y content was the highest in the
soil, it was expected for it to present minerals of a more advanced
clay fraction of the Typic Ustorthent and Zr content in the sand fraction
weathering stage than those of the Lithic Ustorthent; viz. the Typic

Fig. 4. Pearson correlation matrix between pXRF elemental contents in soil fractions. The boxplots and histograms show the concentration of the element in each soil
fraction. The dot plots show the correlation between the elements in soil fractions.

6
F.M. Silva et al.
Fig. 5. X-ray diffractograms of the sand fraction of soils derived from quartzite
in Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1 = Typic Ustorthent, TD =
Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A
horizon, HB = B horizon, HC = C horizon, HH = Histic horizon, Mc = mica, Kt
= kaolinite, Qz = quartz.
Fig. 6. X-ray diffractograms of the silt fraction of soils derived from quartzite in
Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1 = Typic Ustorthent, TD =
Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A
horizon, HB = B horizon, HC = C horizon, HH = Histic horizon, Mc = mica, Kt
= kaolinite, Qz = quartz, Ru = rutile, Mn = magnetite.
Ustorthent had less mica and more kaolinite than the Lithic Ustorthent.
Likewise, more developed soils (Typic Dystrustept, Xanthic Haplustox)
showed less presence of kaolinite in the silt fraction since, due to long-
time weathering, these minerals have been reduced to clay size.
The dominant minerals identified in the clay fraction (Fig. 7) are
kaolinite (most dominant), mica and gibbsite (to a lesser extent). As
observed via pXRF elemental composition data, the K contents in the
clay fractions may be associated to K-bearing micas.
The low peaks of gibbsite, goethite and hematite were associated
7
Journal of South American Earth Sciences 112 (2021) 103634
Fig. 7. X-ray diffractograms of the clay fraction of soils derived from quartzite
in Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1 = Typic Ustorthent, TD =
Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A
horizon, HB = B horizon, HC = C horizon, HH = Histic horizon, Mc = mica, Kt
= kaolinite, Gb = gibbsite, Hm = hematite.
with low levels of Al and Fe in quartzite. Nevertheless, these elements
were mostly found in the clay fraction of studied soils (Fig. 2). The low
intensity peaks of 2:1 clay minerals in the Lithic Ustorthent relate to
parent material mineralogy and leaching of basic cations under acidic
conditions. Higher presence of gibbsite was detected in the relatively
more developed soils (Inceptisol and Oxisol).
3.3. Transfer and accumulation of major and trace elements
The transfer factor of Al, Fe, K, Ti, Ca, Cu, Rb, and Zr, corresponded
to the case in which TFx > 1, whereas transfer factors of Si, Sr, and Y
were TFx < 1 (Fig. 8). The rate of elements transferred from parent
material to soils was estimated by the Ti-normalized transfer factor. TFx/
Ti<=1.0 were computed for Si, Al, K, Cu, Sr and Y. Conversely, TFx/Ti >
1.0 were computed for Ca, Rb, Zr, and Fe (Fig. 9).
Results of accumulation factors of major elements in the soil frac­
tions are presented in Fig. 10. AFx>1 were found for Si in the sand
fraction, as well as Fe, Al and K in the clay fraction. Intermediary values
of AFx were observed for the major elements in the silt fraction.
Nevertheless, the histograms showed rather similar trends of the cor­
responding graphs for each element AFx in the sand fraction. Thus, silt
fractions are somewhat more related to the sand fraction elemental
compositions, regardless of presenting primary and secondary minerals
(Fig. 6).
Si consistently presented AFx<1 at every clay fraction analyzed.
These results are in accordance with the lack of quartz diffraction peaks
in the clay fraction (Fig. 7), i.e. colloidal quartz dissolves more easily.
Regarding the trace elements (Fig. 11), except for Zr, all of them were
accumulated in the clay fraction (AFx >1). Zr showed accumulations in
all soils and respective horizons in the silt fraction, except for the C
horizon of the Lithic Ustorthent. In sand fraction, only the C horizon of
the Lithic Ustorthent accumulated Zr. In general, most elements were
released from the sand fraction of all soil horizons (AFx<1), except for
the C horizon of Lithic Ustorthent, which accumulated Rb, Sr, Y, Zn, and
Zr.
In the silt fraction, Cu, in the relatively more weathered soils (Typic
Dystrustept and Xanthic Haplustox), and Rb, Sr, Y, Zn, and Zr in most
horizons of all soils presented AFx>1. Conversely, Cl was the only
F.M. Silva et al. Journal of South American Earth Sciences 112 (2021) 103634

Fig. 8. Transfer factors (TFx) of major and trace elements of soils derived from quartzite in Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1 = Typic Ustorthent, TD
= Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A horizon, HB = B horizon, HC = C horizon, HH = Histic horizon.

Fig. 9. Ti-normalized transfer factors (TFx/Ti) of major and trace elements of soils derived from quartzite in Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1 = Typic
Ustorthent, TD = Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A horizon, HB = B horizon, HC = C horizon, HH = Histic horizon.

element that was not accumulated in any soil horizon of the silt fraction,
showing greater accumulation in the clay fraction.
4. Discussion
4.1. pXRF analyses of granulometric fractions
The greater Si contents in the sand and silt fractions reported by
pXRF are mainly due to the presence of quartz and muscovite, besides
small amounts of kaolinite, mainly in the silt fraction (Fig. 2) (Cláudio
et al., 2007; Resende et al., 2014). According to Kämpf et al. (2012),
quartz is rather resistant to weathering processes due to null – or very
little – isomorphic substitution. Low concentrations of Si in the clay
fractions corresponded mainly to the presence of kaolinite, formed due
to long-term weathering of tropical soils (Melo et al., 1995).
Desilication corresponds to silica removal of easily-weatherable
primary minerals (EWPM); during this process, 1:1 clay minerals are
formed – depending on the ions’ availability in the soil solution – and Fe-
and Al-oxides precipitate (Kämpf et al., 2012). Thus, a relative accu­
mulation of Al content was observed for soil profiles exposed to
long-term weathering and leaching (i.e., Typic Dystrustept and Xanthic
Haplustox): as quartzite is mainly composed of quartz (SiO2) and Si is

8
F.M. Silva et al.
Fig. 10. Accumulation factors (AFx) of major elements in the particle size fractions of soils derived from quartzite in Minas Gerais, Brazil. LU = Lithic Ustorthent,
TU1 = Typic Ustorthent, TD = Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A horizon, HB = B horizon, HC = C horizon, HH =
Histic horizon.
leached by weathering, the relative Al percentage increases in the su­
perficial horizons for soils with developed B horizons (Fig. 2). This is
further illustrated by Al and Si correlations (Fig. 4). As expected, Al
contents in the clay fraction tended to decrease as depth increased. This
is an indicative of the soil mineralogy being driven by the parent ma­
terial, viz. the closer to quartzite, the greater the presence of EWPM.
The Fe in the soil accumulates as part of the weathering process of
EWPM and formation of secondary minerals. Fe ions are released and
rapidly precipitated under oxidizing conditions (Schaetzl and Anderson,
2005). These conditions are easily attained in well drained soils, which
explains higher Fe contents in the clay fraction (Fig. 2).
The increase with depth of Ca and K concentrations for coarse frac­
tions of the least developed soil (Lithic Ustorthent) is correlated to the
presence of primary micaceous minerals (Fig. 2). According to Melo
et al. (2000), total K content in the sand fraction decreases as the degree
of soil weathering increases.
The Cl can be easily leached out of the soil profile, since it is weakly
adsorbed by positively charged sites in soil particles (Borggaard, 1984).
Therefore, low concentrations were measured. Cu and Zn tend to
accumulate in fine soil fractions as these ions can replace Fe in oxide
structures at advanced degrees of weathering (Acosta et al., 2011; Melo
et al., 2001); whereas Sr and Rb ions can replace Ca and K in micas,
respectively (Capo et al., 1998).
More developed soils presented similar concentration trends for Y
and Zr. The highest contents were measured in the silt fraction. These
may relate to the diversity of minerals in this fraction: mica, kaolinite,
rutile, quartz and magnetite (Fig. 6). According to Marques et al. (2004),
Y may be present in soil within the structures of kaolinite, gibbsite,
hematite and goethite, while Zr occurs in zircon (ZrSiO4), a mineral
resistant to weathering.
pXRF data could detect indications of both natural impurities in
quartz and accessory minerals in quartzite. These impurities are caused
by a scarce isomorphic substitution and were mainly formed through the
9
Journal of South American Earth Sciences 112 (2021) 103634
decomposition/transformation of composite complexes and diffusing
from gas–liquid inclusions (Rakov, 2006). Mica [K(Si3Al)Al2O10(OH)2]
is less resistant to weathering than quartz and it releases Al and K as its
particle size becomes smaller (Goldich, 1938; Melo et al., 2016). Ca2+
and K+ ions are very mobile as they compete for adsorption sites; thus,
they both are eventually leached out of the soil profile as soil horizons
become more developed (Schaetzl and Anderson, 2005; Melo et al.,
2016). Fe- and Al-oxides tend to accumulate in the clay fraction at more
advanced weathering stages of the soils (Uehara, 1986).
Positive correlations found for Al with both Ca and Fe in the sand
fraction and for Al and K in the sand and silt fractions (Fig. 4) are
associated to the presence of EWPM. According to Jackson (1956), K
content within the lattice of K-bearing minerals, such as muscovite, can
range from 70 to 100 g kg− 1 of mineral.
These detailed investigations on soil profiles and properties have
been improved with the help of proximal sensors. Recently, not only
pXRF alone, but pXRF associated with other proximal sensors, such as
visible near infrared diffuse reflectance spectroscopy (Vis-NIR) has
provided new insights on studies on soil genesis. Mancini et al. (2021)
associated pXRF with Vis-NIR data to investigate a 4.5 m deep Oxisol
profile, reporting a variable elemental dynamics even in apparently
homogeneous soil horizons. In this same study, Vis-NIR spectra were
related to differential chemical and mineralogical properties of soil
particle size fractions, enhancing the differentiation of soil horizons.
Souza et al. (2021) combined pXRF and Vis-NIR data to propose a new
index based on differential elemental dynamics in between soil horizons
for identification of changes in soil properties along a soil profile.
Gozukara et al. (2021) combined pXRF and Vis-NIR data to identify soil
parent materials for different soil profiles in the USA based on differ­
ential elemental dynamics. These studies demonstrate that the combi­
nation of sensors may provide new insights and more detailed
information on soil genesis, although herein pXRF and XRD not only
clarified the chemical and mineralogical changes caused by weathering,
F.M. Silva et al.
Fig. 11. Accumulation factors (AFx) of trace elements in the particle size fractions of soils derived from quartzite in Minas Gerais, Brazil. LU = Lithic Ustorthent, TU1
= Typic Ustorthent, TD = Typic Dystrustept, XH = Xanthic Haplustox, TU2 = Typic Ustifolist, HA = A horizon, HB = B horizon, HC = C horizon, HH = His­
tic horizon.
but also specified the correlations between elemental contents and soil
mineralogy of the sand, silt and clay fractions.
4.2. Soil mineralogy via XRD
Discrete peaks of kaolinite were observed for the Typic Ustorthent;
this finding concurs with the results reported by Melo et al. (2000). The
authors reported the presence of kaolinite aggregates in the sand frac­
tion of tropical soils. The predominance of quartz over other minerals is
due to its predominant presence in the parent material (quartzite) and its
high resistance to weathering processes. This agrees with the high
pXRF-measured values of Si contents in the sand fraction of all profiles
(Fig. 2).
According to Cezar et al. (2012), silt fraction mineralogy shows
typical minerals of the sand fraction – simply reduced in grain size – and
typical minerals of the clay fraction already subjected to intense
weathering and leaching processes, but not yet colloidal particles
(nanoparticles). Moreover, Dias et al. (2003) reported clay fraction
mineralogy of sandy soils derived from quartzite with gibbsite, illite, and
colloidal quartz. Because of the parent material, it was expected to find
quartz in all the horizons of the studied soils; nevertheless, the diffrac­
tion peaks were less intense than those observed for the sand fraction
(Fig. 5). It can be inferred that silt-sized quartz grains are somewhat
worn out due to weathering processes, facilitated by their smaller size
and consequent higher specific surface area.
Kaolinite is the result of partial loss of silica due to weathering and
leaching processes (Kämpf et al., 2012). Moreover, kaolinite presents
small cation exchange capacity, which strongly depends on particle size
(broken edges). Greater particle sizes result in lower cation exchange
capacity, and clay-sized kaolinite minerals have some of the greatest
particle sizes among other clay minerals (Ma and Eggleton, 1999).
10
Journal of South American Earth Sciences 112 (2021) 103634
Micas are the third most extensive group of minerals, and most likely
to be found in younger and less weathered soils (Sparks, 1987). Mica
peaks reported in the diffractograms (Fig. 7) concurred to results pre­
sented by Silva et al. (2018b). They found less intense diffraction peaks
of mica in the clay fraction as compared to the diffractogram of the silt
fraction of an Inceptisol derived from phyllite, probably because, in the
clay fraction, this mineral is easily weathered and ,consequently, orig­
inating kaolinite and/or gibbsite.
Null presence of diffraction peaks of maghemite (Fig. 7) – secondary
Fe oxide formed by the oxidation of magnetite (Curi, 1983) – is parent
material driven, since low contents of magnetite are found in quartzite
(Poggere et al., 2018; Silva et al., 2010, 2019). Likewise, characteristic
diffraction peaks for quartz were not detected in clay fractions. This
could be attributed to colloidal quartz proclivity to dissolution when
particle size is smaller than 0.2 μm (Kämpf et al., 2016).
Continuous weathering and leaching of soils drove kaolinite and
gibbsite formation (Watanabe et al., 2006). The presence of gibbsite in
the relatively more developed soils (Inceptisol and Oxisol) (Fig. 7)
agrees with that premise. Conversely, the erosion of the former soils
existing in the surroundings of the Histosol profile and consequent
deposition of their particles at the lower landscape position, at the
surface of the Histosol profile, help understand such occurrence. The
intensities of the kaolinite + gibbsite diffraction peaks were consistent
with the degree of weathering of the soils. Melo et al. (2001) also re­
ported similar results for tropical soils.
Although the XRD analysis is widely used for the identification and
quantification of minerals, proximal sensors have provided data capable
of contributing to such investigations. Vis-NIR spectra at certain wave­
lengths have been able to determine soil minerals present in different
particle size fractions of tropical soils (Coblinski et al., 2021). Jones and
McBratney (2016) found that these two sensors are able to differentiate
F.M. Silva et al.
soil mineralogy in agreement with XRD results, especially with respect
to phyllosilicates, although difficulties were faced in distinguishing
feldspars and quartz since they do not have specific absorption charac­
teristics in the Vis-NIR spectral range of 350–2500 nm. This combination
of proximal sensors for soil mineralogy inferences is a very new and
promising approach (Mendes et al., 2021), although it needs further
evaluation for different soils. Conversely, XRD is more conventionally
used and will serve as a reference method for soil mineralogy determi­
nation, contributing to fine-tuning of pXRF-Vis-NIR-based methods for
soil mineralogy identification. Although not widely evaluated, the
combination of pXRF and Vis-NIR may correlate well with XRD of soil
particle size fractions, since Vis-NIR will allow scientists to identify
minerals based on some mineral-specific wavelengths (Demattê et al.,
2015), while pXRF will complement this information by providing the
chemical composition of the analyzed sample (Silva et al., 2021). Thus,
such combination of proximal sensors data may correlate well with XRD
results, which demands further studies.
4.3. Transfer and accumulation of elements in soil formation
Desilication of minerals causes the release of Si and basic cations,
while elements such as Al, Fe, Ti, Cu and Zr accumulate residually in the
soil during the formation of secondary clay minerals (Acosta et al.,
2009) and pedogenic oxides. The discrepancy between the factor values
may be indicative of the mineralogy of the parent material and/or even
anthropogenic activity; viz. Fe, Ti, Cu, Rb and Sr contents in quartzite are
very low, therefore any slight input results in an increased transfer
factor.
The TFx/Ti ≤1.0 computed values for Si, Al, K, Cu, Sr and Y (Fig. 8)
corresponded to loss of the element due to pedogenic processes, which
agrees well to the expected evolution of tropical soils. Conversely, the
TFx/Ti >1.0 values calculated for Ca, Rb, Zr and Fe (Fig. 9) show the
expected transfer of these elements in the soil, since the accumulation
and release of elements in the soil are widely dependent on parent
material, and mineral susceptibility to weathering. Quartzite miner­
alogy is largely dominated by quartz, a very resistant mineral in soil
coarse fractions.
The value of AFx>1 observed for Si in the sand fraction, as well as Fe,
Al and K in the clay fraction, agrees well to the persistence of quartz in
the coarse fraction and the accumulation of clay-sized minerals observed
in the X-ray diffractograms (Fig. 7). Regarding Fe, besides being part of
the structure of Fe-oxides, such as hematite and goethite, Fe accumu­
lation in the clay fraction has been associated to sesquioxide coatings on
the surfaces of clay minerals, significantly impacting the chemical
properties of tropical soils (Townsend and Reed, 1971; Uzoho et al.,
2019). Graphical representations of accumulation factors for Fe, Al and
K in the sand fraction represent well the degree of weathering of the
soils. These three histogram graphs seem the best representation of soil
weathering/leaching processes in this catena of soils derived from
quartzite (Fig. 10). These results concur to those presented by Acosta
et al. (2011). They found values of AFx<1 for Al, Ca, K and Fe in the sand
fraction of soils derived from quartzite.
The accumulation of Rb, Sr, Y, Zn, and Zr in the C horizon of Lithic
Ustorthent (Fig. 11) may be caused by the low weathering degree of this
soil, not yet enough for the release of these elements (Resende et al.,
2014). As well as in this study, Silva et al. (2018b) also reported Cl
accumulation in the clay fraction in all horizons of an Inceptisol profile
developed from phyllite in Brazilian Cerrado region.
Acosta et al. (2011) obtained data to calculate the discussed accu­
mulation and transfer indices via the chemical digestion of samples.
Here, the calculation of the same indices was possible using pXRF data
instead, avoiding destructive and time-consuming chemical analysis and
at lower cost. Such alternative methods of investigation contribute for
in-depth understanding of how major and trace elements behave in
different particle size fractions along with weathering.
11
Journal of South American Earth Sciences 112 (2021) 103634
5. Conclusions
Data provided by the XRD unveiled the mineralogical composition of
soil particle size fractions. pXRF data allowed for detailed insights about
the behavior of each element across soil profiles without the use of
complex and expensive chemical analyses. Association of XRD and pXRF
data provided in-depth analyses of the changes of soil mineralogy and
chemistry caused by both degree of weathering and the particle size
fractions in different horizons of five soils members of a catena derived
from quartzite.
Based on pXRF elemental data, soil enrichment in Al, Fe, K, Ti, Ca,
Cu, Rb, and Zr (TFx > 1) compared with the parent rock was noted to
only refer to element/compound mobility, whereas accumulation fac­
tors better explained the degree of weathering of soils. Thus, accumu­
lation factors based on pXRF elemental data combined with the XRD
patterns shed light on the occurrence of weathering processes in the
different landscape positions of the catena of soils.
Finally, analyses of pXRF elemental contents and X-ray diffraction
patterns enabled detailed investigations and correlations between the
contents of chemical elements/compounds and minerals present in
granulometric fractions of the soil.
CRediT authorship contribution statement
Fernanda Magno Silva: Data curation, Formal analysis, Investiga­
tion, Methodology, Visualization, Writing - original draft, Writing - re­
view & editing. Sérgio Henrique Godinho Silva: Conceptualization,
Investigation, Methodology, Supervision, Visualization, Writing - re­
view & editing. Salvador Francisco Acuña-Guzman: Methodology,
Supervision, Visualization, Writing - review & editing. Elen Alvarenga
Silva: Data curation, Formal analysis, Investigation, Methodology,
Visualization, Writing - original draft, Writing - review & editing. Bruno
Teixeira Ribeiro: Data curation, Formal analysis, Investigation, Meth­
odology, Visualization, Writing - original draft, Writing - review &
editing. Tatiele Fruett: Data curation, Formal analysis, Methodology.
Alberto Vasconcellos Inda: Data curation, Formal analysis, Investiga­
tion, Methodology, Visualization, Writing - original draft, Writing - re­
view & editing. Anita Fernanda dos Santos Teixeira: Data curation,
Formal analysis, Investigation, Methodology, Writing - original draft,
Writing - review & editing. Marcelo Mancini: Data curation, Formal
analysis, Investigation, Methodology, Writing - original draft, Writing -
review & editing. Luiz Roberto Guimarães Guilherme: Data curation,
Formal analysis, Investigation, Methodology, Writing - review & editing.
Nilton Curi: Conceptualization, Data curation, Methodology, Project
administration, Supervision, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to acknowledge the Brazilian National
Council for Scientific and Technological Development (CNPq), Coordi­
nation for the Improvement of Higher Education Personnel (CAPES) and
Research Support Foundation of the State of Minas Gerais (FAPEMIG)
for the financial support of research funds and fellowships associated
with the research groups involved.
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