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https://doi.org/10.1590/2317-4889202120200092 Brazilian Journal of Geology DE
SDE 1946

Field availability and mobility of metals in Ferralsols

developed on ultramafic rock of Niquelândia, Brazil
Jeremie Garnier1,2* , Cecile Quantin2 , Sophie Raous3 , Edi Guimarães1 , Thierry Becquer4

Abstract
Ultramafic (UM) rocks are defined as igneous rocks that contain more than 90% of mafic minerals. Soils derived from ultramafic rock are gen-
erally nutrient-deficient and have concomitant high concentrations of potentially phytotoxic trace elements (Ni, Cr, Co, Mn). Consequently,
to assess the dynamics of nutrients and metals in the ultramafic complex of Niquelândia (Brazil), soil solutions have been sampled in soils
characterized by high Cr(VI) availability. The metal contents in surficial water have also been analyzed to investigate the metals’ leaching and
mobility. Soil solutions featured low nutrient contents, a large Ca:Mg imbalance, and high Ni and Cr concentrations. Chromium was present
in its toxic dissolved form (Cr(VI)) in the soil and surficial solutions. Metals concentrations were often above the toxic limit for biota and
were therefore able to affect soil functioning. Ni behavior in the topsoil appeared to be primarily controlled by organic matter, while Cr was
more likely to be released from Fe-oxides by anionic exchange. This result agreed with the Cr(VI) lability assessed using isotopic exchange
kinetics in a companion study. In these serpentinic tropical soils, the highly leached Fe-oxide horizons appear to play a large role in the se-
questration and diffuse leaching of labile Cr(VI) and Ni, respectively, in the deeper part of soil profiles and the topsoil. At the catchment scale,
surficial solutions results suggest that metals may be exported to surrounding ecosystems that are not adapted to these metals.
KEYWORDS: chromium; nickel; soil solution; runoff; serpentine syndrome; metal toxicity.

INTRODUCTION • low plant productivity;

Ecosystems developed on ultramafic (UM) rocks have • a high degree of endemism;
long been known as unique (1). Serpentinitic or ultramafic • vegetation types distinct from those of neighboring areas;
substrates are harsh environments for biota due to their low • the presence of certain “hyperaccumulators” of metals
levels of nutrients (N, P, and K), the imbalance between cal- (Ni) ( Jaffré et al. 1976, Proctor and Nagy 1992, Reeves
cium (Ca) and magnesium (Mg), and the presence of metals, et al. 2007, Kazakou et al. 2008, Anacker 2014, Bini et al.
such as nickel (Ni), chromium (Cr) and cobalt (Co) (Whittaker 2017, Kanellopoulos et al. 2015, Ratié et al. 2018, 2019).
1954, Brooks 1987, Kazakou et al. 2008, Pędziwiatr et al. 2018).
These chemical characteristics have contributed greatly to the These features are magnified in tropical areas where strong
consideration of certain ultramafic ecosystems as “hot spots” leaching conditions have led to the formation of deep later-
of biodiversity (Myers et al. 2000). Moreover, the chemical itic profiles.
characteristics of UM ecosystems explain the major ecolog- Tropical soils developed in ultramafic rock have been
ical traits of these environments, which are often called the widely studied due to their edaphic particularities and lateritic
serpentine syndrome: Ni mining. However, most of the research has focused on the
solid component, including subjects such as soil characteris-
tics, mineral compositions, metal solid speciation behavior, and
Supplementary data
more recently, Ni isotopic compositions (Quantin et al. 2002,
Supplementary data associated with this article can be found in the
online version: Supplementary Table and Figure.
Oze et al. 2004, Becquer et al. 2006, Fandeur et al. 2009, Dublet
et al. 2012, Ratié et al. 2015, Hseu et al. 2017). During the past
Instituto de Geociências, Instituto Central de Ciências, Campus
1
few decades, the availability of Ni and hexavalent Cr has been
Universitário Darcy Ribeiro, Universidade de Brasília – Brasília (DF), highlighted by laboratory investigations of tropical soils devel-
Brazil. E-mails: [email protected], [email protected]
oped in ultramafic rock from New Caledonia (Quantin et al.
2
French National Centre for Scientific Research, Université Paris Saclay –
Orsay, Cedex, France. E-mail: [email protected] 2002, Becquer et al. 2003, Becquer et al. 2006). Metal con-
3
Institut Régional du Développement Durable – Abbaye aux Dames, centrations in “ultramafic” soil solutions remain incompletely
Cedex, France. E-mail: [email protected] and poorly documented (Anderson et al. 1973, Johnston and
4
UMR Eco&Sols, Institut de Recherche pour le Développement – Proctor 1981, Gasser et al. 1994), particularly under tropical
Montpellier, Cedex, France. E-mail: [email protected] conditions. However, a recent investigation of soil solutions
*Corresponding author. from New Caledonia has shown significant concentrations
© 2021 The authors. This is an open access article distributed of metals in toxic forms, i.e. free-ion species (Becquer et al.
under the terms of the Creative Commons license. 2010). The concentration, speciation and availability of Cr

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 Braz. J. Geol. (2021), 51(1): e20200092

have been studied in soils of the Niquelândia ultramafic mas- ultramafic mineralized in nickel, sometimes chromium (e.g.,
sif in Brazil. The high availability of Cr in its most toxic form, New Caledonia, Brazil, the Philippines, and Indonesia), par-
i.e., hexavalent Cr (Cr(VI)), has been quantified using several ticularly under anthropogenic pressures, such as mining and
laboratory approaches, that is, chemical extractions, kinetics mineral extraction.
and XANES isotopic exchange (Garnier et al. 2006, Garnier A long-term investigation of the serpentine syndrome,
et al. 2009a, Garnier et al. 2013). metal availability and metal mobility associated with the soils
Metals, such as Co, Cr, Mn, and Ni, are known to be poten- and surface solutions of Niquelândia (Goiás State, Brazil) is
tially toxic in soils, even at low concentrations, and may lead required to complete our knowledge of metal behavior in nat-
to major limitations to root and leaf development and even ural soils developed in UM rocks, i.e., to understand whether
the death of non-adapted organisms. The phytotoxicity of and, if so, how metal mobility occurs. The aims of this study
such metals depends on their mobility, uptake, and biological based on field approach were, therefore, to assess to the metal
impact (Anderson et al. 1973, Sharma et al. 1995, L’Huillier availability in two soils developed in ultramafic rock known
and Edighoffer 1996, Samantary 2002, Becquer et al. 2010). to present large nickel and chromium contents. In addition,
Therefore, in addition to their concentrations, the phytotox- to address the possible mobility of metals and transfer to sur-
icity of metals in soil solutions is controlled by speciation, rounding areas, metal contents in surface waters were moni-
complexation with organic and/or inorganic components, tored during a complete hydrological cycle.
ionic strength, pH, and exposure duration. Moreover, the
uptake of metals by roots and microorganisms is complex
and depends on bio-physico-chemical interactions in the MATERIALS AND METHODS
solid-solution-biota continuum (Alexander 2000, Zayed
and Terry 2003). Site and materials
A large spatiotemporal variability in soil solution compo- The study area is located in the ultramafic complex of
sition is expected with regard to different edaphic conditions. Niquelândia, Goiás, Brazil (S14°18’-E48°23’). The regional
Thus, soil solution sampling under field conditions, with native climate is tropical humid; the region experiences an annual
biota and seasonal climate variations, is complementary to lab- average temperature of 20°C and receives rainfall amount-
oratory approaches that study potential metal availability, fate, ing to 1,500 mm. Two contrasting seasons are present: a
and toxicity. Field approaches and large datasets that describe wet and hot season occurs from November to April, and a
the spatial and temporal variations in soil solution composi- dry season occurs from May to October. The vegetation,
tion are essential and required to identify the main processes which is dominated by herbaceous plants and bushes, is sim-
that control the release and mobility of both nutrients and ilar to “Campo limpo” (Cerrado), a portion of the Brazilian
metals concentrations. Savanna dominated by grasses and herbaceous subshrubs.
Due to the relatively high metals concentrations of UM Several Ni-hyperaccumulating plants have been found in the
bedrock (Ni, Co, and Cr), weathering products can repre- ultramafic complex and have been described by Reeves et al.
sent an important source of metals for surface and ground- (2007), such as Justicia Lanstyakii., Heliotropium aff. salicoide.,
water. Nonetheless, in UM complexes, few authors have pre- and Cnidoscolus aff. urens.
viously reported natural transfers of trace elements (Weng Two Geric Ferralsols (NIQ II and NIQ III; WRB, 2006)
et al. 1994, Robles-Camacho and Armienta 2000, McClain located on the footslope of a toposequence representative of
and Maher 2016). In the Putah Creek watershed (California the Niquelândia massif and previously described by Garnier
Coast Range Mountains, USA), riverine Cr concentrations et al. (2006, 2009b) were selected for this study due to their
and speciation in ultramafic catchments are governed by the high Cr(VI) lability (Garnier et al. 2006, 2009b, 2013).
balance between ultramafic rock weathering and elemen- The studied soils (NIQ II and III) come from the massif
tal cycling along water flow paths, mainly by the availabil- consists of a hilly landscape controlled by a level of silcrust
ity of electron donors and acceptors (e.g. Fe(II), organics, (a hardened accumulation of silica) and containing eroded
Mn(III/IV)-oxides) (Mcclain and Maher 2016). In addi- backslope and footslope composed of debris stripped from the
tion, the exported dissolved Cr can occur as soluble hexava- entire landscape (Fig. 1). The weathering profiles are charac-
lent Cr(VI) species (CrO42-, MgCrO4), and as trivalent Cr terized by the presence of a relatively thick upper Fe-rich zone
species (Cr(OH)3, CrOH(CO3)22-) (Mcclain and Maher overlying a saprolite containing Mg-Ni clay silicates (“garn-
2016). Concentrations of Cr as high as 19 μg.L -1 have been ierite”) in contact with the ultramafic bedrock (Garnier et al.
reported in surface waters (Kruckeberg 1984, McClain and 2009b). The mineralogy of the soils is dominated by iron oxides
Maher 2016). However, the sources, fate, and fluxes of nat- (goethite and haematite); other accessory minerals are also
ural Cr(VI) remain poorly inventoried. Speciation is a key present, such as chromite and quartz (Garnier et al. 2009b).
parameter controlling both the mobility of metals, e.g., their These soils are particularly rich in Fe, with more than 400 g
potential transfer from a soil profile to water resources, and kg-1, and feature high concentrations of “trace” metals, such
the eco-toxicological consequences (Kalis et al. 2008, Brown as Ni and Cr (3,156–6,252 and 5,687–9,268 mg kg-1, respec-
Jr. and Calas 2011). Dispersion of geogenic contaminants (in tively) (Suppl. Tab.). The organic C content ranges between
this paper, metals) is a crucial environmental issue in ecosys- 20 and 22 g kg-1 in the surface horizons and decreases rapidly
tems developed in lateritic terrains, whose source rocks were with depth (Suppl. Tab.).

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 Braz. J. Geol. (2021), 51(1): e20200092

Figure 1. The map and sampling sites of the Niquelândia toposequence (S14.3034 - W48.3973; adapted from Cordeiro and Oliveira (2017)
and Garnier et al. (2009b), location of waters sampling.

Water sampling (Dionex) column and conductivity detection. The eluent

Soil solutions were collected from plots under natural was 3.5 mM Na2CO3 and 1.0 mM NaHCO3 under isocratic
vegetation developed on the Ferralsols NIQ II and NIQ conditions with a flow rate of 1.2 ml min-1. The third aliquot
III (Fig. 1). Ceramic cup samplers (No. 653X02B1 M3, was also stored at 4°C until analyses of anions and dissolved
Soilmoisture Equipment Corp., Goleta, CA, USA) were used. organic carbon (DOC) were performed. DOC concentrations
Studies that have tested the metal sorption in these ceramic were determined using a TOC-Vcsh Shimadzu analyzer, cali-
cups have shown that they are suitable for monitoring metal brated using potassium hydrogen phthalate (Fisher Scientific,
concentrations in soil solutions, with the exception of Cr(III) Analytical Reagent grade) with an accuracy of 0.01 mmol C L-1.
(Becquer et al. 2003, Becquer et al. 2010). After cleaning with Uncertainties were lower than 5%, and the detection limits cal-
1.10-3 M HCl and rinsing the ceramics with ultrapure water culated for ICP-AES, DPC, and ionic chromatography were
four times, the samplers were carefully inserted into the soil 0.001, 0.002, and 0.002 mmol L -1, respectively. A water internal
at depths of 20, 70, and 150 cm for NIQ II and 20 and 150 cm standard was used to check the validity and reproducibility of
for NIQ III. For each ceramic cup, a soil hole has been previ- each water analysis (less than 5% using the same instrument).
ously opened using a soil sampler. Six replicates were collected As it was not possible to measure it in the field, the alkalinity
at each depth. The soil solutions were sampled approximately of the samples was calculated as the difference between the
every 2 weeks between December 2006 and June 2007 (i.e., cation and anion concentrations.
during the rainy season until water was no longer extractable) R ainwater (collected twice on 01/29/2007 and
and again in February 2008. It was possible to collect soil solu- 03/14/2007) and water from the nearby stream draining the
tions at 20 cm depth until April 2007, and deeper samples studied catchment area were both analyzed. The stream water
could be collected until June 2007. Typically, 50 to more than was regularly collected at the spring and at its outlet at the ultra-
500 ml of solution was collected at each sampling location and mafic complex boundary 8 and 7 times in 2007, respectively
depth, depending on the seasonal period, but sometimes no (Fig. 1). These samples were analyzed using the same proce-
water could be extracted because the soil was dry. After pH dures as those applied to the soil solutions. Rain infiltration
measurement, the soil solutions were filtered using cellulose is highly efficient and rapid in both of the studied Ferralsols,
membranes (0.22 μm) and separated into three aliquots in the as observed by Reatto et al. (2007). Nevertheless, runoff has
field. The first aliquot was acidified with pure HNO3 for cat- occasionally been observed in the field during rainstorms.
ion analysis and stored at 4°C. Cations were measured using Thus, runoff solution samples (n = 3) were taken from tem-
ICP-AES (Varian Liberty 200 at UPS-GEOPS Laboratory). porary streams on the footslope uphill of NIQ II during three
As Cr(III) is known to sorb onto the ceramic cups, the Cr heavy rain events. The same methodologies have been used
measured in the soil solutions was expected to be hexava- to analyze the concentrations of cations, Cr(VI), anions, and
lent (Becquer et al. 2010). Nevertheless, a few hours after DOC of surface samples.
sampling, the Cr valence was verified in the second aliquot In both soil solutions and surface waters, chromium has
using the 1,5-diphenylcarbazide (DPC) method described by been found entirely in the hexavalent form due to the total
Bartlett and James (1996). Inorganic anions were analyzed concentrations (Cr tot = Cr(III)+Cr(VI)) determined via
in the second aliquot using an ionic chromatograph (Dionex ICP‑AES and Cr(VI) determined via DPC having been sta-
ICS1000 at UPS Laboratory) equipped with an IonPac AS14 tistically equivalent (p > 0.70).

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 Braz. J. Geol. (2021), 51(1): e20200092

Simplified Pourbaix diagrams were generated from the were performed under N2 pressure with acetate membranes and
average water compositions and physicochemical parame- polyethersulfone Millipore membranes, respectively, in a 47 mm
ters of the surface waters collected during the experiment. filter holder.
This was performed using the Act2 module of the Geochemist
Workbench (GWB) 14 software.
Since colloidal particles have been proven to play a key role RESULTS
in metal mobility in solutions of soils developed on ultramafic
rock (Gasser et al. 1994, Zelano et al. 2013, Bolaños-Benítez Soil solution
et al. 2018), a special investigation was conducted using all solu- The pH of the soil solutions was slightly acidic, ranging
tions sampled during the sampling of February 2008, includ- from 5.60 ± 0.15 to 6.10 ± 0.08, and increased slightly with
ing runoff waters. A size fractionation approach was performed depth in both soils (Tab. 1). At a depth of 20 cm, the pH was
on soil and surface solutions using the frontal cascade filtration low (pH 5.60–5.70) at the beginning of the rainy season (Dec.
technique (Patel-Sorrentino et al. 2007, Garnier et al. 2011). In 2006 – Jan. 2007) and subsequently increased. At deeper lev-
the field, solutions were successively filtered at nominal cut-offs els, the pH fluctuations were smaller, and the pH remained
of 0.22 μm, 0.025 μm, and 10 kDa, leading to the collection of close to pH 6.00 during the entire sampling period (Fig. 2).
four θ fractions (unfiltered, θ0; 0.22 > θ1 > 0.025 μm; 0.025 > θ2 Cations concentrations in soils solutions were always low,
> 10 kDa; 10 kDa > θ3). The first filtration was performed using ranging from 4.7 to 58.0 μmol L -1 (Tab. 1), with Silicon (Si) as
a syringe filter holder, and the 0.025 μm and 10 kDa filtrations the most abundant element, followed by cations Mg, Ca, and Na

Table 1. pH and Mg, Ca, Na, Si, Cr, Ni, and Mn mean concentration of the soils solutions from NIQ II and NIQ III and the surfaces water.
(All the water were filtered at 0.2 μm; d.l. detection limit; X ± Y mean ± SD., min / max value minimum and maximum observed). The K, Al,
and Fe content of all solutions filtered were always below detection limit (< d.l.).
Depth Mg Ca Na Si Cr Ni Mn NO3- SO42- Cl- DOC number of
pH
cm μmol l-1 samples
mg L -1
5.7 ± 28.1 ± 18.5 ± 4.7 ± 58 ± 0.9 ± 1.2 ± 89.2 ± 8.2 ± 31.2 ± 10.9 ±
< d.l.
0.15 14.6 10 4.3 8.1 0.6 0.8 58.1 5.6 25 0.3
20 40 / 10*
5.4 / 4.2 / 0.3 / 38.4 / d.l. / d.l. / 3.6 / 5.8 /
6.0 / 52 < d.l. 3.7 / 21
6.05 54.7 13.3 74.1 2.6 3.2 201 122
6.00 ± 9.8 ± 10.1 ± 6.1 ± 52.5 ± 1.7 ± 0.15 ± 18.2 ± 6.1 ± 19.4 ± 11.6 ±
< d.l.
Soil 0.05 4.0 4.8 4.0 12.5 0.8 0.2 17 3.1 35 2.0
70 56 / 15*
NIQ II 5.85 / 4.4 / 5.8 / 39.7 / 0.3 / d.l. / 6.8 /
0.8 / 17 < d.l. 2.3 / 78 2.3 / 78
6.05 29.4 23.5 75.4 3.9 1.5 204
6.00 ± 9.8 ± 9.7 ± 7.6 ± 39.6 ± 1.2 ± 0.15 ± 12.6 ± 4.0 ± 8.4 ± 10.7 ±
< d.l.
0.06 3.3 5.2 4.0 8.1 0.7 0.2 4.7 2.5 4.2 3.0
150 70 / 18*
5.9 / 2.8 / 5.8 / 0.8 / 26.5 / 0.3 / d.l. / 1.5 /
< d.l. 5.5 / 23 3.7 / 25  
6.15 19.1 23.5 16.8 67.4 3.9 0.7 9.1
5.85 ± 22.6 ± 20.1 ± 3.0 ± 56.4 ± 1.1 ± 0.5 ± 65.5 ± 17.7 ± 7.0 ± 7.4±
< d.l.
0.16 12.6 10.8 2.2 8.3 0.7 0.7 0.7 8.2 2.6 4.1
20 36 / 7*
5.6 / 5.6 / 4.6 / d.l. / 39.6 / 0.3 / d.l. / 2.0 2.8 /
< d.l. 2.5 / 44
Soil 6.1 47.1 41.6 7.5 71.5 2.9 2.6 /154 9.2
NIQ III 6.05 ± 7.2 ± 9.5 ± 5.3 ± 54.2 ± 1.0 ± 0.8 ± 16.3 ± 11.8 ± 4.2 ± 11.2 ±
< d.l.
0.08 2.5 6.2 2.9 7.8 0.5 0.7 7.9 8.2 2.3 2.2
150 68 / 18*
5.85 / 0.4 / 36.4 / 0.3 / d.l. / 1.7 /
3.6 / 18 1.5 / 49 < d.l. 8.5 / 33 5.0 / 31  
6.2 13.1 69.6 2.2 2.8 6.7
7.25 ± 254 ± 21 ± 6.2 ± 275 ± 0.5 ± 1.0 ± 0.3 ± 22.9 ± 1.3 ± 5.2 ± 10.5 ±
0.12 36.4 8.8 2.3 45 0.3 0.6 0.5 33.5 2.2 3.0 0.9
spring 8 / 3*
7.05 / 219 / 9.3 / 3.8 / 226 / 0.1 / 0.2 / d.l. / d.l. / d.l. / 3.2 /
7.4 324 34.1 9.2 364 0.9 1.7 1.1 61.3 3.8 8.6
8.00 ± 383 ± 21 ± 8.5 ± 308 ± 0.4 ± 0.7 ± 0.3 ± 6.7 ± 2.4 ± 4.4 ± 8.4 ±
Surface 0.05 39 8.8 5.7 66 0.6 0.3 0.3 7.0 0.8 1.6 3.5
outlet 7 / 3*
water 7.9 / 344 / 11.3 / 3.8 / 242 / 0.1 / 0.4 / d.l. / 1.8 / 2.7 /
2.5 / 15
8.2 442 38 16.6 446 1.7 1.1 0.9 3.2 5.8
2.3 ± 1.3 ± 12.3 ± 0.8 ± 0.2 ± 1.6 ± 9.9 ±
- - 3 / 3*
2.1 0.5 3.1 0.4 0.1 0.2 2.6
runoff
0.4 / 0.9 / 9.1 / 0.4 / 0.2 / 1.3 /
- -          
1.9 1.9 15.2 1.2 0.3 1.8
*Number of analyses of dissolved organic carbon.

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 Braz. J. Geol. (2021), 51(1): e20200092

Figure 2. Mean pH of the soil’s solutions from NIQ II-20, 70 and 150 and from NIQ III-20 and 150 (20, 70, and 15 refer of the sampling
depth in cm). 

Figure 3. Si, Ca, and Cr concentrations for all NIQ II-20, 70, and 150 ceramics cups (Si a, b and c; Ca d, e and f; Cr g, h and i), in μmol
L -1 from December 2006 to June 2007; (●soils solution of February 2008) (20, 70, and 15 refer of the sampling depth in cm).

(Tab. 1 and Fig. 3). In NIQ II, Si concentrations decreased with were slightly higher than those of Ca for both soils and ranged from
depth, whereas they were homogeneous in the NIQ III solutions 28.1 ± 14.6 to 22.6 ± 12.6 μmol L -1 in both NIQ II and NIQ III;
(Tab. 2). Calcium concentrations decreased with depth from 18.5 the values in both soils decreased considerably with depth (Tab.
± 10.0 to 9.7 ± 5.2 μmol L -1 in NIQ II and from 20.1 ± 10.8 to 9.5 1). The Ca:Mg ratios ranged from 0.65 to 0.88 at a 20 cm depth
± 6.2 μmol L -1 in NIQ III (Tab. 1). Mg concentrations at 20 cm and increased to 1 and 1.32 in the deeper parts of the profiles.

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 Braz. J. Geol. (2021), 51(1): e20200092

Table 2. Mean Ca:Mg ratios of leaching topsoil solutions (C.P. Ceramic Cup).
Mean 2006-2008
C.P.1 C.P.2 C.P.3 C.P.4 C.P.5 C.P.6
NIQ II-20
1.6 1.4 1 1.6 0.7 0.9
samplers
NIQ III-20
2 1.4 1.1 2.8 1.5 -
samplers
Date of sampling
12/19/06 01/17/07 01/31/07 02/15/07 02/24/07 03/15/07 03/30/07 04/18/07 05/10/07 02/25/08
NIQ II-20
0.6 1.1 0.9 1 1 1.5 0.9 2.3 0.3 2.7
mean
NIQ III-20
1.2 1.5 1.3 2.1 1.5 2.6 - 2.5 - -
mean

The variability of the Ca:Mg ratio at 20 cm depth was particu- waters, Si and Mg concentrations were dramatically higher than
larly high (Tab. 2). Finally, the concentrations of Na were very in the soil solutions and increased between the spring and the
low and variable, ranging between 3 and 7.6 μmol L -1, and the outlet, from 254 to 383 and 275 to 308 μmol L -1, respectively
concentrations of K were below the quantification limit (Tab. 1). (Tab. 1). Finally, the Ca and Na concentrations were equiva-
The dominant inorganic anions were NO3- and, to a lesser lent to those measured in the soil solutions.
extent, SO42- and Cl- (Tab. 2). In soil solutions, the concen- The stream solution was free of Fe and Al, but traces of Mn
tration of anions, particularly NO3-, decreased below 20 cm. were present (0.3 ± 0.5 μmol L -1) (Tab. 1). The Ni concentra-
The concentrations of other anions, such as H2PO4-, were tions at the spring and outlet were in the same range as the soil
always below the detection limit. The DOC concentration in concentrations (0.7–1 μmol L -1), whereas the concentrations
the soil solution was homogeneous in both soil profiles and of Cr, which occurred as Cr(VI), were lower, with values of
ranged between 7.4 ± 4.1 and 11.6 ± 2.0 mg L -1. 0.5 and 0.4 μmol L -1 for the spring and outlet, respectively.
Metal concentrations in the soil solutions were more vari- Elemental concentrations in the runoff waters filtrated at
able among the soil profiles and during the seasonal cycle. Iron, 0.22 μm were lower than those observed in the stream solu-
Al, and Mn concentrations were below the detection limits tions. Si was the dominant element, with a concentration of
throughout the sampling period (Tab. 1). Mean Ni concen- 12.3 ± 3.1 μmol L -1. Importantly, the Cr(VI), Ni, and Mn con-
trations varied from 0.15 ± 0.2 to 1.2 ± 0.8 μmol L -1 (Tab. 1) centrations were significant, with values of 0.8 ± 0.4, 0.2 ± 0.1,
and decreased drastically with depth for NIQ II, but increased and 1.6 ± 0.2 μmol L -1, respectively (Tab. 1).
slightly with depth in NIQ III. Ni concentrations were hetero-
geneous both spatially and temporally, particularly in NIQ Filtration fractionation
III. For example, in the ceramic cup at 20 cm depth and that at More than 20 samples collected in February 2008 were
150 cm depth in NIQ III, the Ni content was always particularly analyzed following the filtration fractionation protocol, and the
high compared to the others, indicating significant lateral vari- results are presented in Table 3. The concentrations of Cr, Ni,
ability. Hexavalent chromium concentrations in the soil solu- Ca, Mg, and Si in the different subsamples (unfiltered, θ0; 0.22
tions were relatively high, reaching 3.9 μmol L -1 in December > θ1 > 0.025 μm; 0.025 > θ2 > 10 kDa; 10 kDa > θ3) of both
2006 (Tab. 1). In NIQ II, Cr(VI) concentrations tended to the soil and stream solutions were in the same range within
increase between 20 to 70cm and decrease slightly below, with the limits of analytical error (Tab. 3). The concentrations of
a higher concentration observed at 70 cm, whereas the Cr(VI) Fe and Al in all soil solution fractions were always below the
concentrations in NIQ III remained homogeneous with depth detection limits in all subsamples. However, in the runoff water,
(approximately 1.0 μmol L -1) (Tab. 1). Over time, Cr(VI) con- the Fe concentration was particularly high (3,253 μmol L -1) in
centrations tended to decrease from December 2006 to January the unfiltered water, whereas it was below the detection limit
2007, followed by a long-term increase from January to June after filtration (Tab. 3). To a lesser extent, the concentrations
2007 (as shown for NIQ II at 20 and 70 cm depth in Figure 3). of Mn, Cr, and Ni in the unfiltered runoff water also sharply
decreased after filtration at 0.22 μm: only 30% of the Mn, 7%
Surface waters of the Cr, and 1% of the Ni remained after the 0.22 μm fil-
The pH of the rainwater was acidic (pH = 4.8 ± 0.05), and tration. The concentrations in all filtered fractions remained
the ion concentrations were below the detection limits of the equivalent, at approximately 1.8, 1.0, and 0.2 μmol L -1, for
ICP-AES and the ionic chromatograph. Mn, Cr, and Ni, respectively. Therefore, metals are present
The pH of the water at the spring was neutral (7.25 ± 0.12), in the runoff samples associated with Fe-colloids > 0.22 μm
and the pH was higher at the outlet (8.00 ± 0.05). In surface and as free ions. Finally, the Si concentration in the unfiltered

6
 Braz. J. Geol. (2021), 51(1): e20200092

Table 3. Result of Si, Ca, Mg, Fe, Al, Mn, Cr, and Ni of all filtration fractionation solution performed using a cascade filtration approach on
a selection of soils and surface’s solutions, and ratio between concentrations in the different size fractions expressed in %. (n.f no filtered), <
d.l. as below detection limit.
Si Ca Mg Fe Al Mn Cr Ni
μmol L (%)
-1

n.f. 60.20   9.00   7.50   < d.l.   < d.l.   < d.l.   1.62   0.35  
0.22 μm 61.40 102 9.20 99 7.40 99 < d.l. - < d.l. - < d.l. - 1.65 102 0.32 91
NIQ II-20
0.025 μm 61.60 102 10.30 114 8.50 114 < d.l. - < d.l. - < d.l. - 1.63 100 0.36 104
10 kDA 58.20 97 10.50 103 7.70 103 < d.l. - < d.l. - < d.l. - 1.51 93 0.28 80
n.f. 38.80 13.90 12.40 < d.l. < d.l. < d.l. 1.35 0.41
0.22 μm 38.20 98 13.60 105 12.90 105 < d.l. - < d.l. - < d.l. - 1.38 102 0.41 99
NIQ II-70
0.025 μm 39.40 101 14.80 109 13.50 109 < d.l. - < d.l. - < d.l. - 1.3 96 0.27 66
10 kDA 39.30 101 15.20 116 14.30 116 < d.l. - < d.l. - < d.l. - 1.24 92 0.28 68
n.f. 33.30   7.90   7.60   < d.l.   < d.l.   < d.l.   0.56   0.42  
0.22 μm 33.30 100 6.00 88 6.70 88 < d.l. - < d.l. - < d.l. - 0.6 107 0.39 93
NIQ II-150
0.025 μm 34.30 103 7.40 109 8.30 109 < d.l. - < d.l. - < d.l. - 0.61 109 0.34 81
10 kDA 33.70 101 8.30 103 7.80 103 < d.l. - < d.l. - < d.l. - 0.54 97 0.41 98
n.f. 364.40   34.10   324.40   < d.l.   < d.l.   0.44   0.86   1.45  
0.22 μm 351.20 96 35.80 103 332.70 103 < d.l. - < d.l. - 0.4 92 0.87 101 1.43 98
Stream
0.025 μm 368.10 101 36.20 105 342.00 105 < d.l. - <d.l. - 0.37 85 0.87 100 1.16 80
10 kDA 367.50 101 35.40 102 330.30 102 < d.l. - < d.l. - 0.37 86 0.94 109 1.58 108
n.f. 44.50 4.40 9.60 3,253 42 5.81 12.84 14.34
0.22 μm 15.20 34 1.90 48 4.60 48 < d.l. 0 < d.l. 0 1.97 34 1.09 8 0.16 1
Runoff
0.025 μm 16.20 37 3.70 71 6.80 71 < d.l. 0 < d.l. 0 1.61 28 0.93 7 0.2 1
10 kDA 16.40 37 4.00 73 7.00 73 < d.l. 0 < d.l. 0 1.55 27 0.86 7 0,16 1

runoff solution was higher (44.5 μmol L -1) than in the filtered The chemical composition exhibited high variability, in agree-
solutions, in which it remained at approximately 16 μmol L -1. ment with the fact that several parameters control the content
and speciation of soil solutions over time (e.g., local mineral-
ogy, vegetation and biological activities, as well as water con-
DISCUSSION tent and saturation).
Silica dominated the solution composition. In such slightly
Serpentine syndrome and metal acidic solutions, aqueous Si species occurred predominantly
concentrations in soil solutions in the form of neutral species, primarily H4SiO4° (Gérard
Niquelândia Ferralsols developed on ultramafic rocks are et al. 2008). The concentrations remained relatively constant
highly weathered and leached and, thus, poor in the most mobile throughout the soil profiles during both the rainy and dry sea-
elements, such as Ca, Mg, and Si, and enriched in less mobile sons. Silica appears to be only slightly affected by edaphic con-
elements, such as Fe, Al, Mn, Cr, and Ni (Garnier et al. 2006, ditions or biological processes (Fig. 3). Moreover, the concen-
2009a, 2009b, 2013). Accordingly, the soil solution chemistry trations observed are consistent with the solubility of quartz
was slightly acidic and poorly mineralized in the (B) horizon, (Log[H4SiO4°] of -4.4 to -4) (Maitat et al. 2000, Wonisch et al.
although the solution was slightly more mineralized inside the 2008). The results also indicate that the Si buffering capacity
topsoil due to the biodegradation of soil organic matter and of these soils is large, in agreement with the soil mineralogy
the surface recycling. The particularly low concentration of and the presence of quartz as the only silicate minerals in both
nutrients, such as K, has been recognized as one explanation the bulk and fine fractions (Garnier et al. 2009b).
for the low fertility of this type of soil. Solutions were not bal- Ca and Na concentrations were in the same range as
anced with the main primary minerals of the dunite bedrock, those reported by Lilienfein et al. (2000) in soil solutions
such as olivine, but the dominant cations, i.e., Si and Mg, were from Brazilian savanna oxisols, highlighting the high degree
in agreement with the “ultramafic” nature of the soils. Soil of weathering of these Ferralsols. However, Mg concentra-
solutions were free of Fe, Al, and Mn, which is in agreement tions were slightly higher in the Niquelândia soil solutions,
with the immobilization of such elements as oxides in unsat- which is explained by the UM nature of the parent material.
urated soil profiles. In contrast, the presence of metals, such Mg and Ca concentrations were in the same range as those
as Ni and Cr, which are slightly more soluble, was significant. reported by other studies on ultramafic soils (Proctor 1970,

7
 Braz. J. Geol. (2021), 51(1): e20200092

Anderson et al. 1973, Johnston and Proctor 1981, Gasser et al. chemical weathering, cannot be compared to presents results
1994) but lower than those reported by Becquer et al. (2010). obtained in highly leached soils. The vertical distribution of
The chemical discrepancies between the topsoil and deeper Cr(VI) concentrations over the hydrological cycle agreed with
horizons suggest that for different soil processes; the higher the distribution of Cr(VI) availability in both the NIQ II and
nutrient content in the topsoil solutions is associated with NIQ III profiles, as assessed via IEK (Garnier et al. 2009a).
nutrient recycling. Nutrient cycling appears to be located at Moreover, Garnier et al. (2009a) also identified a high cor-
the surface and is likely related to plant development (Lucas relation between the granulometric clay content and Cr(VI)
et al. 1993). The rapid mineralization of organic matter likely availability. An increase in the sorption of oxyanions onto
promotes this feature and is emphasized by the large decrease Fe-oxides, consistent with the pH increase with depth, may
in NO3- with depth. Moreover, given the presence of Mg-rich also significantly influence Cr(VI) mobility. Finally, the pres-
plants (Reeves et al. 2007) and consequently Mg-enriched lit- ence of organic matter can explain the lower concentrations
ter in the topsoil, Mg concentrations are 3-fold higher in the of Cr(VI) in topsoil solutions compared to mineral horizons,
topsoil than in deeper horizons. as it can reduce Cr(VI) into Cr(III) in topsoil, which is subse-
Ca:Mg molar ratios measured in the soil solutions were quently immobilized in its trivalent form. However, given the
extremely low (0.65 to 1.32), as were the total and extract- contrasting effects of the various components or properties of
able Ca:Mg molar ratios measured in the soil matrix (data not the soils, no simple relationship exists between Cr concentra-
shown). This imbalance has already been considered to be a tions in soil solutions and other soil properties, e.g., pH, and
specific feature of ultramafic soils (Whittaker 1954). Here, organic matter and iron oxide contents.
the ratio was lower than the values reported by Johnston and Cr(VI) concentrations in soil solutions were higher than
Proctor (1981), who studied less-developed “ultramafic” soils. toxicity standards, such as recommended levels for irrigation
In quite similar soils in New-Caledonia, Becquer et al. (2010) water (< 0.15 μmol L -1) or freshwater life (< 0.02 μmol L -1)
showed that the Mg:Ca molar ratio was close to unity. In a (Pawlisz et al. 1997, WHO 1998). Therefore, Cr(VI) proba-
vegetation survey of the Brazilian ultramafic massifs, Reeves bly contributes to the endemism seen within the study region,
et al. (2007) showed that leaves from plants growing in the i.e., one of the features of the serpentine syndrome (Reeves
soils of these massifs have a low Ca:Mg ratio, which ranges et al. 2007). However, unlike Ni, the content of Cr in all ana-
from 0.26 to 2.26. Moreover, this study noted the presence of lyzed plant leaves was low (Reeves, personal communica-
plants that are particularly rich in Ca or Mg in those soils and tion). Thus, Cr seems not to be absorbed by plants and stored
contain 12,910 and 28,270 mg kg-1 of Ca and Mg, respectively in roots, as observed by Shanker et al. (2005). However, due
(Reeves et al. 2007). Given the composition of the soil solu- to the high toxicity of Cr(VI) even at low concentrations, Cr
tions and the ratio in plant tissues, it appears that the plants must have an indirect effect on the biota, and the ecosystem
of the Niquelândia massif can concentrate Ca relative to Mg has likely acquired a tolerance capacity.
or vice versa. The data obtained in this study (Tab. 2) demon- Ni concentrations in solutions were of the same order of
strates that the Ca:Mg ratio varies spatially and temporally; magnitude as those observed in a New Caledonian UM out-
thus, variations in Ca and Mg in soil solutions can explain crop (Becquer et al. 2010). However, the local variability in Ni
the large variations in the concentrations of these elements concentrations was large. In NIQ II, the Ni concentrations were
observed in plants. larger in the topsoil than in the deeper horizons, whereas the
Hexavalent chromium always represents more than 95% of concentrations were homogeneous in NIQ III, except for local
the total Cr quantified by ICP-AES in surface waters. Even if anomalies. Ni concentrations can be analyzed using the profile
the sampling method is not suitable for Cr(III) sampling structures of both soils, which were presented in a previous
(Becquer et al. 2010), given the slightly acidic pH and the study (Garnier et al. 2009b). NIQ II presents a superficial hori-
large amount of iron oxides present in the soils (Garnier et al. zon with a larger content of organic matter and deeper horizons
2009b), the Cr(III) is expected to be entirely sorbed (Fischer rich in iron oxides. In the surface horizons, it is thought that the
et al. 2007) and consequently not mobile (Kotas and Stasicka high Ni content in the soil solutions is controlled by organic
2000). The Cr(VI) concentrations remained high throughout matter or litterfall mineralization in the topsoil. Litter-fall from
the complete hydrological cycle (Fig. 3), and the field results Ni-hyperaccumulating plants (Reeves et al. 2007) contributes
confirm the high Cr(VI) lability measured in the laboratory to the addition of Ni to the surface horizon. This feature is in
by KH2PO4-extraction, Isotope Exchange Kinetic (IEK) and agreement with the solid speciation of Ni in these soils, with
XANES (Garnier et al. 2006, 2009a, 2013). Cr(VI) was pres- high contents of Ni associated with organic matter (between
ent in “truly” dissolved forms, as shown by the filtration frac- 100 and 400 mg kg-1, Garnier 2008). In deeper horizons, the
tionation (Tab. 3). Cr speciation is in agreement with other slight increase in the content of iron oxides, associated with
results obtained from tropical UM soils by Becquer et al. (2003, the decrease in the organic matter content and the increase of
2010) (Suppl. Fig.). Gasser et al. (1994) found that the Cr pH, promotes Ni sorption on goethite (Fischer et al. 2007)
in soil solution was primarily (65–75%) present in colloidal (Suppl. Fig.). Otherwise, the local variability in Ni concen-
form. These results, being obtained from a poorly weathered trations in the NIQ III solutions collected at the same depth
serpentine soil developed under a cold mountain climate (from the detection limit to 2.8 μmol L -1) could be related
where the dominant pedogenetic process was cryofraction- to local-scale mineralogical variability. The presence of rel-
ation, leading to the production of rock fragments and low icts composed of weathered Ni-smectite in the upper part of

8
 Braz. J. Geol. (2021), 51(1): e20200092

the NIQ III profile may locally increase Ni availability and agrees with the alkaline pH. These findings are in good agree-
mobility. This finding is in good agreement with the results of ment with those of McClain and Maher (2016) and with the
Becquer et al. (2010), who showed a lower availability of Ni solubility of the main silicate minerals in the soil and the sap-
in a highly weathered, iron-rich soil in a mountain piedmont rolite, i.e., UM rock-solution equilibrium. The Mg, Ca, and Si
(OUE1) relative to a colluvio-alluvial soil containing some concentrations were lower than those reported by McClain
poorly weathered silicates (OUE3). Nickel concentrations and Maher (2016), whereas those of Cr (considering both
in the soil solutions also often exceed the toxic threshold for Cr(VI) and Cr(VI) + Cr(III) reported) and Ni are higher. On
freshwater given in the WHO (1998) guidelines for drinking the one hand, the Si concentrations in the soil, which are nearly
water quality or for biota reported by L’Huillier and Edighoffer 40 to 100 μM l-1, are closely related to the solubility product
(1996) and Becquer et al. (2010). However, Ca2+ and Mg2+ of quartz, which is close to a Log[H4SiO4°] value of -4.4 to -4
are known to alleviate the phytotoxicity of Ni (Proctor and (Maitat et al. 2000, Wonisch et al. 2008). In turn, the Si con-
McGowan 1976, Gabrielli and Pandolfini 1984, Robertson centrations in the spring and the outlet, which are nearly 300
1985), and their presence may limit Ni toxicity. μM l-1, are much higher due to the lower resistance to weath-
The serpentine syndrome has been proposed and is related ering of the olivine or serpentine encountered in the deeper
to a low level of nutrients (N, P, and K), a Ca:Mg imbalance, parts of the profiles.
as well as the presence of metals that can decrease fertility Particular attention was given to the composition of the
(Whittaker 1954, Brooks 1987, Bini et al. 2017). Nutrient con- solutions collected during February 2008 to verify the presence
tents were not lower than those observed in other oxisols of of colloids and their role as metal-bearing phases, as observed
the Cerrado region (Lilienfein et al. 2000), i.e., high leached by Gasser et al. (1994) for soils developed on ultramafic rock
soils. However, Ca:Mg ratios were low in the topsoil, and both in the Davos region. For a given element, lower concentrations
Ni and Cr(VI) are highly labile. At a minimum, the present in one of two different size fractions indicate the presence of a
results are in agreement with two of the three serpentine syn- particulate form of this element. This finding, as well as varia-
drome conditions, i.e., the low Ca:Mg ratio and the presence tions in the ratios between certain elements among different
of labile metals, leading to limited fertility of the ultramafic size fractions, can be used to determine the impact, if any, of
outcrop area of Niquelândia. This limitation likely contributes different components on metals and colloid formation (Garnier
to the high degree of endemism observed in the ultramafic et al. 2011). The presence of Cr(VI) and Ni in the filtered solu-
massif. Rapid recycling of nutrients and Ni, i.e., via uptake of tions, even at 10 kDa, in both soil and surface waters from the
the elements released by the mineralization of litter, appears stream and runoff, proves that these elements are mobile at the
to occur, thereby limiting the leaching of essential elements. catchment scale in “truly” dissolved forms. More than 66% of
This feature confers greater fertility through the enhanced avail- the Ni and 92% of the Cr(VI) in the soil solutions, as well as all
ability of nutrients, which mitigates one of the typical traits of the Ni and Cr(VI) in the stream, were present in dissolved
of areas with ultramafic substrates. This feature also produces form, the remainder being in colloidal forms. The Ni concen-
higher Ni concentrations in the topsoil solutions. The present tration in the spring was close to the soil concentrations, and
results suggest that, in deep, leached soils developed in ultra- the concentration decreased slightly, whereas the Cr concen-
mafic rock, the (hyper)accumulation of Ni by plants and the tration in the spring was lower than the soil concentrations
recycling of Ni-rich organic matter can indirectly contribute and remained constant along the watercourse. The behavior of
to maintaining high Ni concentrations in the topsoil and thus Ni and Cr(VI) is very different than that of Si and Mg. Unlike
contribute to the high degree of endemism on the outcrop. those of the latter species, the concentrations of Ni and Cr(VI)
Similar features seem to occur at Mg concentrations that can in the soil solutions did not increase after passing through the
maintain higher Mg bioavailability relative to Ca in topsoil. saprolite. This difference in Ni and Cr dynamics from the soil
Both features are in agreement with the ecological traits of to the spring with regards to Si and Mg can be explained by
these environments, as reflected by the serpentine syndrome. different mechanisms, including:
• dilution by soil solutions that are relatively poor in Cr or
Metal mobility Ni (in less developed soils);
The pH value of the spring water (7.25) was higher than • weathering and precipitation of different kinds of met-
the values observed in the soil solutions (6.05), likely due to al-bearing phases;
hydrolysis processes in the deeper part of the profiles, i.e., the • sorption/desorption mechanisms operating between
saprolite, where Ni-bearing clays and weatherable primary Ni, which occurs as cations, and Cr(VI), which occurs as
minerals are abundant. In surface water, cation concentrations oxyanions, and the surface charges of minerals;
decrease in the order Mg2+ > Ca2+ > Na+ > K+, and the Ca/Mg • the reduction of Cr to a less mobile form, i.e., Cr(III).
ratio for all water samples was lower than 1, due to the low Ca
concentration in ultramafic bedrocks, similar to the findings The adsorption of Ni on goethite, which forms quickly
of Kaprara et al. (2015) for UM water in Greece and Mcclain during weathering of UM primary minerals, appears to be a
and Maher (2016) in the United States. The elevated Mg and key factor. Indeed, the increase beyond pH 7 in the saprolite
Si concentrations in the stream solutions in relation to the leads to the total sorption of Ni in goethite (Fischer et al. 2007).
soil solutions underline this feature. The large content of Mg Therefore, soil solutions coming from the highly weathered
and Ca may be balanced by alkalinity (not measured), which upper part of the soil profile are the main source of mobile

9
 Braz. J. Geol. (2021), 51(1): e20200092

nickel in the environment. For Cr(VI), the increase in pH in vegetation. Moreover, Cr, mainly in its hexavalent form, and
the saprolite should decrease the retention of Cr(VI) anions by Ni occurred in the topsoil solutions as “truly” dissolved ions.
goethite (Garnier et al. 2009a). According to Dai et al. (2009), Cr(VI) concentrations remained high, and no change in the
free Cr(III) ions and [CrOH]2+ are the forms of Cr(III) that oxidation state was observed in the soil solutions through a
oxidize to Cr(VI) most readily. However, these Cr species complete hydrological cycle. These metals’ lability, coupled
disappear beyond pH 7. Therefore, the production of Cr(VI) with the large Ca:Mg imbalance, contribute to the biodiversity
would be limited in the saprolite, unlike the weathered soil. selectivity within the outcrop area of these UM rocks, high-
Soil solutions coming from the highly weathered upper part lighting once again the close relationship between the serpen-
of the soil profile are also the main source of mobile Cr(VI) tine syndrome and the availability of metals in soils.
in the environment. Niquelândia UM soils might constitute a source of labile
Runoff waters filtered at 0.22 μm were entirely free of Fe metals, mainly Ni and Cr(VI), which are partly exported to
and Al, whereas the unfiltered samples featured high concentra- surrounding areas of the ultramafic massif. Two main environ-
tions of Fe, showing that Fe was mobile as a particulate mate- mental dispersal forms of metals have been: “truly” dissolved
rial. This observation is in agreement with in situ observations metals and colloidal transfer of Ni and Cr associated with
during rainstorms, in which oxide particles were mobilized at Fe-oxides. The highly weathered upper parts of the soil are more
the catchment scale in this area, where UM rocks outcrop. In the likely to be the source of mobile, “truly” dissolved Ni and Cr,
sample tubes, these particles (> 0.22 μm) remained dispersed in whereas saprolite can act as a sink of metals. Colloidal transfer
the runoff waters for several months. Thus, despite being larger of Fe-oxides and associated metals occurs during intense rain
in size than the typical cut-off for colloids, this fraction behaved events. However, this metal’s mobility may have an impact on
as a colloidal fraction. A XANES measurement on this fraction the surrounding ecosystems, particularly for plants and micro-
has revealed that a portion of the Cr was present in its hexava- organisms not adapted to these metals.
lent form in this fraction (Garnier et al. 2013). This fraction,
the > 0.22 μm fraction, involved metal transfer on the outcrop
in “colluvial” transport from the hill to the footslope, as already ACKNOWLEDGMENTS
discussed by Garnier et al. (2009b), as well as to the surround- This work was supported by the Collège Doctoral Franco-
ing ecosystems. This fraction is also rich in Al, Mn, Ni, and Cr, Brésilien and by the CNPq (Conselho Nacional de Desenvolvimento
and this colloidal transport and mobility may promote metal Científico e Tecnológico, Brazil) under contract No. 475124/2006-5
dispersion, thereby acting as a vector of metal mobility. and No. 445423/2014-5; 420697/2018-7 and 302722/2018‑1.
The authors wish to thank the Votorantim Metais and more
particularly the staff of the mine of Niquelândia. The authors
CONCLUSION are thankful to A. Becquer, Dr M.I. Lopes de Oliveira, Dr D.
This investigation of soil solutions and surface waters from Néia Eberhardt, and Dr N.P. Benito for their assistance during
the Niquelândia ultramafic massif improves our understanding soil solutions sampling, and the IRD and Embrapa of Brasilia
of the unique qualities of this ultramafic area and the serpen- for technical supports. The authors also wish to thank for the
tine syndrome. The low Ca:Mg ratio in the soil solutions was DOC measurement and tribute the paper to C. Garnier from
consistent with both the ultramafic features and the Mg-rich the University of Toulon.

ARTICLE INFORMATION
Manuscript ID: 20200092. Received on: 04/18/2020. Approved on: 10/14/2020.
All authors participated in all phases of the study, sampling, analyses, discussion, and writing of the paper.
Competing interests: The authors declare no competing interests.

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