Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405

https://doi.org/10.1007/s42729-022-00816-w

ORIGINAL PAPER

Adsorption of Zerovalent Iron Nanoparticles in the Inorganic Fraction

of Volcanic Soils
Manuel Gacitua1,2 · Lynda Pavez1,3 · Mauricio Escudey1,2 · Mónica Antilén3

Received: 26 October 2021 / Accepted: 2 March 2022 / Published online: 5 April 2022
© The Author(s) 2022

Abstract
Zerovalent (ZVI) iron has been used in environmental remediation, but the environmental fate of its nanoparticles (NZVI) is
hard to find. The present study aimed to characterise the adsorption processes of commercial ZVI in the inorganic fraction
of volcanic soils, contributing to the knowledge of the adsorption process on the whole soil. Volcanic soil samples were
obtained by calcination method and characterised. A nano-ZVI stable suspension is prepared and characterised to know its
size-particle distribution. Adsorption points (kinetical and isothermal) were obtained by adapting the procedure for homo-
geneous analyte adsorption. Kinetical, solute transport and isothermal adsorption and desorption models were adjusted to
obtain more conclusive information about the process. Analysis of the results revealed that adsorption is a fast process. The
inorganic fraction of an Andisol presented pH-dependant surface charge, requiring highly consistent control of the working
pH to obtain proper adsorption points. Isothermal adsorption indicates that a combination of physical and chemical mecha-
nisms contributes to the NZVI adsorption process. Desorption studies suggested chemisorption on specific surface-active
sites of adsorbents, with the inorganic fraction of soil irreversibly retaining most of the NZVI particles. NZVI become
irreversibly adsorbed over the inorganic fraction of soils, extending particle reactivity through time, affecting the stability
of organic matter and microbial communities. In turn, this increases the possibility for plant uptake. Nevertheless, there is
a low risk for the transport of NZVI through soil profiles or co-transport of other components that becomes adsorbed over
iron, lowering the risk of aquifer pollution.

Keywords Adsorption of particles in suspension · Mineral fraction of soil · pH-effect on adsorption · Environmental fate of
zerovalent iron · Nano zerovalent iron

1 Introduction is placed in contact with soil, pollutants become oxidised

Zerovalent iron (ZVI), including zerovalent iron nanoparti-
cles (NZVI), has been used for environmental remediation of
different pollutants present in soils (Luna et al. 2015; Orozco
et al. 2015; Guo et al. 2021; Qiao et al. 2020). When ZVI
* Manuel Gacitua
manuel.gacitua@usach.cl
1
Facultad de Química Y Biología, Universidad de
Santiago de Chile (USACH), Av. L.B. O’Higgins 3363,
7254758 Santiago, Chile
2
Centro Para El Desarrollo de La Nanociencia Y
Nanotecnología (CEDENNA), Av. L.B. O’Higgins 3363,
7254758 Santiago, Chile
3
Facultad de Química Y de Farmacia, Pontificia
Universidad Católica de Chile, Vicuña Mackenna 4860,
7820436 Santiago, Chile
through a Fenton reaction mechanism leaving iron oxide as
an innocuous by-product. ZVI slurry comprised of micro
and nanoparticles in liquid suspension represents a new
generation of environmental remediation technologies (Bru-
movsky et al. 2021; Hosseini and Tosco 2015; Luna et al.
2015; Mondino et al. 2020; Tosco et al. 2014). Because of its
reduced size, when NZVI are injected into soils have higher
reactivity and mobility than conventional iron powder,
contributing to their broad use for the decontamination of
groundwater and soil remediation (Yang et al. 2018). After
remediation, the excess of NZVI may generate problems
in the ecosystem. For instance, some studies have reported
the negative impact of NZVI on soil microbial community
structures (Lefevre et al. 2016). Due to the complexity of
soils, there is a significant knowledge gap regarding the fate
of NZVI in soils; specifically, more information is needed

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Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
regarding the adsorption and mobility processes (Simonin
& Richaume 2015).
In the literature, the few studies of NZVI adsorption or
transport processes generally employ soil models. Zhang
et al. reported outcomes of NZVI over quartz sand and iron
oxide coated quartz sand (M. Zhang et al. 2017). Others
studied NZVI transport through model adsorbents of sim-
ple composition (Ibrahim et al. 2019; Zhang et al. 2017).
Moreover, Micic et al. were able to describe the effect of Na-
humate on the mobility enhancement of poly(acrylic acid)-
coated ZVI nanoparticles through standard sand mediums,
but this effect was not observed when using natural minerals
as adsorbents due to the surface heterogeneity (Micic et al.,
2017). While these studies have set the ground for under-
standing the environmental fate of NZVI on simple-compo-
sition adsorbent, none has still analysed the adsorption pro-
cess of NZVI on complex soils. NZVI has been employed to
remediate volcanic soils as Nitisols with banana plantations
(Mouvet et al. 2020); however, there are no studies regarding
the fate of the NZVI excess in these matrixes.
Regarding the effect of NZVI on plants, results are
contradictory depending mostly on particle concentration
and plant species. For instance, Martinez-Fernandez and
Komarek tested the distinct effect of ­Fe2O3 and ZVI nano-
particles on tomatoes plants, with no harmful effects from
zerovalent particles found (Martinez-Fernandez & Komarek
2016). In addition, Teodoro et al. reported on the effect of
NZVI on growth of Agrostis capillaris and Festuca rubra,
evidencing that the amendments had increased shoot growth
and elongation rate (Teodoro et al. 2020). On the other hand,
Wang et al. reported the effect of NZVI on rice seedling with
growth inhibition at high nanoparticle concentration (Wang
et al. 2016). Also, Sun et al. presented that starch-stabilised
NZVI decreased germination rate, increased iron uptake rate
and altered nutritional balance of mung bean seeds up to
phytotoxic effects depending on nanoparticle concentration
(Sun et al. 2019). Nevertheless, it is important to point out
that all these studies are made on hydroponical conditions,
which does not represent the effect of ZVI nanoparticles
when immersed in soil–water matrix. The main reason for
the lack of studies regarding the effects and fate of NZVI
particles using full complex soils, including volcanic soil,
is the high complexity of these systems acting as adsorbent
surfaces hindering the obtainment of consented conclusions.
For instance, some volcanic soil orders possess consider-
able organic matter percentages and important contents of
shortly ordered minerals (Escudey et al. 2004) with particu-
lar adsorption behaviour, hindering repeatable results. More-
over, studying the adsorption of nanoparticles is complicated
because of solution parameters on aggregation and reactivity
of suspended nanoparticles, such as pH and ionic strength
(Flory et al. 2013; Mpinda Tushiminine 2014). Thus, further
adsorption studies using NZVI and natural volcanic soils are
2393
required to fully understand their fate and consequences in
the environment. A strategic approach to assess the com-
plete full soil adsorption process could be to determine the
relative contribution from volcanic soil constituents to the
adsorption process, employing soil fractions.
In the present report, we present the adsorption of a com-
mercial zerovalent iron particle slurry, containing NZVI,
over the inorganic fraction of two Chilean volcanic soils.
The use soil fractions in NZVI adsorption experiments
would permit to establish the relative importance of soil
components on the NZVI-interaction until reaching to an
appropriate interpretation of NZVI behaviour in full soils.
This information is also important to eventually assess the
potential environmental fate ZVI in nature. For this study,
the inorganic fraction of soil was obtained through the cal-
cination method, removing the organic layer and exposing
the mineral fraction (Escudey et al. 1999). Adsorption kinet-
ics, solute transport mechanism, adsorption and desorption
isotherm curves were obtained, modelled and discussed,
permitting evaluation of the NZVI fate in volcanic soils.
2 Materials and Methods
2.1 Soils
Two volcanic soils from the southern central area of Chile,
an Ultisol (Collipulli, 36°58′ S; 72°09′ W) and an Andisol
(Ralun, 41°32′ S; 73°05′ W), were chosen and have been
previously characterised (Cáceres-Jensen et al. 2013; Cac-
eres-Jensen et al. 2019). The samples were collected at a
depth of 0–15 cm and stored at field moisture.
Nitrogen contents and organic carbon (OC%) was quan-
tified using the Walkley–Black method (Allison 1965).
Organic phosphorus (OP) was determined using sequen-
tial extraction method adapted for volcanic soils (Steward
& Oades 1972). The amounts of ­Fe2O3, ­Al2O3 and ­SiO2
(wt%) were obtained after chemical analysis by complete
dissolution of samples and quantification using ICP-OES
spectrometer. Soil pH was measured at the supernatant of
the mixture soil:solution with ratio equal to 1:2.5 in mass.
The solution corresponded to distilled water or 1.0 mol
­L−1 KCl. Conductivity was measured at the supernatant in
the same soil:solution mixture with distilled water after a
10 min centrifugation (8000 rpm) step (Sadzawka 1991).
Cation exchange capacity was calculated as the sum of
exchangeable bases (­ CH3COONH4 extract and determina-
tion by atomic absorption spectroscopy) and extractable
acidity ­(BaCl2-triethanolammine extract and determination
by HCl-titration) (Sadzawka, 1991).
Surface charge was determined through electropho-
retic mobility measurements. Samples were suspended in
­10−3 M NaCl to perform electrophoretic measurements in
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2394 Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405

a zeta metre to establish the isoelectric point (IEP) and Table 1  Characterisation of full and calcined soil samples
pH was adjusted with 1­ 0 −2 M HCl or NaOH. The zeta Collipulli Ralun
potential (ZP) was calculated using the Helmholtz-Smolu-
chowski equation (Hunter 1981). Full soils
External specific surface area (ESSA) was determined Dominant mineralogy > 50% kaolinite > 50% allo-
< 1% halloysite phane
by the adsorption–desorption isotherms of ­N2 at − 195 °C < 1% vermiculite 1–5% chlorite-
(77 K), changing the relative pressure (P/Po) of the gas < 1% α-cristobalite AL
and recording the volume adsorbed on the solid’s surface. 1–5% plagio-
ESSA was calculated from the amount of N ­ 2 adsorbed clase
< 1%
employing the Brunauer–Emmett–Teller or BET equation α-cristobalite
(Brunauer et al. 1938). < 1% mont-
Prior to adsorption experiments, soil samples were morillonite
sieved to collect the < 2 mm size particles and calcined at Texture Sand% 13.7 47.3
550 °C for 3 h. Properties of soil samples are presented Silt% 40.7 38.5
in Table 1. Clay% 45.7 12.9
Collipulli and Ralun exhibit differences in soil texture. N% 0.20 0.74
Both soils possess comparable amounts of silt at about OC% 2.3 9.8
40%. But the sand- and clay-size fractions behave in an OP (mg ­kg−1) 274 451
inverse fashion on both soils, with ca. 15% and 45% for ­Fe2O3 (wt%) 13.8 9.5
Collipulli soil and vice versa for Ralun. Nitrogen (N%), ­Al2O3 (wt%) 19.8 17.5
organic carbon (OC%) and organic phosphorus contents ­SiO2 (wt%) 46.7 43.5
(OP) decreased dramatically after heat treatment on both pH-H2O 5.5 5.4
soils. Metallic oxides contents (wt%) ­Fe 2O3, ­Al2O3 and pH-KCl 4.4 4.6
­SiO2 increased in proportion after calcination. Soil pH (in CE (mS) 0.10 0.23
water or KCl) got elevated after organic matter destruc- CEC (cmol ­kg−1) 37.5 44.1
tion especially for Ralun, the Andisol. This soil possesses IEP 2.0 3.3
higher amounts of organic matter, and its acid pH is highly ESSA ­(m2 ­g−1) 70 2.1
dependent on the acid–base reactions from organic moie- Calcined soils
ties located at the surface. Therefore, calcination would N% 0.08 0.09
intensely shift Ralun pH, while for Collipulli this effect is OC% 0.7 0.5
less important. Electrical conductivity (EC) increases on OP (mg ­kg−1) 129 130
both soil samples after calcination, due to concentration ­Fe2O3 (wt%) 14.3 12.7
of soluble salts from the mass-loss generated by the heat ­Al2O3 (wt%) 23.6 21.3
treatment. Determination of the isoelectric point (IEP) ­SiO2 (wt%) 51.0 51.6
of the resulting calcined soils is presented in Figure S1. pH-H2O 5.6 7.8
Extrapolation of the curve until zeta potential is 0 yields pH-KCl 4.6 7.2
an IEP around pH 2.2 for Collipulli. On the other hand, CE 0.34 0.54
calcined Ralun samples an IEP of 7.4. Permanent and CEC (cmol ­kg−1) 26.3 2.1
variable surface charge calcined soil samples are mainly IEP 2.2 7.4
explained by their mineralogy (Table 1). Thus, permanent ESSA ­(m2 ­g−1) 65 2.1
and variable surface charge on Collipulli and Ralun cal-
cined samples, respectively, are mainly explained by their
mineralogy (Table 1); while permanent charge mineral 2.2 Zerovalent Iron
kaolinite is highly abundant on Collipulli soils, a variable
surface charge mineral as allophane dominates Ralun min- A sample of zerovalent iron (ZVI) slurry for remediation
eralogy. The IEP for Ralun got dramatically elevated after of contaminated soil and ground water was provided by
calcination, a behaviour not observed on Collipulli sample. Regenesis (Regenesis 2020). This product corresponds to a
Regarding external specific surface area (ESSA), there are colloidal suspension of metallic sulphidated ZVI, dark grey
great differences between soil series, up to ca. 30 times colour and with slight odour. Its pH is typically between 7
greater for calcined Collipulli samples over Ralun, which ­ −1. The iron concen-
and 9 and it has a density of 1.79 kg L
can be explained by its higher clay content. Therefore, tration was determined as 425.5 mg ­mL−1. The ZVI slurry
calcined soil samples display different features that could was used directly from original container to prepare a stable
determine distinct NZVI adsorption behaviours. suspension of NZVI particles as explained on Fig. 1a.

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Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405 2395

Probe ultra Vacuum filtration Dilution to desired

(a) 500 µL ZVI +
sonication at 100% with 5.0 and 1.0 µm scattered light value at
50 mL H2 O
amplitude for 10 min membrane filters 500 nm.

ZVI Regenesis® Ultrasound probe Vacuum filtration Dilution

(b) 3 x (1.2 g soil and 12 mL Orbital-shake of Filtration with 1.0 Scattered

ZVI) + ZVI + soil-blank tube sat 65 rpm µm syringe filters light at 500 nm

Soil + ZVI ZVI Soil + H2 O

Adsorption point set-up Orbital shaker Syringe filtration Measurement

Fig. 1  a NZVI stable suspension preparation steps. b Experimental adsorption points construction

As presented in Fig. 1a, a stable NZVI suspension was
prepared using 500 μL from original slurry and diluted with
50 mL of double distilled water. To enhance particle disper-
sion, this solution was sonicated by means of an ultrasound
probe at 100% amplitude for 10 min. Afterwards, the suspen-
sion was vacuum filtered using Whatman® nitrocellulose
membranes with 5.0 and 1.0 µm pore size. Then, the filtered
solution was diluted to the desired concentration by checking
its absorbance at 500 nm wavelength by means of a Thermo
Fisher Scientific Genesys 30 vis/UV spectrophotometer. In
this report, absorbance values provided by spectrophotom-
eter are interpreted as scattered light (S) by the nanoparticle
suspension. This solution was prepared daily to ensure its
stability and repeatability of results. Particle size distribution
of this solution was controlled using a Malvern Zetasizer
Nano ZS dynamic light scattering (DLS) system. This device
uses classical single-scattering DLS methods to calculate
particle sizes in a range from 0.3 nm to 10 µm with 633 nm
laser and detects the backscattered light at 173°. This device
also features a temperature-controlled holder for a cuvette.
According to the DLS report (Figure S2), 97.6% and 2.4% of
particles have 47.4 and 272.2 nm of diameter, respectively.
The concentration of the NZVI suspension was determined
by gravimetric analysis. Solutions were prepared to fixed
S values (0.300, 0.600, 0.900 and 1.200) at 500 nm wave-
length by means of a vis/UV spectrophotometer. Aliquots of
adequate volumes for each solution were transferred in trip-
licate to tared beakers and placed in lab-oven at 50 °C until
reaching constant mass. Beakers were weighted to obtain
the mass from dry NZVI particles, and a calibration curve
was constructed to check the dependence between S and
mass concentration (mg L ­ −1) of NZVI suspension. A linear
relationship between ZVI concentration and scattered light
at 500 nm is observed (Figure S2). Thus, prepared NZVI
suspension possesses most of its particles below 50 nm and
there is a linear relationship between ZVI nanoparticle con-
centration and scattered light at 500 nm.
2.3 Sorption Experiments
2.3.1 Experimental Points Construction
A NZVI stable suspension of appropriate concentration was
employed for adsorption experiments following the proce-
dure illustrated in Fig. 1b. A set of five 50 mL centrifuge
tubes was prepared for each point to assure repeatability:
three with NZVI suspension and soil; one with NZVI sus-
pension and one with soil and water to control particle
liberation from adsorbent. After reaching equilibrium, S
was measured at 500 nm. The S values for each experi-
mental point correspond to the average between the three
soil + NZVI tubes, minus the S value from the soil + ­H2O

13
2396
tube. The S value for the NZVI tube was controlled to check
NZVI stability during the duration of the experiment. This
type of methodology assures repeatable results for nanopar-
ticle adsorption experiments.
Adsorption Kinetics Experimental points were made at
different times (0–10 min) until reaching stable S values
through time. Equilibration time was determined for each
adsorbent at the conclusion of the experiment. Constructed
curves were adjusted using adsorption kinetic models
(Table 2).
2.3.2 Adsorption Isotherms
For Collipulli calcined soil, points were constructed
using an increasing concentration of ZVI suspension
(0–500 mg ­mL−1) using the procedure outlined in ‘Sec-
tion 2.3.1’. Experimental points were made using the equi-
libration time determined after adsorption kinetics. Con-
structed curves were adjusted using adsorption isotherm
models (Table 2).
Due to significant pH variations upon mixing Ralun
calcined soil samples and NZVI suspensions of different
concentrations, pH adjustment was required. To adjust the
pH, prior to isotherm adsorption experiments Ralun soil was
treated with HCl 0.01 M. Three portions of 0.2 mL of the
acid were added to 5 mL of water and 1.2 g of Ralun cal-
cined soil. The tubes were placed on an orbital shaker for
30 min at 50 rpm after every addition. Then NZVI suspen-
sions were added to reach a total volume of 12 mL using
same concentration range (0–500 mg ­mL−1) as the procedure
from ‘Section 2.3.1’. The pH of the mixtures was measured
at the conclusion of the procedure.
2.3.3 Desorption Isotherms
Once the adsorption process had ended and all supernatant
was removed, 12 mL of water was added to remnant adsor-
bent. The mixtures were subsequently agitated in an orbital
shaker for 10 min at 65 rpm. The supernatants were filtered
through a 1.0 µm pore-size filter and the quantification of
NZVI was carried out in a UV/vis spectrophotometer at
500 nm.
2.3.4 Sorption Theory
Equations, parameter description and interpretation of the
adsorptions kinetic (Evangelou 1998; Fernández-Bayo et al.
2008), kinetic involving solute transport (Önal 2006; Wu
et al. 2009a, 2009b; Ioannou & Simitzis 2009) and isother-
mal models (Evangelou 1998; Escudey et al. 2004; Ayawei
et al. 2017) considered for the adjustment of experimental
are presented in Table 2.
13
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
3 Results
3.1 Adsorption Kinetics
Sorption of NZVI nanoparticles as a function of time is
presented in Fig. 2. Saturation was reached during the first
10 min of the experiment. After each kinetic experimental
point, the pH of the supernatant in contact with Ralun and
Collipulli calcined samples was measured, with average
values of 5.2 ± 0.1 and 6.3 ± 0.2, respectively.
Figure 2 shows sorption kinetics and kinetic model
adjustment. The maximum experimental NZVI absorbed
at the end of the kinetic adsorption process (Cm) was 0.729
and 0.797 mg ­g−1 for Ralun and Collipulli, respectively.
Experimental data were fitted to three simple kinetic mod-
els: hyperbolic, pseudo-first (PFO) and pseudo-second
order (PSO) models; the resulting kinetic parameters are
presented in Table 3. The PFO model did not fit either of
the experimental data sets with R 2 values of 0.448 and
0.479 for Collipulli and Ralun, respectively. Calculated
maximum concentration (Cm-cal) for the PSO model agrees
with Cm and this model yielded the highest R2 parameter,
indicating that PSO best describes the adsorption kinetics.
Data were fitted to several solute transport mechanism
models: Elovich, intraparticle diffusion and their dimen-
sionless versions. The resulting parameters are presented
in Table 3.
3.2 Solute Transport Mechanism
Values obtained from R2 for the Elovich equation are close
to 1, indicating that this model describes the experimental
data for both soils (Fig. 3a). The initial rate constant α is
higher for Collipulli than for Ralun. The number of surface
sites given by β parameter was similar on both soils.
From the Elovich linear equation (Figure S3), the slope
(1/β) is considered to be the sorption rate as a function
of time during the slow stage of the reaction, while the
intercept (1/β)ln(αβ) corresponds to the amount absorbed
during the initial equilibrium stage (fast phase reaction).
As established by the analysis of the Elovich parameters
described above, intercepts 0.461 and 0.357 are calculated
for Collipulli and Ralun soil, respectively.
Figure 3b shows the plot for the intraparticle diffusion
model for the adsorption of NZVI on both soils. The intra-
particle diffusion model developed by Weber and Mor-
ris could present multilinearity indicating simultaneous
occurrence of several adsorption stages; in this adsorption
process, two stages can be identified. The intraparticle dif-
fusion constants can be calculated using Eq. (5). Table 3
shows the intraparticle diffusion constants (k int1, kint2), the
 Table 2  Kinetic and adsorption models
Name Equation Parameters Theoretical and empirical description

Kinetic models
t 1 1
Pseudo-second order model
Ct
= (Cm−cal )2 k2
+ Cm−cal
t(1) k2 is the rate constant of second order adsorption (mg The pseudo-second order kinetic model postulates that
­g−1 ­s−1) solute adsorption occurs on two available surface sites
of the adsorbent (Evangelou 1998)
1 B 1
Hyperbolic model
Ct
= Cm−cal ∙t
+ Cm−cal
(2) B (s) in an empirical constant This model uses hyperbola function to fit kinetic adsorp-
tion data (Fernández-Bayo et al., 2008)
Kinetic models involving solute transport mechanisms
Elovich equation Ct = 𝛽1 ln(𝛼 ∙ 𝛽) + 𝛽1 ln(t)(3) α is the initial sorption rate (mg ­g−1 ­s−1), and β (g ­mg−1) This model considers that the adsorption kinetic takes
is related to the extent of surface coverage and activa- place in two stages: a fast initial reaction associated
tion energy for chemisorption with the movement of the adsorbate to the most accessi-
ble parts of the adsorbent followed by a slower reaction
due to particle diffusion in and out of the adsorbent
micropores (Önal 2006)
Dimensionless Elovich Ct t tref is the longest operating time in the adsorption pro- This version of Elovich model uses dimensionless units,
Cref
= RE ln tref
+1
(4) cess (s), Cref is the amount adsorbed at time t = tref (mg dividing Ct and t experimental values by the highest
( ) ( )
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405

Intraparticle diffusion
­g−1) and RE = 1/(Crefˇ) is the approaching equilibrium obtained. This allows to describe adsorption process
factor. Based on this parameter obtained by plotting mechanism in stages defined by zones (Wu et al. 2009a)
Ct/Cref versus t/tref, these authors defined four char-
acteristic behaviours: when RE > 0.3 the curve rises
slowly (zone I); when 0.3 > RE > 0.1 the curve rises
moderately (zone II); when 0.1 > RE > 0.02 the curve
rises rapidly (zone III) and when RE < 0.02 the curve
reaches equilibrium instantly (zone IV)
Ct = kint t1∕2 + C(5) kint (mg ­g−1 ­s−1/2) is the intraparticle diffusion con- The pore-diffusion model of Webber-Morris is a single-
stant and C is a constant that gives an indication of resistance model derived from Fick’s second law of
the thickness of the boundary layer; the larger the diffusion. This process is controlled for adsorption on
intercept, the greater the boundary layer effect. If the pores; the initial rate is proportional to the solute
intraparticle diffusion occurs, the plot of Ct versus t1/2 concentration (Ioannou & Simitzis 2009)
follows a straight line and kint is determined from the
slope and the constant, C from the intercept. If the
plot passes through the origin, then the rate limiting
process is only due to the intraparticle diffusion. Oth-
erwise, some other mechanism along with intraparticle
diffusion is also involved

13
2397
 Table 2  (continued)
2398

Name Equation Parameters Theoretical and empirical description

13
Ct t Ri is obtained by plotting Ct/Cref versus t/tref from non- This version of intraparticle diffusion model uses dimen-
Cref
= 1 − Ri 1 − tref linear analysis data. There are four zones according sionless units, dividing Ct and t experimental values by
[ ]
Intraparticle diffusion dimensionless ( ) ( )1∕2

(6)
to the Ri value: 1 > Ri > 0.9 is called the weakly initial the highest obtained. This allows to describe adsorption
adsorption (zone I); 0.9 > Ri > 0.5, intermediately ini- process mechanism in stages defined by zones (Wu
tial adsorption (zone II); 0.5 > Ri > 0.1, strongly initial et al. 2009b)
adsorption (zone III) and Ri > 0.1, approaching com-
pletely initial adsorption (zone IV). When Ct = 0 (i.e.
there is no initial adsorption behaviour in an adsorp-
tion system), Ri = 1. In this case, the curve passes
through the origin. When Ct = Cref (i.e. adsorption
occurs at the very beginning of the process), Ri = 0.
Each adsorption system has its specific characteristic
curve
Adsorption isotherm models
Freundlich model CS is the concentration of adsorbed species (mg ­g−1), The Freundlich model does not have a mechanistic inter-
CS = KF CSe n(7)
CSe is the concentration in the supernatant solution pretation; it only represents an empirical approach to
( )1

(mg ­L−1), KF is the empirical Freundlich adsorption predict the species distribution between a solid/solution
coefficient and n is a linearity factor phase (Evangelou 1998)
Langmuir model K CSe CS and CSe have the same meaning as in the Freundlich The Langmuir model assumes that the adsorption of the
CS = Cm−cal 1+KL (8)
L CSe
model, Cm-cal is the maximum adsorption capacity (mg solute occurs at specific homogenous sites on the adsor-
­g−1) given by the model and KL is the empirical affin- bent (Escudey et al. 2004)
ity Langmuir coefficient
n
Sips or Langmuir–Freundlich model Cm−cal (CSe ) Kd is the apparent equilibrium Ce and Cs have the same The Langmuir–Freundlich model includes knowledge
CS = n
Kd +(CSe ) (9) meaning as in the Freundlich model, Cm-cal is the of adsorption heterogeneous surfaces. At low adsorb-
maximum adsorption capacity (mg ­g−1) given by the ate concentration, this model becomes the Freundlich
model and KL is the empirical affinity Langmuir coef- isotherm model, while at high adsorbate concentration
ficient it becomes the Langmuir isotherm (Ayawei et al. 2017)
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
0.8
Ct (mg g-1)
0.6
0.4
Collipulli
0.2 Ralun
PSO
Hyperbolic
0 (D%) and hysteresis index (HI), calculated using Cm-cal
0 100 200 300 400 500 600
Time (s)
Fig. 2  Sorption kinetic of NZVI on calcined Collipulli (●) and Ralun
(▲) soils. Symbols represent experimental data and lines represent
the curves described by pseudo-second order (-) and hyperbolic (···)
models
C constants and the correlation coefficient (R2). Finally,
Figure S4 presents dimensionless Elovich and intraparticle
diffusion adjustment on experimental data.
3.3 Adsorption Isotherms
Sorption isotherms were carried out at the equilibra-
tion time determined after the kinetics adsorption stud-
ies. When mixing soils with increasing concentrations of
NZVI, the mixtures produced extremely high Cs variations
between on Ralun calcined samples (Fig. 4).
The above results demonstrated that greater, on Ralun
calcined soil samples, control of the working pH was nec-
essary to obtain adsorption isotherms that can be described
by models. On the other hand, pH pre-treatment procedure
was not necessary to obtain adsorption isotherms on Col-
lipulli calcined samples. Figure 5 shows the adsorption
isotherms for both soils. After measuring S from adsorp-
tion curve points, an average pH = 5.4 ± 0.4 for Collipulli
and 6.3 ± 0.3 for Ralun was determined for each curve.
For Collipulli and Ralun soil, the maximum experimen-
tal amount of adsorbed NZVI corresponded to 2.127 and
2.205 mg ­mL−1, respectively. Data analysis by three iso-
therm models is presented in Table 4.
The best fit was obtained with the Langmuir–Freundlich
model for both soils, indicating that NZVI adsorption pro-
cess is formed by the contribution of chemical and physi-
cal interactions. Calculated maximum concentration was
higher over Collipulli than Ralun soil, while Kd values
for Collipulli and Ralun are 121.4 and 5996, respectively.
2399
3.4 Desorption Isotherms
The corresponding desorption isotherms were obtained,
and data were analysed with the Langmuir–Freundlich
model (Figure S5). After measuring S from desorption
curve points, an average pH = 5.9 ± 0.2 for Collipulli and
6.6 ± 0.1 for Ralun was determined for each curve, which
are consistent with the pH values of adsorption isotherms.
Desorption data was fitted using Langmuir–Freundlich
model adjustment. Table 4 displays desorption percentage
values for adsorption and desorption processes (Ma et al.
1993). Parameters indicate that NZVI adsorption is an
irreversible process, more pronounced over Collipulli
than Ralun soil. Desorption equilibrium constant, Kd, is
about 2000 times higher for Ralun. This agrees well with
the D% for both soils. Finally, both soils present negative
hysteresis index (HI) suggesting a chemically irreversible
process.
4 Discussion
Adsorption kinetics results determine the equilibrium
time, necessary for the construction of isothermal adsorp-
tion points, and are used to fit the kinetic and solute
transport mechanism models to provide a more detailed
description of the process. Equilibrium during absorption
kinetics experiments was a fast process (Fig. 2), reaching
maximum adsorption after the first 10 min on both adsor-
bents. Regarding kinetic model adjustment, the PFO model
did not fit either of the experimental data sets (Fig. 2) evi-
denced by low correlation coefficients (Table 3). On the
other hand, calculated maximum concentration (Cm-cal) for
the PSO model agrees with Cm and this model yielded the
highest R2 parameter, indicating that PSO best describes
the adsorption kinetics. Accordingly, this implies that the
interaction occurs at two sites of union and might suggest
that NZVI interacts by chemisorption with the calcined
soil. Solute transport mechanism model adjustment of
kinetic data enables to identify the steps involved in the
NZVI transport process. For instance, experimental data
for calcined Ralun soils are well-described by the Elovich
equation (Fig. 3a), including linear regression analysis
(Figure S3), meaning heterogeneous surface character-
istics. Cáceres-Jensen et al. (2013) observed that high
organic matter content can confer some characteristics
of energetically homogeneous surfaces on Andisol full
soil samples, which is lost after Ralun calcination due
to degradation of organic matter (Table 1). The higher α
for Collipulli over Ralun (Table 3) implies that, if part of
the process is controlled by chemisorption, this possibly
occurs much faster over Collipulli than Ralun surfaces at
13
2400 Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405

Fig. 3  Fitting of Elovich (a)

a b
1.0
and intraparticle diffusion (b)
model for the kinetic adsorp- 0.8
tion of NZVI on Collipulli and

Ct (mg g-1)
Ralun soils 0.6

0.4
Collipulli
0.2 Ralun
Elovich
0
0 100 200 300 400 500 600
Time (s)

are found in zone III, which indicates that the adsorption

Fig. 4  Adsorption isotherm of NZVI on calcined Ralun soil without
pH adjustment. Measured pH for each experimental point is presented
over the data
the beginning of the process. The β parameter was similar
on both soils; thus, despite the process initially occurring
faster over Collipulli, the amount of surface covered by
the adsorbate was most likely similar on both calcined
soils. From the Elovich linear equation fitting (Figure S3),
intercepts indicate that while adsorption is relatively rapid,
it is not instantaneous and takes place in two consecutive
stages. Accordingly, as Wu et al. (2009a) proposed after
dimensionless Elovich analysis (Figure S4a), both soils
increases rapidly at the beginning of the process.
Going deep in NZVI transport mechanism description,
the intraparticle diffusion model permits adsorption stages
definition which has been applied for modelling nanopar-
ticle adsorption processes before (Hamouda & Abhishek
2019). Accordingly, NZVI adsorption process takes place
in two stages (Fig. 3b). Model adjustment indicates that
another process besides intraparticle diffusion takes place
in the adsorption of NZVI. As has been described for other
solute-sorbents systems (Cáceres-Jensen et al. 2013), if the
external resistance to mass transfer surrounding is discarded,
the first line will describe the gradual adsorption stage and
depicts macropore diffusion, while the second line repre-
sents micropore diffusion until equilibrium achievement
(Önal 2006). The calculated intraparticle diffusion constants
reveal a noticeable change in slope for both soils (Table 3).
Initially, the NZVI were adsorbed by the external macropore
structure of soil, and consequently the sorption rate was
very high. After saturation of the macroporous structure,
the NZVI diffused in the internal surface pores within the
soil particle (micropore structure) and were adsorbed. Later,
the diffusion resistance increased, which caused the diffu-
sion rate to decrease. When the NZVI concentration was
decreased, the diffusion rate became lower, and the diffusion
processes reached the final equilibrium stage. The intercept
C (Table 3) is proportional to the extent of the boundary
layer thickness; that is, the larger the intercept the greater

Fig. 5  Adsorption of NZVI

on soil. The symbols and lines
represent the experimental data
and the model description,
respectively. a Collipulli soil. b
Ralun soil

13
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405 2401

Table 3  Parameters from adsorption kinetic and solute transport Table 4  Isothermal model fit parameters
mechanism model adjustments
Collipulli Ralun
Collipulli soil Ralun soil
Adsorption
Cm (mg ­g−1) 0.80 0.73 Langmuir
Kinetic models Cm-cal (mg ­g−1) 3.01 3.84
Pseudo-second order KL (L ­mg−1) 8.89 × ­10−3 6.99 × ­10−3
Cm-cal (mg ­g−1) 0.81 0.73 R2 0.984 0.963
k1 (g ­mg−1 ­s−1) 0.095 0.085 Freundlich
R2 0.998 0.997 KF (mg ­g−1) 0.133 9.9 × ­10−2
Hyperbolic N 1.998 1.691
qmax (mg ­g−1) 0.81 0.73 R2 0.970 0.939
B (s) 13.06 15.97 Langmuir–Freundlich
R2 0.998 0.997 Cm-cal (mg ­g−1) 2.9 2.4
Solute transport mechanism models Kd 121 5996
Elovich N 1.028 2.087
α (mg ­g−1 ­s−1) 311.8 26.9 R2 0.984 0.986
−1
β (g ­mg ) 18.8 17.2 Desorption
R2 0.920 0.969 Langmuir–Freundlich
Elovich dimensionless Cm-cal (mg ­g−1) 6.7 × ­10−5 0.104
RE 0.06 0.08 Kd 470 982427
R2 0.916 0.969 N 1.312 2.954
Intraparticle diffusion R2 0.951 0.999
kint1 (g ­mg−1) 1.56 × ­10−2 1.35 × ­10−2 D% 0.002 4.370
−1
C1 (g ­mg ) 0.55 0.49 HI − 99.9 − 95.6
R2 0.866 0.927
kint2 (g ­mg−1) 5.99 × ­10−3 6.96 × ­10−3
−1
C2 (g ­mg ) 0.66 0.56
compared to a solved solute system, nanoparticle suspen-
R2 0.951 0.957
sion stability depends on their size (Cornelis et al. 2013),
Intraparticle diffusion dimensionless
concentration (Ibrahim et al. 2019), pH (Flory et al. 2013;
Ri 0.18 0.23
Mpinda Tushiminine 2014), among other parameters. Thus,
R2 0.834 0.930
special experimental procedures to ensure particle stabil-
ity during the duration of the adsorption experiments are
required (‘Section 2.3.1’). Second, results-modelling for
boundary layer effect. Positive intercepts indicate a rapid nanoparticle adsorption isotherms is a controversial topic.
sorption in a short time on adsorbents with a wide distribu- Two major theories are commonly used to model soil
tion of pore sizes (Wu et al. 2009b). This intercept decreases adsorption or sorption equilibrium processes: the Freundlich
with increasing surface heterogeneity of soils (Cáceres- and the Langmuir approach (Evangelou 1998). While Fre-
Jensen et al. 2013). The intraparticle diffusion dimension- undlich model has no mechanistic interpretation, the Lang-
less model (Figure S4b) displays Ri that falls in zone III for muir model was developed to describe vapour adsorption on
both soils, indicating strong initial adsorption. This agrees a homogeneous surface. Considering the contrast between
with assumptions of the pseudo-second order, Elovich and the complexity of nanoparticle suspension adsorption sys-
intraparticle diffusion models, describing a fast adsorption tem, the simplicity of the Freundlich model interpretation
process comprised of an initial fast equilibrium that takes and the specificity of the Langmuir model assumptions,
place at the external micropore structure of the calcined soil. the validity of the interpretation of adjusting these models
Equilibrium between solved solute solutions with to NZVI-adsorption should be matter of discussion. At a
increasing concentration and adsorbents is a common pro- minimum, acknowledgement, and discussion of differences
cedure used to evaluate isothermal adsorption in soils or between systems is essential if model adjustments and their
its fractions (Evangelou 1998), achieving a thermodynamic parameters are compared between different systems (parti-
description of the process. However, equilibria to evalu- cle composition, size and adsorbents characteristics, from
ate adsorption of suspended particles in solution, as nano- same or different authors). For instance, at present report,
particles, are still a complex aspect for two main reasons: during isotherm experimental point obtainment, when mix-
experimental and results-modelling. First, experimentally, ing soils with increasing concentrations of NZVI at first,

13
2402
the mixtures produced extremely high Cs variations between
repetitions—particularly for calcined Ralun soil—preclud-
ing attainment of conclusive results (Fig. 4). Later, it was
discovered that calcined Ralun soil-NZVI mixture provoked
high system-pH variations. Considering that pH values were
different at each experimental point of the isotherm and the
variable surface charge of calcined Ralun soil (Figure S1),
the imprecise Cs results are not surprising, preventing con-
ventional isothermal construction. Such an unpredictable
behaviour of variable surface charge adsorbents for NZVI
has been reported by other authors. Micic et al. observed
that the mobility poly(acrylic acid)-coated ZVI nanopar-
ticles through columns filled with variable surface charge
natural minerals (dolomite, muscovite) (Nosrati et al. 2009;
Zhou et al. 2020) did not behaved as predictable than when
using sand and glass beads as adsorbents (Micic et al. 2017).
Therefore, a greater control of the working pH when using
variable surface charge adsorbents as Ralun calcined sam-
ples is necessary to obtain isotherm points adequate for fit-
ting; this may be carried out by the addition of HCl solution
before adsorption point obtainment (Fig. 5). The effect of
pH on the adsorption process is important as it could vary
the number of binding sites on the adsorbent, especially on
a variable surface charged adsorbent at calcined Ralun soil.
Additionally, pH could influence loading of the NZVI and
cause agglomeration between particles, which can be mis-
takenly interpreted as an adsorption phenomenon. Collip-
ulli soil does not present this pH-mediated effect due to its
marked permanent charge character (Figure S1). Therefore,
the pre-treatment HCl addition procedure was not necessary
to obtain adsorption isotherms with Collipulli calcined soil.
Regarding isothermal model adjustment of experimental
data, Langmuir–Freundlich model fitted best for both soils
(Table 4), suggesting that NZVI adsorption process does not
correspond to a single type of process and consist of a com-
bination of both chemical and physical process. Zhang et al.
(2017) described that the adsorption of carboxymethyl cel-
lulose stabilised NZVI over glass beads, sand, aluminium-
oxide- and iron-oxide-coated sands obeyed the Langmuir
model. A later work by Zhang et al. (2019) reported that
adsorption of macromolecule-stabilised NZVI over Argosols
and Cambosols was described by the Langmuir isothermal
model. Thus, as anticipated, adsorption depends highly on
particle and adsorbent nature. The isotherm produced by the
Langmuir–Freundlich model for Collipulli soil corresponds
to L-type according to the classification of isotherms by
Giles et al. (1974). The curve slope steadily falls with rise
in NZVI concentration as vacant sites become more difficult
to find with the progressive covering of the soil surface.
This describes a high affinity between NZVI and calcined
Collipulli soil. On the other hand, the isotherm obtained for
the Ralun soil is a S-type, which indicates that adsorption
can occur through interactions between the NZVI particles
13
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
and then over calcined Ralun soil surface adsorption sites
(Giles et al. 1974). Calculated maximum concentration was
higher over Collipulli than Ralun soil (Table 4), which may
be in part explained by the different ESSA values measured
(Table 1). Kd values suggests that adsorption equilibrium is
thermodynamically more stable over Ralun calcined soil,
attributed to the lower crystalline degree of dominant miner-
als present this Andisol sample (Table 1). Therefore, NZVI
isothermal adsorption over the inorganic fraction of the vol-
canic soils under study is a complex system that, depend-
ing on soil surface characteristics, requires monitoring and
control of parameters such as pH to obtain repetitive results.
The interaction between NZVI and calcined soils consist
of a combination between physical and chemical processes
that most likely depends on adsorbents surface area and
mineralogy. To establish reversibility degree of the process
more definitively, desorption isotherm analysis should be
considered (Figure S5). The difference between adsorbed
and desorbed NZVI amounts indicates the existence of an
irreversible adsorption attributed to specific interaction in
high energy sites on calcined soils. This agrees with the
pseudo-second order model that fitted best kinetic adsorp-
tion data which is typically associated with dominant chemi-
cal interactions. Moreover, according to the calculated maxi-
mum concentration desorbed (Table 4), NZVI are mostly
retained by the absorbents; a more pronounced behaviour on
Collipulli than Ralun calcined soil. The desorption equilib-
rium constant (Table 4), Kd, is about 2000 times higher for
Ralun, highlighting the strength of the bond formed between
NZVI and Collipulli calcined soil. This behaviour is also
corroborated by the D% for both soils. Finally, the highly
negative hysteresis index (HI) suggests that adsorption over
both calcined soils is essentially a chemically irreversible
process and possibly dominated by electrostatic interactions.
This observation is more prominent in Collipulli than Ralun
soil. Thus, in mild conditions NZVI adsorbed will not be
removed over either surface.
Taken together, the outcomes from this work suggest
that the NZVI adsorption process over the inorganic frac-
tion of volcanic soil is a kinetically fast process described
by pseudo-second order model, implying that it takes places
over two different bonding sites on the adsorbent. This is
consistent with information obtained by the Elovich and
intraparticle diffusion models: adsorption takes place at
two consecutive stages, begging with fast adsorption at
macropores followed by diffusion to micropores until reach-
ing equilibrium. Adsorption isotherms demonstrate that the
inorganic fraction of Collipulli soil reaches higher maximum
amounts of adsorbed NZVI, possibly due to its higher sur-
face area. Modelling allowed thermodynamic description
of the adsorption process and was better adjusted by the
Langmuir–Freundlich model, indicating that the process is
a combination of physical and chemical interactions. The
Journal of Soil Science and Plant Nutrition (2022) 22:2392–2405
modelling parameters reveal that the adsorption process is
almost 50 times stronger over the inorganic fraction of Ralun
than that of Collipulli. Finally, desorption demonstrated
that while both physical and chemical processes are at play,
chemical adsorption dominates markedly, as evidenced by
the desorption percentages and negative hysteresis indexes.
These outcomes elucidate the adsorption process of com-
mercially available ZVI particles over the inorganic frac-
tion of volcanic soils. Therefore, despite the effect of NZVI
has been thoroughly described for hydroponical systems, it
is reasonable to induce that the irreversible adsorption of
NZVI onto the inorganic fraction of Chilean volcanic soils
determines low concentration of nanoparticles on the water
soil phase; thus, probably low plant uptake is forecast in this
type of soils.
5 Conclusions
Zerovalent iron slurry is a widespread remediation tool for
organic pollutant degradation in soils, but there is a lack of
knowledge on the environmental fate of its leftovers due in
part to the difficult description of the adsorption process
of particle suspension over full soil. A way to shorten this
information gap could be to previously study the adsorption
process of zerovalent iron particle suspension on soil frac-
tions by composition. Thus, the system comprised of com-
mercial zerovalent iron, that includes nanoparticles (NZVI),
and the inorganic fraction of two volcanic soils was fully
characterised regarding the adsorption processes. Kineti-
cally, the interaction of NZVI is a fast process that takes
place in two stages and in two active sites over the adsor-
bents. Isothermal adsorption proved to require pH adjust-
ment of the system that considered the Andisol as adsorbent,
due the significant influence of pH on adsorbent surface
charge. Experimental adsorption isotherms were better fit-
ted by the Langmuir–Freundlich; thus, NZVI adsorption is
a mix of physical and chemical interactions. Finally, the low
amount of NZVI desorbed suggests an irreversible chemical
adsorption on specific active sites of the adsorbents.
This reveals that NZVI adsorption over the inorganic
fraction of volcanic soils is a complex process that requires
strict pH monitoring and control during adsorption to pre-
vent surface charge variation between measurement points.
Collectively, these results suggest that NZVI will tend to
become irreversibly adsorbed over the inorganic fraction of
soils. Regarding environmental implications, these results
likely indicate that retention of NZVI particles by inorganic
components of volcanic soils will extend their reactivity.
This implies that there are overall low risks of NZVI trans-
port through soil profiles, co-transport of iron-adsorbed
2403
compounds (pollutants or nutrients) into aquifers and low
possibility of plant uptake.
Supplementary Information The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 42729-0​ 22-0​ 0816-w.
Acknowledgements We thank Alyssa Grube for assistance in language
support.
Funding The authors are grateful for funding provided by FOND-
ECYT (11170300) and CEDENNA (AFB180001).
Declarations
Conflict of Interest The authors declare no competing interests.
Open Access This article is licensed under a Creative Commons Attri-
bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
as you give appropriate credit to the original author(s) and the source,
provide a link to the Creative Commons licence, and indicate if changes
were made. The images or other third party material in this article are
included in the article's Creative Commons licence, unless indicated
otherwise in a credit line to the material. If material is not included in
the article's Creative Commons licence and your intended use is not
permitted by statutory regulation or exceeds the permitted use, you will
need to obtain permission directly from the copyright holder. To view a
copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/.
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