3.889 5.

Article

Design and Construction of a

Prototype for Arsenic Retention in
Mining-Contaminated Waters by
Application of Nanoparticles-Based
Technosols

Darío Bolaños-Guerrón, Iván Galarza, Erika Llumiquinga, Theofilos Toulkeridis and Luis Cumbal

https://doi.org/10.3390/su15021286
 sustainability
Article
Design and Construction of a Prototype for Arsenic Retention
in Mining-Contaminated Waters by Application of
Nanoparticles-Based Technosols
Darío Bolaños-Guerrón 1,2 , Iván Galarza 1 , Erika Llumiquinga 2 , Theofilos Toulkeridis 1, *
Citation: Bolaños-Guerrón, D.;
Galarza, I.; Llumiquinga, E.;
Toulkeridis, T.; Cumbal, L. Design
and Construction of a Prototype for
Arsenic Retention in
Mining-Contaminated Waters by
Application of Nanoparticles-Based
Technosols. Sustainability 2023, 15,
1286. https://doi.org/10.3390/
su15021286
Academic Editor: Guannan Liu
Received: 19 September 2022
Revised: 21 November 2022
Accepted: 6 December 2022
Published: 10 January 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Sustainability 2023, 15, 1286. https://doi.org/10.3390/su15021286
and Luis Cumbal 2
1 Departamento de Ciencias de la Tierra y la Construcción, Universidad de las Fuerzas Armadas ESPE,
Sangolquí 171103, Ecuador
2 Centro de Nanociencia y Nanotecnología (CENCINAT), Universidad de las Fuerzas Armadas ESPE,
Av. Gral. Rumiñahui s/n, Sangolquí 171103, Ecuador
* Correspondence: ttoulkeridis@espe.edu.ec
Abstract: A large number of heavy metals are usually contained in mine-derived liquids, which could
cause contamination of surrounding water sources. Due to the detrimental effects on the environment
and health, conventional treatments have been employed to capture heavy metals in mining-polluted
streams. This study shows the results of the operation of a built prototype for the retention of arsenic
contained in waters contaminated by mining activities using Technosols (mixtures of local soil with
nanoparticles). Our team previously run laboratory tests using fixed-bed columns to find out the
best dose of the Technosol (97% soil + 3% nanoparticles). Based on these results, the sizing and
building of a scale model were conducted, which in turn was used to evaluate the performance of the
treatment in a concrete channel packed with reactive barriers. Variations in water volume, barrier
separation and gate opening were tested to analyze the behavior of the proposed system and to obtain
the most optimal hydraulic retention time that allowed the prototype to reach an arsenic retention
level of a minimum of 70%. Moreover, to analyze the procedure under conditions of high arsenic
contamination, samples of mine tailings were enriched with the toxic metalloid. It was found that
the content of Fe in the local soil allowed adsorption of the contaminant, which was subsequently
compared with the increase in the uptake of As due to the Fe/FeS multicomponent nanoparticles
(NPs), dosed in the Technosol in a proportion of 97% soil + 3% NPs. The best treatment achieved
70.5% of As removal in ten cycles with a volume of 44 L. Tests were run at a maximum input flow
rate of 43.8 L·min−1 , an output flow rate of 13.2 L·min−1 , a speed of 6.0 m·min−1 and a hydraulic
retention time of 3.4 min per cycle. Results of arsenic retention using this prototype suggest that this
simple and inexpensive technological setup could be scaled up to a functional field application to
effectively capture the toxic metalloid.
Keywords: arsenic retention prototype; reactive barriers channel; Technosols; nanoparticles
1. Introduction
A worldwide problem is the contamination of the environment due to mining pro-
cesses, and even more so when such activities are developed in sensitive areas and without
any legal control [1–3]. In this respect, a rise in artisanal and illegal mining has led to
an increase in heavy metal pollution in the province of El Oro, Ecuador [4–6] (Figure 1).
These mining activities have caused serious damage in areas near rivers or effluents [7,8].
In response to the encountered mining pollution problems, this current study proposes
the use of Technosol combined with nanoparticles in order to recover polluted soil and
water [9–11]. In previous studies, the uptake of heavy metals by Technosols prepared in
Ecuador has been evaluated mainly at the laboratory level [12–15]. Moreover, iron-based
nanoparticles prepared by green or conventional synthesis have been used to remove toxic
metals from polluted water and soils under laboratory experimental conditions, such as the
https://www.mdpi.com/journal/sustainability
Sustainability 2023, 15, 1286 2 of 17

multicomponent nanoparticles biosynthesized with orange peel (Citrus sinensis) extract [16].
These tiny particles contain Fe0 in the core and are surrounded by a cover of FeS precipi-
tates. This chemical composition gives the nanoparticles enhanced sorption properties to
selectively capture heavy metals. Particularly, the active groups of the zero-valent iron and
ferrous sulfide chemically retain arsenic through the formation of Fe-oxide-As3+ complexes,
complexation with iron hydroxides, reduction to As0 or As3+ in the presence of Fe0 [17]
and surface complexation by FeS [18] The capability of nanoparticles to immobilize heavy
metals dissolved in water was over 80%, reaching even 99% for arsenic, allowing the design
and elaboration of Technosol mixed with nanoparticles [13,14]. A silty clay extracted from
a mining area was used as Technosol. A fast removal of metals was observed within 5 min
with the best dose of 99.75% soil + 0.25% nanoparticles, and an immobilization higher than
90% was achieved. On the other hand, it was analyzed the retention of arsenic with the
use of Technosol prepared with ferric soil and nanoparticles [13]. Using Vensim software,
a model was developed capable of scaling and predicting the behavior of the adsorbent.
These results allowed the understanding of the process of adsorption and saturation of
the system, an aspect of great importance for a precise application in the field (Figure 1).
Finally, it was possible to evaluate the heavy metal retention process in a laboratory-scale
column prototype [19]. The best treatment was discovered to be a Technosol prepared with
3% nanoparticles + 97% soil, reaching a removal of 70% on average.

Figure 1. Location of sampling points.

Therefore, the main objective of the current study has been to design, build and
evaluate a prototype for arsenic removal from mining-polluted water using Technosol
combined with multicomponent nanoparticles as sorbent material. The results are expected
to provide the needed information to move from a small-scale prototype toward a functional
field application.
Sustainability 2023, 15, 1286 3 of 17

2. Materials and Methods

2.1. Soil and Water Sampling
Sampling was performed within an area between towns of Zaruma, Portovelo and
Piñas, El Oro province, Ecuador (Figure 1). Soil samples were taken from two locations (S1
and S2). Zip plastic bags were used to collect soil samples. Mine tailings were collected in
sedimentation pools (A1) located in Santa Mónica Plant, Portovelo. Plastic bottles were
used for the collection, stored in a freezer at 5 ◦ C of temperature and transported to the
laboratory for the corresponding chemical analysis.

2.2. Laboratory Tests

The selected soil samples were tested using the ASTM D2487-11 method (Unified Soil
Classification System) in order to characterize the content of gravel, sand, silt or clay [20].
For the determination of the cation exchange capacity of soil, ammonium acetate, sodium
chloride, formaldehyde, phenolphthalein and sodium hydroxide were used [21]. Exchange-
able or macrometal cations were obtained with the ammonium acetate method [22]. While
for carbonates, sulfuric acid, phenolphthalein and ethanol were used. Moisture was deter-
mined by method ASTM D-2216, granulometry by ASTM D422, liquid and plastic limits
ASTM D-4318 [23–25]. Electrical conductivity was measured using ISO 11265 Standard [26]
and [27] protocols, the organic content and pH were measured by the AASHTO Stan-
dards [28] and ISO 10390 Standard [29], respectively. Concentrations of mg/L and µg/L
were converted to mg/kg according to the following equation [30]:
mg

mg Concentrationofmetal L ∗ [Samplevolume(mL)]
   
Metal = (1)
kg
h i
Sampleweight(kg) ∗ 1000
1L
mL

Heavy metals dissolved in the mine tailings were chemically analyzed using a flame
Perkin Elmer AA800 atomic absorption spectrometer coupled with FIAS 100. Standardized
procedures were used for chemical analysis of metals and arsenic [31]. For As we added
1 mL of tailing, 1 mL of pure hydrochloric acid and 1 mL of the solution of 5% potassium
iodide plus 5% ascorbic acid in each test tube, stirred and after 45 min, 7 mL of distilled
water was added. Readings of As were performed in the AA-FIAS system. For equipment
calibration, heavy metal AA standards of 1000 mg/L were utilized.

2.3. Synthesis of Multicomponent Nanoparticles (Fe/FeS)

With the need to produce nanomaterials on a larger scale while maintaining their
nanometric size and chemical properties, two protocols were combined. Protocols devel-
oped by Stael & Cumbal and Yaacob & How were used [32,33]. The process is summarized
in Figure 2.

2.4. Nanoparticle Characterization

Transmission electron microscope (TEM) images were digitally recorded for morpho-
logical studies (Tecnai G2 Spirit TWIN, FEI, Eindhoven, The Netherlands). The size and
morphology of the nanostructures were characterized using a field emission gun scanning
electron microscope (FEG-SEM, Mira3 Tescan). Samples were directly deposited on alu-
minum simple holders. The operation voltage ranged between 3 and 5 kV. In a classic pro-
cedure, low-magnification (Å~2000) micrographs were obtained to determine the size dis-
tribution. Analysis of the crystalline structure of the nanoparticles was performed by XRD
diffractometer (PANalytical EMPYREAN) operating in a θ–2θ configuration in the Bragg-
Brentano geometry and equipped with a copper X-ray tube (Kα radiation = 1.54056 Å)
operating at 45 kV and 40 mA and energy dispersive spectroscopy (EDS) techniques as
used to determine the chemical properties.
Sustainability 2023, 15, 1286 4 of 17

Pour 3 L of water
Add 60 g of clay from
previously filtered in a 5
soil S2.
L container.

Pass only the liquid Shake for 5 min and let

phase to the reactor. the mixture settle for 2
min.

In the reactor, add 12

mL of FeCl3 and 10.2
Finally add 120 mL of
mL of Na2SO4, close the
NaBH4 0.4M.
reactor and shake at 40
rpm.

Figure 2. Scheme of the nanoparticle synthesis of the current study.

2.5. Set Up of the Treatment System (Prototype)

The prototype was built up with concrete and its surface was treated with a paint-type
waterproofing. The prototype has two storage tanks, one for polluted water and another
for treated water, connected through a rectangular channel where removal of heavy metals
takes place (Figure 3). The as-prepared sorbent material was placed in bags fabricated
with a geotextile and secured with plastic ties to supports. Those elements were built with
a frame of metallic square tube and an electro-welded mesh. To fix the supports in the
desired positions, sections of welded angles were placed over the plates anchored to the
walls and the floor of the reaction tank (Figure 4). The latter metallic structure was used
also as rails. Moreover, rsliding
(PANalytical EMPYREAN)
metal gates were used operating in aflow
to control the θ–2θofconfiguration in
polluted water.
ray tube (Kα
Figure 5 illustrates the steel supports to hold the barriers containing Technosols. radiation =

Figure 3. Prototype construction scheme.

Sustainability 2023, 15, 1286 5 of 17

Figure 4. Steel plates and angles detail.

Figure 5. Steel support detail.

Dimensions of the polluted water storage tank are 0.8 × 0.8 × 0.7 m3 with a maximum
capacity of 416 L, leaving 5 cm off. The treated water storage tank is 0.8 × 0.8 × 1.0 m3 .
The channel where the reaction barriers are fixed is 3 m long, with 0.8 m of width and
0.4 m of depth having a slope of 2%. The central channel and storage tanks are connected
by gutters of 0.5 m length and 0.2 m width. The prototype was built to accommodate a
Sustainability 2023, 15, 1286 6 of 17

series of reactive barriers packed with Technosol and nanoparticles, placed alternately. This
setup is located inside the Universidad de las Fuerzas Armadas ESPE campus, Sangolquí,
central Ecuador, within the green area next to the wastewater treatment plant, to which the
drainage of the prototype was connected.

2.6. Construction of the Treatment System Prototype

The development and construction of the prototype began with the cleaning and
stakeout of the designated area for implementing the prototype inside the Universidad
de las Fuerzas Armadas ESPE. This was followed by excavation with a backhoe and the
with f’c = 140of
application kg.cm
an improvement layer. On this surface, the 5 cm concrete blinding was cast
with f’c = 140 kg·cm2 , then a 5 mm × (15 × 15 cm2 ) electro-welded mesh was formed and
placed, tof’cgive
resistance waykg.cm
= 240 to the casting of the floor and walls of 10 cm thick concrete with a resis-
tance f’c = 240 kg·cm2 (Figure 6A). The casting was carried out in two stages, starting with
the final tank which is deeper, and then the channel and the initial tank. After the drying
and curing period, the entire surface was waterproofed. Finally, labors related to metal
parts were carried out, such as placing the plates, gates and covers. Figure 6B shows the
prototype after finishing the concrete construction. Figure 6C shows one of the 60 × 40 cm2
metal panels that serves as a support for the Technosol barrier in a 40 × 30 cm2 bag made
of geotextile as shown in Figure 6D.

Figure 6. Components of the prototype. (A) Concrete casting of the prototype; (B) prototype
completed construction; (C) steel support; (D) geotextile bag.
Sustainability 2023, 15, 1286 7 of 17

2.7. Prototype Experimentation

Before conducting the removal of arsenic(V) with the prototype, hydraulic properties
of the treatment section were estimated. For these experiments, barriers were fixed on the
reaction channel separated by 30, 20 and 10 cm (Figure 7). Then, from 13.33 to 75 kg of
only soil was put in geotextile bags and secured with plastic ties to the supports of the
metal frame and to the electro-welded mesh. Next, the right storage tank was filled with
potable water from the ESPE network up to 100 or 200 L. Hydraulic experimentation started
when the right gate was opened and time was recorded. With the purpose of avoiding the
waste of water, a pump was installed to recirculate it at the end of each cycle. For the tests
of As(V) removal from mine tailings, bags were filled with 12.33 kg of soil and 0.4 kg of
nanoparticles. Tables 1 and 2 list the data of the described experimental work.

Figure 7. Metal panel placement scheme.

Sustainability 2023, 15, 1286 8 of 17

Table 1. Experimental data.

Useful Width of Channels

Code Tank 1 Volume (L) Barrier Separation (cm) Gate 1 Opening (cm) Gate 2 Opening (cm)
between Barriers (cm)
P1 100 10 5 1 2
P2 200 10 5 1 2
P3 100 20 15 1 2
P4 200 20 15 1 2
P5 100 30 25 1 2
P6 200 30 25 1 2
P7 100 10 5 0.5 0.5 after 1 h of stagnation
P8 100 10 5 1 0.5
P9 44 10 5 0.5 0.5 after 1 h of stagnation
P10 44 10 5 0.5 0.2

Table 2. Barriers’ data for the tests.

Code # Barriers Barrier Dosing Soil Weight (kg) NPs Weight (kg) Distribution of Material in Barriers
P1 25 100% soil 75 0 Evenly divided across all barriers
P2 25 100% soil 75 0 Evenly divided across all barriers
P3 13 100% soil 39 0 Evenly divided across all barriers
P4 13 100% soil 39 0 Evenly divided across all barriers
P5 9 100% soil 27 0 Evenly divided across all barriers
P6 9 100% soil 27 0 Evenly divided across all barriers
Divided 50% between 15 initial barriers
P7 25 100% soil 60 0
and 50% between 10 final barriers
Divided 50% between 15 initial barriers
P8 25 100% soil 60 0
and 50% between 10 final barriers
P9.1 25 100% soil 13.33 0 Evenly divided across all barriers
P10.1 25 100% soil 13.33 0 Evenly divided across all barriers
P9.2 25 97% soil + 3% NPs 12.93 0.40 Evenly divided across all barriers
P10.2 25 97% soil + 3% NPs 12.93 0.40 Evenly divided across all barriers

In the first stage, six options were tested without restriction in Gate 2, varying the
barrier separations between 10, 20 and 30 cm and using a volume of polluted water of 100
and 200 L, under the conditions described in Tables 1 and 2. Considering the results of the
hydraulic calculations, to examine the retention of As, experimental conditions of test P1
and P2 were chosen. For each option, five cycles were introduced with recirculation of the
tailing samples. Due to the low retention percentages of As (V) achieved with the previous
tests, some parameters were changed keeping the separation of barriers in 10 cm.
To restrict the output of the liquid and increase the residence time in the system, the
opening of Gate 2 was changed to 0.5 cm in tests P7, P8, P9 and 0.2 cm in P10 (Figure 8). In
options P7 and P9, the exit gate was closed for 1 h to find out the effect of the long-term
contact between water and reactive barriers. Water samples were taken every 15 min. In
cases P8 and P10 the gate was opened throughout the test. In P7 and P8 were treated
100 L and in P9 and P10, 44 L was used. This variation was performed considering the
total amount of nanoparticles that were synthesized at the time of testing. Therefore, the
volume of water was decreased depending on the amount of soil to be used to maintain a
proportion equal to 97% soil + 3% NPs.
Sustainability 2023, 15, 1286 9 of 17

Figure 8. Prototype arrangement. (A) Inflow channel for treatment of As-polluted tailings; (B) loca-
tion of barriers separated by 10 cm; (C) output gate flow restriction.

In all four cases, increased hydraulic retention times were specified with the restriction
of the final gate, so As retention tests were enhanced. Additionally, a variation of P9
and P10 was included in relation to the composition of the barriers for determining the
contribution of nanoparticles compared with the use of only soil. In cases P7, P9.1 and P9.2
were performed five cycles, while ten cycles were completed in P8, P10.1 and P10.2.

2.8. Hydraulic Calculations

Hydraulic tests were conducted using a fixed volume of water (see Table 1) without
continuous input. The flow rate was calculated assuming a flow under a flat gate using the
following equation:
𝑄== ab
𝑎𝑏∈∈C𝐶𝑣 √2𝑔(𝐻 −∈∈ 𝑎)
q
Q 2g( H 𝑜−
v a)
o (2)
−1
where Q is the flow rate passing −1
 through the gate (L.s ), a is the opening of the gate (m),
b is the width of the gate (m), ∈ is the contraction coefficient, Cv is the
 speed coefficient
and Ho is the total load before the gate (m). The contraction coefficient ∈ depends on the
degree of opening of the gate and the load H. For small openings, the contraction coefficient,
∈ = 0.615. The speed coefficient for flat gates in channels, Cv = 0.96 [34]. Similar conditions
to those of a baffled channel flocculator with horizontal flow were assumed for the flow
path through the barriers. The total length, useful channel width, maximum normal depth
(measured at hydraulic tests) and maximum flow are taken to calculate the system speed
and retention time using the following equations:
𝑄
𝑣=
𝐴
Q
v= (3)
𝐴 = 𝑏A ∗ℎ (4)
A 𝑇= b ∗𝐿 h
𝑟 = (4)
ℎ
L
Tr = (5)
−1 h
where Q is the maximum flow calculated with Equation (2), v is the flow rate between bar-
riers (m·s−1 ), b is the useful width of the channels between barriers (m), h is the maximum
Sustainability 2023, 15, 1286 10 of 17

normal depth measured at experimentation (m), L is the total length of travel between
barriers (m), Tr is the hydraulic retention time (s).

3. Results and Discussion

3.1. Soil Characterization
Organic matter (OM) is formed of a wide variety of substances, and their specific nature
is determined by plants and animal waste that break down in a site continuously [35,36].
The measured values were 1.68% for S1 and 2.64% for S2, demonstrating a low content of
OM. Cation exchange capacity (CEC) reflects the total exchangeable cations of a soil; the
higher the CEC, the greater the number of cations that the soil is able to retain [37,38]. It
depends mainly on the quantity and type of clays and the organic matter content present
in the soil, being CEC of 10.22 and 18.4 meq/100 g for S1 and S2, respectively [39–41]. The
values are consistent with the content of organic matter and are classified as low, being
between 10 and 20 meq/100 g. The low levels of OM and CEC are related to their condition
as inert soils, so they are not used for agricultural purposes [42].
Hydrogen potential (pH) measures the degree of acidity of a soil, meaning the concen-
tration of hydrogen ions (H+ ) in the soil, related by pH = −log(H+ ). It is an indicator of
the availability of essential nutrients and the toxicity action of other elements. At an acidic
pH (pH < 6) there is a decrease in N, P, K, Ca and Mg due to solubility restrictions and
adsorption drop, while Al and Mn increase their concentrations in the exchange process
that causes toxicity [43–45]. The results were 5.61 for S1 and 5.52 for S2. Therefore, both
soils are moderately acidic.
The type of soil texture is quite related to water properties. Sandy soils are very per-
meable, the clayey ones have greater water retention capacity and the silty types are more
impermeable. Depending on the degree and type of structure, the hydraulic characteristics
may vary [46–48]. Soil S1 exhibited the following characteristics: < 50% passed through a
No. 200 sieve size, a liquid limit of 37%, a plastic limit of 20% and a plastic index of 17%.
Under the criteria of the Unified Soil Classification System (USCS), this soil is a clayed sand
(CS) [49]. Soil S2 yielded > 50% of granules passing through a No. 200 sieve size, a liquid
limit of 40%, a plastic limit of 30% and plastic index of 10%. Moreover, using the USCS
classification, this soil is a lean clay (CL).
Both soils failed to meet the regulated limits given in the national regulations of
Ecuador for soil quality criteria in regard to Cr, Ni, Zn and As [50]. Soil S1 exceeded
3.2 times the limit for Cd and 1.74 times for Pb and soil S2 surpassed 2.1 times for Cd.
Moreover, the content of total Fe was 5890 y 9127 mg.kg−1 for S1 and S2 soils, respectively,
thus reflecting a high content of iron oxides (see Table 3).

Table 3. Trace element composition.

Cu Cd Cr Pb Ni Zn As Fe
(mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 ) (mg.kg−1 )
S1 16.00 1.62 7.06 33.18 18.88 20.35 0.30 5890.03
S2 7.99 1.03 2.75 11.58 12.67 7.84 0.16 9127.05
Limits 25.00 0.50 54.00 19.00 19.00 60.00 12.00 -

S1 was selected to be part of the barriers because it has characteristics similar to those
used in previous studies, with fines close to 50%, levels of organic matter and CEC less
than 5% and 20 meq/100 g soil, respectively. S2 was chosen to be part of the synthesis of
nanoparticles because of its higher content of Fe and clay.

3.2. Tailings Characterization

A slightly acidic pH with a value of 6.49 was measured and meets the allowable
limit fixed in TULSMA between 6 and 9 [50]. Conductivity is the property of aqueous
Sustainability 2023, 15, 1286 11 of 17

solutions that drives the flow of electric current and depends on the presence of ions, their
concentration and the temperature [51,52]. The measured value of 1336 ms.cm−1 is typical
of sewage. The redox potential is the oxidizing or reducing capacity of the medium and it is
measured in millivolts or volts. A high positive value indicates an environment that favors
oxidation reactions. On the other hand, a low negative value implies a highly reducing
environment [53]. The measured value of 117.38 mV is associated with a fresh sewage (see
Table 4).

Table 4. Some properties of mine tailings.

Property Value
pH 6.49
Electrical conductivity (ms·cm−1 ) 1336
Rodox potential (mV) 117.38
Temperature (◦ C) 29 (in situ)

The majority of heavy metals in mine tailings (Cr, Pb, Ni, Zn, Fe and As) were below
the allowed levels for discharge into a freshwater [50]. However, Cu and Pb exceeded 23.2
and 3.3 times the regulated limit, in that order. To evaluate the removal efficiency of As(V),
we prepared tailings with an approximated concentration of 5 mg·L−1 (see Table 5).

Table 5. Heavy metals concentrations of mine tailing.

Cd Cr Pb As Ni Cu Zn Fe
(mg·L−1 ) (mg·L−1 ) (mg·L−1 ) (mg·L−1 ) (mg·L−1 ) (mg·L−1 ) (mg·L−1 ) (mg·L−1 )
Tailing 0.065 0.141 0.115 0.039 0.138 23.244 3.238 0.045
Limits 0.020 0.500 0.200 0.100 2.000 1.000 5.000 10.000

3.3. Nanoparticle Characterization

The XRD spectrum of nanoparticles shows a peak at 44.7955◦ (2θ) that corresponds
to elemental iron (α-Fe) and the peaks at 44.7955◦ and 35.6349◦ (2θ) associated with the
presence of iron sulfide (Figure 9). SEM images showed that the as-prepared NPs are
spherical with a size of 67.8 ± 12.4 nm, surrounded by a rough surface (Figure 10). EDS
results revealed that the iron content on the nanoparticles is 41.05%. This is around tenfold
compared to soil that is only 3.85% Fe (Table 6. These results confirm the fact that these
tiny particles have elemental iron nanoparticles coated with iron sulfide.

Figure 9. X-ray diffraction pattern of multicomponent nanoparticles.

Sustainability 2023, 15, 1286 12 of 17

Figure 10. A SEM image of multicomponent nanoparticles.

Figure 10. A SEM image of multicomponent nanoparticles.

Table 6. EDS analysis.

Normalized Mass Percentage

C O Al Si S Fe
Nanoparticles 13.51 28.16 7.85 6.76 1.28 41.05
S2 12.95 50.38 14.16 17.06 - 3.85

3.4. Prototype Experimentation

In the P1 test, reactive barriers were separated by 10 cm and the water volume was
100 L. With these experimental conditions, the highest retention time was achieved (39.1 s).
In P2, changing the volume to 200 L, a decrease in time was observed (35.2 s). In tests P3 and
P4 with barrier separations of 20 cm, holding times reached 31.4 s and 28.8 s, respectively.
Tests P5 and P6 with barrier separations of 30 cm, retention times were 28.4 s and 27.5 s,
in that order. It is remarkable to observe that there is a time decrease by increasing the
separation of barriers and the volume of water to be treated. This is obviously related to
the decrease in the travel length between barriers and the increase in flow rate.
As illustrated in Figure 11, for the P1 test, in the first cycle, a 15.1% of As retention was
obtained, and the following cycles showed variations such as follows: 6.0%, −6.4%, 10%
and 2.2%. At the end of the five treatments, a retention of 25.6% was reached. For the P2
test, the first cycle showed 12.3% retention, an 8.3% increase in the second cycle, a decrease
of 6.2%, 0.2% and 4.9% in the third, fourth and fifth cycles, respectively. A total retention
of 6.7% was reached. The release of As observed in several cycles may be because of the
short times between cycles (~5 min). This may prevent contaminant bonding to soil and
nanoparticles’ reaction sites. This effect is even greater in the P2 test because there is an
increase in flow and speed. Thus, there is not enough time for the As(V) to react with the
reaction sites of the sorbent material.
Sustainability 2023, 15, 1286 and nanoparticles’ reaction sites. This effect is even greater in the P2 test because there
13 of 17is

Figure 11. Total retention of As in P1 and P2 cases.

In case P7 with a water volume of 100 L (Figure 12), the tailings remained stagnant
for 1 h. Furthermore, the retention times for the inflow and outflow were calculated as
39.3 s and 115.1 s, respectively. In P9 with 44 L (Figure 12), the period of stagnation was
maintained and the holding times were 68.3 s and 218.7 s. For P8 with a water volume of
100 L (Figure 13), the calculated retention time was 96.6 s. In P10, with the same separation
of barriers and 44 L (Figure 13), the time was raised to 204.7 s.

Figure 12. Total retention of As in P7 and P9 cases.

In P7, 65.5% of As retention was achieved after five cycles (Figure 12). Note that the
greatest adsorption occurs in the first 15 min of the treatment. In between cycles, there was
1 h in which the flow of liquid was stopped for equilibration of the sorbent material. It is
noteworthy to realize that adsorption increased after all the liquid was released, showing
that uptake reactions of As(V) are more effective when the liquid was moving compared
to stagnation because, during stagnation, only a small volume of contaminated water
remained in contact with the reactive material of the barriers. Cycles 1 and 4 showed
the highest release of the contaminant, with 18.5% and 20.6%, respectively. The sorption
characteristics of heavy metals on soils depend largely on the residence time of the adsorbate
in contact with the adsorbent [54]. The results of As release showed that the treatment time
was insufficient to stabilize the reaction.
Sustainability 2023, 15, 1286 14 of 17

Figure 13. Total retention of As in P8 and P10 cases.

Tests P9.1 and P9.2 reached an As(V) retention of 69.8% and 68.3%, respectively
(Figure 12). For these tests, the volume of the mine tailings was decreased to 44 L. As a
result, there was a decrease in flow and speed and an increase in retention time. These tests
exhibited a similar uptake of As(V) compared to P7 (Figure 12) and there was a relatively
low As release with a maximum of 6.4% for P9.1 and 5.7% for P9.2. It is remarkable to verify
that the contribution of nanoparticles in test P9.2 for the removal of As(V) was insignificant
(97% soil + 3% NPs) compared to the P9.1 test (100% soil), achieving only a 1.02 times
higher retention percentage at the end of the five cycles.
The retention rates of As at the end of 10 cycles for tests P8, P10.1 and P10.2 were
31.9%, 54.5% and 70.5%, respectively (Figure 13). All these tests did not show As release
in any cycle. P10.1 and P10.2 tests yielded higher As retention, which was linked to their
hydraulic parameters. The retention times of P10.1 and P10.2 were 2.1 times longer than P8.
Results and experimental conditions of P10.2 revealed this is the best treatment because it is
the only one that exceeded 70% of As retention. Therefore, Technosol with multicomponent
nanoparticles demonstrated a higher capacity for adsorption of the pollutant.
Arsenic is able to be strongly attracted to the sites of sorption on the surface of various
solid materials [55,56]. Excellent sorption efficiency has been found using iron oxides
and hydroxide-based materials [57,58]. Reactivity is limited by the characteristics of the
medium, contaminant and sorbent material. One way to improve reactivity is to increase
the specific surface area of the material, as this increases the area/volume ratio [59,60].
As proven, barriers packed with Technosols containing 97% soil + 3% MCNPs showed
an enhanced adsorption of arsenic because their reactivity was improved due to the in-
volvement of the nanoparticles. The sizes of these minuscule particles are in the range of
67.8 ± 12.4 nm (Figure 10) and certainly influence their chemical properties and therefore
the reactivity [61,62]. The combination of Fe0 and FeS in the nanoparticle provides a syner-
getic reactivity for the selective capture of As from mine tailings. The oxidized iron retains
As forming stable inner-sphere complexes [63,64], while As surface complexation is the key
mechanism for arsenic removal by FeS [18,65]. Moreover, iron-rich soil also uptakes As by
the interaction with the hydrated iron oxides through Lewis acid-base and electrostatic
forces [61,62].
From the perspective of Technosol management, once it gets saturated with arsenic. It
should be withdrawn from the geotextile bags and collected to be disposed of in an aerobic
landfill. The latter is a need to avoid reduction of iron oxides and the release of the arsenic
into the environment. Despite the amount of the exhausted Technosol might be a little high,
its cost is not so expensive. In addition, it shows good performance in the treatment of
arsenic-contaminated aqueous wastes and most importantly, this sorbent material can be
±
prepared locally.
Sustainability 2023, 15, 1286 15 of 17

In terms of costs, in the local market, a ton of Technosol would be approximately

$4900; however, this amount of material can treat 23,110 L of mine tailings with an average
concentration of 5 mg/L of arsenic, removing 70% of the metalloid. Compared to other
sorbent materials such as carbon-based [66], the cost is approximately two-fold, but the
Technosol, due to the properties explained before, can operate in a broad range of pH,
which secures the removal of arsenic from acidic and basic mine tailings.

4. Conclusions
The built prototype containing a concrete structure with two storage tanks and a
rectangular channel furnished with barriers filled with Technosols and multicomponent
nanoparticles, was used to treat As-polluted water. Results indicate that Test P10.2 reached
70.5% of As retention after 10 cycles of treatment. This test was run with a maximum inflow
rate of 43.8 L·min−1 , outflow rate of 13.2 L·min−1 , speed of 6 m·min−1 and a hydraulic
retention time of 3.4 min per cycle. The sorbent material containing 97% soil + 3% NPs
was the best sorbent material for As removal. Nevertheless, the indigenous iron-rich soil
yielded also a high As retention capacity by itself. Therefore, barriers could be filled with
only soil, but the treatment should have an increase in the hydraulic retention time to
reach an equivalent As retention. On the contrary, with less than five minutes between
cycles yielded a release of the metalloid, because there was not enough time for adsorption
reactions to take place and reach equilibration. As a sorbent material, the Technosol showed
good performance in the treatment of arsenic-contaminated aqueous wastes, and most
importantly, the material can be prepared locally. Thus, this simple and not expensive
technological setup could be scaled up to a functional field application to effectively capture
arsenic from aqueous tailings.

Author Contributions: Conceptualization, D.B.-G. and L.C.; Methodology, D.B.-G., E.L. and L.C.;
Software, E.L.; Validation, T.T.; Formal analysis, D.B.-G., I.G. and E.L.; Investigation, D.B.-G., I.G. and
E.L.; Data curation, I.G.; Writing—original draft, T.T.; Writing—review & editing, T.T.; Visualization,
D.B.-G.; Supervision, D.B.-G. and L.C. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by Universidad de las Fuerzas Armadas ESPE project number
2018-PIC-005 and the APC will be funded by Universidad de las Fuerzas Armadas ESPE.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Walter, I.; Ugelow, J.L. Environmental policies in developing countries. Ambio 1979, 8, 102–109.
2. Azapagic, A. Developing a framework for sustainable development indicators for the mining and minerals industry. J. Clean.
Prod. 2004, 12, 639–662. [CrossRef]
3. Newbold, J. Chile’s environmental momentum: ISO 14001 and the large-scale mining industry–Case studies from the state and
private sector. J. Clean. Prod. 2006, 14, 248–261. [CrossRef]
4. Mestanza-Ramón, C.; Paz-Mena, S.; López-Paredes, C.; Jimenez-Gutierrez, M.; Herrera-Morales, G.; D’Orio, G.; Straface, S.
History, Current Situation and Challenges of Gold Mining in Ecuador’s Litoral Region. Land 2021, 10, 1220. [CrossRef]
5. Marshall, B.G.; Veiga, M.M.; Da Silva, H.A.M.; Guimarães, J.R.D. Cyanide Contamination of the Puyango-Tumbes River Caused
by Artisanal Gold Mining in Portovelo-Zaruma, Ecuador. Curr. Environ. Health Rep. 2020, 7, 303–310. [CrossRef]
6. Gonçalves, A.O.; Marshall, B.G.; Kaplan, R.J.; Moreno-Chavez, J.; Veiga, M.M. Evidence of reduced mercury loss and increased
use of cyanidation at gold processing centers in southern Ecuador. J. Clean. Prod. 2017, 165, 836–845. [CrossRef]
7. Pesantes, A.A.; Carpio, E.P.; Vitvar, T.; López, M.M.M.; Menéndez-Aguado, J.M. A Multi-Index Analysis Approach to Heavy
Metal Pollution Assessment in River Sediments in the Ponce Enríquez Area, Ecuador. Water 2019, 11, 590. [CrossRef]
8. Veiga, M.M.; Angeloci, G.; Hitch, M.; Velasquez-Lopez, P.C. Processing centres in artisanal gold mining. J. Clean. Prod. 2014, 64,
535–544. [CrossRef]
9. Leguédois, S.; Séré, G.; Auclerc, A.; Cortet, J.; Huot, H.; Ouvrard, S.; Watteau, F.; Schwartz, C.; Morel, J.L. Modelling pedogenesis
of Technosols. Geoderma 2016, 262, 199–212. [CrossRef]
10. Séré, G.; Schwartz, C.; Ouvrard, S.; Renat, J.-C.; Watteau, F.; Villemin, G.; Morel, J.L. Early pedogenic evolution of constructed
Technosols. J. Soils Sediments 2010, 10, 1246–1254. [CrossRef]
Sustainability 2023, 15, 1286 16 of 17

11. Wahsha, M.; Bini, C.; Argese, E.; Minello, F.; Fontana, S.; Wahsheh, H. Heavy metals accumulation in willows growing on Spolic
Technosols from the abandoned Imperina Valley mine in Italy. J. Geochem. Explor. 2012, 123, 19–24. [CrossRef]
12. Paz, J. Estudio de la inmovilización de metales pesados presentes en relave líquido de minería empleando tecnosoles, a nivel de
laboratorio. Undergraduate Thesis, Universidad de las Fuerzas Armadas ESPE, Sangolquí, Ecuador, 2018.
13. Bolaños-Guerrón, D.R.; Sánchez-Gómez, V.P.; Paz, J.; Izquierdo, A.R.; Stael, C.; Balseiro-Romero, M. Arsenic Retention on
Technosols Prepared with Nanoparticles and Ferric Soil from Mine Drainage Water. J. Nanotechnol. 2018, 2018, 1–8. [CrossRef]
14. Bolaños, D.; Sánchez, V.; Paz, J.; Balseiro, M.; Cumbal, L. Arsenic retention on technosols prepared with nanoparticles for
treatment of mine drainage water. In Environmental Arsenic in a Changing World; CRC Press: Boca Raton, FL, USA, 2019; pp.
463–466. [CrossRef]
15. Guerrón, D.B.; Capa, J.; Flores, L.C. Retention of heavy metals from mine tailings using Technosols prepared with native soils and
nanoparticles. Heliyon 2021, 7, E07631. [CrossRef]
16. López, E. Biosíntesis de nanopartículas multicomponente mediante el extracto de Citrus sinensis para inmovilización de metales
pesados en aguas contaminadas. Undergraduate Thesis, Sangolquí, Ecuador, 2017.
17. Ramos, M.A.V.; Yan, W.; Li, X.-Q.; Koel, B.E.; Zhang, W.-X. Simultaneous Oxidation and Reduction of Arsenic by Zero-Valent Iron
Nanoparticles: Understanding the Significance of the Core−Shell Structure. J. Phys. Chem. C 2009, 113, 14591–14594. [CrossRef]
18. Bostick, B.C.; Fendorf, S. Arsenite sorption on troilite (FeS) and pyrite (FeS2). Geochim. Cosmochim. Acta 2003, 67, 909–921.
[CrossRef]
19. Capa, C. Aplicación de Tecnosoles para la recuperación de suelos y aguas afectados por actividades de obras civiles, urbanas y
minería. Undergraduate Thesis, Sangolquí, Ecuador, 2019.
20. ASTM D2487-17e1. Standard Practice for Classification of Soils for Engineering Purposes; American Society for Testing and
Materials: West Conshohocken, PA, USA, 2017.
21. Rhoades, J. Cation exchange capacity. In Methods of Soil Analysis: Part 2 Chemical and Microbiological Properties; American Society of
Agronomy: New York, NY, USA, 1983; pp. 149–157.
22. Pham-Anh, T.; Sillanpää, M. Fractionation of Macro and Trace Metals Due to Off-Time Interrupted Electrodewatering. Dry.
Technol. 2010, 28, 762–772. [CrossRef]
23. ASTM D2216; Standard Test Methods for Laboratory Determination of Water (Moisture) Content of Soil and Rock by Mass;
American Society for Testing and Materials: West Conshohocken, PA, USA, 2019.
24. ASTM D422; Standard Test Method for Particle-Size Analysis of Soils; American Society for Testing and Materials: West
Conshohocken, PA, USA, 2007.
25. ASTM D4318; Standard Test Methods for Liquid Limit, Plastic Limit, and Plasticity Index of Soils; American Society for Testing
and Materials: West Conshohocken, PA, USA, 2017.
26. ISO 11265; Soil Quality—Determination of the Specific Electrical Conductivity; International Organization for Standardization:
Geneva, Switzerland, 1994.
27. Zagal, E.; Zadzwaka, R. Protocolo de Métodos de Análisis para Suelos y Lodos; Universidad de Concepción: Santiago, Chile, 2007.
28. AASHTO T267. Standard Method of Test for Determination of Organic Content in Soils by Loss on Ignition; American Association
of State Highway and Transportation Officials: Washington, DC, USA, 1984.
29. ISO 10390; Soil Quality—Determination of pH; International Organization for Standardization: Geneva, Switzerland, 2005.
30. Jankiewicz, B.; Ptaszynski, B.; Turek, A. Spectrophotometric determination of copper (II) in samples of soil from selected allotment
gardens in Lodz. Pol. J. Environ. Stud. 1999, 8, 35–38.
31. Rice, E.; Baird, R.; Eaton, A. (Eds.) Standard Methods for the Examination of Water and Wastewater; American Public Health
Association: Washington, DC, USA, 2017.
32. Stael, C.; Cumbal, L. Optimized synthesis of multicomponent nanoparticles for removing heavy metals from artificial mine
tailings. Biol. Med. 2016, 8, 2016. [CrossRef]
33. Yaacob, W.Z.W.; How, H.K. Synthesis and Characterization of Marine Clay-Supported Nano Zero Valent Iron. Am. J. Environ. Sci.
2015, 11, 115–124. [CrossRef]
34. Sandoval, W. Principios de Hidráulica 2; EDIESPE: Quito, Ecuador, 2013.
35. Wolters, V. Invertebrate control of soil organic matter stability. Biol. Fertil. Soils 2000, 31, 1–19. [CrossRef]
36. Kögel-Knabner, I. The macromolecular organic composition of plant and microbial residues as inputs to soil organic matter. Soil
Biol. Biochem. 2002, 34, 139–162. [CrossRef]
37. Dohrmann, R. Cation exchange capacity methodology I: An efficient model for the detection of incorrect cation exchange capacity
and exchangeable cation results. Appl. Clay Sci. 2006, 34, 31–37. [CrossRef]
38. Solly, E.F.; Weber, V.; Zimmermann, S.; Walthert, L.; Hagedorn, F.; Schmidt, M.W.I. A Critical Evaluation of the Relationship
Between the Effective Cation Exchange Capacity and Soil Organic Carbon Content in Swiss Forest Soils. Front. For. Glob. Chang.
2020, 3, 98. [CrossRef]
39. Tisdall, J.M.; Oades, J.M. Organic matter and water-stable aggregates in soils. Eur. J. Soil Sci. 1982, 33, 141–163. [CrossRef]
40. Hassink, J.; Whitmore, A.P. A Model of the Physical Protection of Organic Matter in Soils. Soil Sci. Soc. Am. J. 1997, 61, 131–139.
[CrossRef]
41. Sarkar, B.; Singh, M.; Mandal, S.; Churchman, G.J.; Bolan, N. Clay Minerals—Organic Matter Interactions in Relation to Carbon
Stabilization in Soils. In The Future of Soil Carbon; Academic Press: Cambridge, MA, USA, 2018; pp. 71–86.
Sustainability 2023, 15, 1286 17 of 17

42. Loveland, P.; Webb, J. Is there a critical level of organic matter in the agricultural soils of temperate regions: A review. Soil Tillage
Res. 2003, 70, 1–18. [CrossRef]
43. Peech, M. Hydrogen-ion activity. In Methods of Soil Analysis: Part 2 Chemical and Microbiological Properties; American Society of
Agronomy: New York, NY, USA, 1965; Volume 9, pp. 914–926.
44. McCauley, A.; Jones, C.; Jacobsen, J. Soil pH and organic matter. Nutr. Manag. Modul. 2009, 8, 1–12.
45. McLean, E.O. Soil pH and lime requirement. Methods of Soil Analysis: Part 2. Chem. Microbiol. Prop. -Agron. Monogr. 1983, 9,
199–224.
46. Klute, A. Laboratory measurement of hydraulic conductivity of saturated soil. In Methods of Soil Analysis: Part 1 Physical and
Mineralogical Properties, Including Statistics of Measurement and Sampling; American Society of Agronomy: New York, NY, USA,
1965; Volume 9, pp. 210–221.
47. Cosby, B.J.; Hornberger, G.M.; Clapp, R.B.; Ginn, T.R. A Statistical Exploration of the Relationships of Soil Moisture Characteristics
to the Physical Properties of Soils. Water Resour. Res. 1984, 20, 682–690. [CrossRef]
48. Kool, J.B.; Parker, J.C. Development and evaluation of closed-form expressions for hysteretic soil hydraulic properties. Water
Resour. Res. 1987, 23, 105–114. [CrossRef]
49. Warren, S.N.; Kallu, R.R.; Barnard, C.K. Correlation of the Rock Mass Rating (RMR) System with the Unified Soil Classification
System (USCS): Introduction of the Weak Rock Mass Rating System (W-RMR). Rock Mech. Rock Eng. 2016, 49, 4507–4518.
[CrossRef]
50. Capparelli, M.V.; Moulatlet, G.M.; Abessa, D.M.D.S.; Lucas-Solis, O.; Rosero, B.; Galarza, E.; Tuba, D.; Carpintero, N.; Ochoa-
Herrera, V.; Cipriani-Avila, I. An integrative approach to identify the impacts of multiple metal contamination sources on the
Eastern Andean foothills of the Ecuadorian Amazonia. Sci. Total. Environ. 2019, 709, 136088. [CrossRef] [PubMed]
51. Morgan, F.D.; Williams, E.R.; Madden, T.R. Streaming potential properties of westerly granite with applications. J. Geophys. Res.
Earth Surf. 1989, 94, 12449–12461. [CrossRef]
52. Varghese, K.S.; Pandey, M.C.; Radhakrishna, K.; Bawa, A.S. Technology, applications and modelling of ohmic heating: A review. J.
Food Sci. Technol. 2012, 51, 2304–2317. [CrossRef]
53. Krumbein, W.C.; Garrels, R.M. Origin and Classification of Chemical Sediments in Terms of pH and Oxidation-Reduction
Potentials. J. Geol. 1952, 60, 1–33. [CrossRef]
54. Wu, H.; Wen, Q.; Hu, L.; Gong, M. Effect of Adsorbate Concentration to Adsorbent Dosage Ratio on the Sorption of Heavy Metals
on Soils. J. Environ. Eng. 2018, 144, 04017094. [CrossRef]
55. Bowell, R. Sorption of arsenic by iron oxides and oxyhydroxides in soils. Appl. Geochem. 1994, 9, 279–286. [CrossRef]
56. Chutia, P.; Kato, S.; Kojima, T.; Satokawa, S. Arsenic adsorption from aqueous solution on synthetic zeolites. J. Hazard. Mater.
2009, 162, 440–447. [CrossRef]
57. Yu, X.-Y.; Liu, Z.-G.; Huang, X.-J. Nanostructured metal oxides/hydroxides-based electrochemical sensor for monitoring
environmental micropollutants. Trends Environ. Anal. Chem. 2014, 3–4, 28–35. [CrossRef]
58. Uddin, M.J.; Jeong, Y.K. Efficiently performing periodic elements with modern adsorption technologies for arsenic removal.
Environ. Sci. Pollut. Res. 2020, 27, 39888–39912. [CrossRef]
59. Roy, J. Economic benefits of arsenic removal from ground water—A case study from West Bengal, India. Sci. Total Environ. 2008,
397, 1–12. [CrossRef]
60. Kumar, R.; Patel, M.; Singh, P.; Bundschuh, J.; Pittman, C.U., Jr.; Trakal, L.; Mohan, D. Emerging technologies for arsenic removal
from drinking water in rural and peri-urban areas: Methods, experience from, and options for Latin America. Sci. Total Environ.
2019, 694, 133427. [CrossRef] [PubMed]
61. Wang, Y.; Herron, N. Nanometer-sized semiconductor clusters: Materials synthesis, quantum size effects, and photophysical
properties. J. Phys. Chem. 1991, 95, 525–532. [CrossRef]
62. Grassian, V.H. When Size Really Matters: Size-Dependent Properties and Surface Chemistry of Metal and Metal Oxide Nanoparti-
cles in Gas and Liquid Phase Environments. J. Phys. Chem. C 2008, 112, 18303–18313. [CrossRef]
63. Cumbal, L.; SenGupta, A.K. Arsenic Removal Using Polymer-Supported Hydrated Iron(III) Oxide Nanoparticles: Role of Donnan
Membrane Effect. Environ. Sci. Technol. 2005, 39, 6508–6515. [CrossRef]
64. Cumbal, L.H.; SenGupta, A.K. Preparation and Characterization of Magnetically Active Dual-Zone Sorbent. Ind. Eng. Chem. Res.
2005, 44, 600–605. [CrossRef]
65. Murgueitio, E.; Cumbal Flores, L.H.; Toulkeridis, T. Removal of arsenic and heavy metals from contaminated water with emerging
sorbents. In Proceedings of CIT 2022, Smart Innovation, Systems and Technologies (SIST) Series; Springer: Berlin/Heidelberg, Germany,
2022.
66. Di Natale, F.; Erto, A.; Lancia, A.; Musmarra, D. A descriptive model for metallic ions adsorption from aqueous solutions onto
activated carbons. J. Hazard. Mater. 2009, 169, 360–369. [CrossRef] [PubMed]

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