Environmental Technology & Innovation 27 (2022) 102452

Contents lists available at ScienceDirect

Environmental Technology & Innovation

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

Application of natural organic residues in the remediation of

metals from e-waste
Luana Maria Tavares Rosa a , Wander Gustavo Botero b ,
Janaina Braga do Carmo a,c , Gabriele V.M. Gabriel a,d , Walter Ruggeri Waldman d ,
∗
Alexandre D.M. Cavagis d , Danielle Goveia e,f , Luciana Camargo de Oliveira a,d ,
a
Federal University of São Carlos (UFSCar), Postgraduate Program in Biotechnology and Environmental Monitoring, Rodovia João
Leme dos Santos, SP-264, km 110, 18052-780, Sorocaba, São Paulo, Brazil
b
Federal University of Alagoas (UFAL), Postgraduate Program in Chemistry and Biotechnology, Av. Manoel Severino Barbosa, s/n,
Arapiraca, Alagoas, 57309-005, Brazil
c
Federal University of São Carlos (UFSCar), Department of Environmental Sciences, Rodovia João Leme dos Santos, SP-264, km 110,
Sorocaba, São Paulo, 18052-780, Brazil
d
Federal University of São Carlos (UFSCar), Department of Physics, Chemistry and Mathematics, Rodovia João Leme dos Santos,
SP-264, km 110, Sorocaba, São Paulo, 18052-780, Brazil
e
São Paulo State University (UNESP), Rua Geraldo Alckmin, 519, 18409-010, Itapeva, São Paulo, Brazil
f
FCLAr, Rodovia Araraquara-Jaú, km 1, 14800-901, Araraquara, São Paulo, Brazil

article info a b s t r a c t

Article history: Contaminants, such as potentially toxic metals from e-waste, have been affecting soil,
Received 16 September 2021 water and ecosystems throughout the world. Thus, the search for low cost natural
Received in revised form 27 January 2022 substances, able to complex such metals, is a matter of both environmental and
Accepted 23 February 2022
economic interest. Humic substances (HS) are the main natural organic complexing
Available online 8 March 2022
agents in ecosystems, and their alkaline extraction leads to a poorly soluble residue,
Keywords: which is often discarded, in spite of its great potential for chelating potentially toxic
Humic substances metals. Since both the structure and complexing capacity of HS might be significantly
e-waste affected by the way of extraction, this study comparatively evaluated the implications of
Potentially toxic metals exhaustive and non-exhaustive extractions on physical–chemical and structural proper-
ties of different natural organic residues (NOR) obtained. Furthermore, adsorption studies
were carried out in order to compare the influence of different extractions on the
resulting NOR capacities to retain copper ions. The milder extractions, involving non-
exhaustive procedures, led to a NOR with better copper adsorption, which was then
selected to test the retention of copper from an e-waste leachate. Results evidenced
the potential use of NOR for copper removal (340 µg Cu2+ g−1 of NOR), as well as
other potentially toxic metals, such as iron, manganese and chromium, thus showing
a promising application of this material in the environmental remediation of soils and
waters.
© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

The progressive development of numerous activities in agricultural and industrial sectors brings environmental issues,
which have been a cause of concern throughout the world (Gavrilescu et al., 2015; Starling et al., 2019). An example is

∗ Corresponding author at: Federal University of São Carlos (UFSCar), Postgraduate Program in Biotechnology and Environmental Monitoring,
Rodovia João Leme dos Santos, SP-264, km 110, 18052-780, Sorocaba, São Paulo, Brazil.
E-mail address: [email protected] (L.C. Oliveira).

https://doi.org/10.1016/j.eti.2022.102452
2352-1864/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.
org/licenses/by-nc-nd/4.0/).
L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

the electronics industry, which has grown considerably over the last decades, increasing the amount of electronic waste
(e-waste) in the environment (Bilgen and Sarıkaya, 2015; Camioto et al., 2014; Du et al., 2020).
The ever-increasing amount of pollutants in the environment has been affecting the soil, water and ecosystems (Li
et al., 2019; Shi et al., 2020; Tkaczyk et al., 2020; Wang et al., 2021). In this scenario, certain residues, such as gasoline
additives, potentially toxic metals, surfactants, e-waste, pesticides and personal hygiene products stand out due to their
high toxicity (Bezerra et al., 2019; Deblonde et al., 2011; Lapworth et al., 2012).
In living organisms, potentially toxic metals may cause hazardous effects, leading to biochemical and physiological
disorders (Andreas and Zhang, 2014; Park et al., 2019; Shi et al., 2020; Tchounwou et al., 2012). The e-waste, in
turn, presents potentially toxic metals, and its inadequate management significantly contributes to a worsening of the
environmental contamination. Importantly, according to Forti et al. (2020), only 17.4% of the e-waste generated in the
world is recycled.
Based on the foregoing, devising strategies involving low-cost, easily obtainable and non-polluting materials to retain
potentially toxic metals from e-waste is socially and environmentally important (Awasthi et al., 2016). In this way, humic
substances (HS), which are the main naturally occurring organic complexing agents in ecosystems, may be a promising
alternative.
The extraction of HS commonly involves an alkaline step, which leads to a poorly soluble organic residue that is
usually discarded (Rice, 2001; Stevenson, 1994). Uncovering new practical applicabilities for such residue is a matter
of both economic and environmental interest, since humic substances are extracted on a large scale. The low solubility
represents an additional advantage of using this residue for environmental remediation, considering that it may function
as a biosorbent, resistant to microbial degradation (Almendros and Sanz, 1991; Chen et al., 2017; Rice, 2001). Even though
the ability of the insoluble residue to chelate toxic metals has already been evidenced, it may undergo structural changes,
depending on the treatment used during the extraction of the soluble fraction (Trevisan et al., 2010). Thus, further research
is required in order to find out the effects of different extracting agents on structural characteristics and properties of the
insoluble residue from HS (Cunha et al., 2012; De la Rosa et al., 2003).
In view of the above, the present study aimed to compare the influence of different extraction procedures on properties
of the resulting organic residues (NOR) from HS, especially those related to their capacity of retaining copper from e-waste.
To this end, exhaustive and non-exhaustive extractions were carried out, by using sodium hydroxide (NaOH), potassium
hydroxide (KOH) and sodium pyrophosphate (Na4 P2 O7 ). The different NOR obtained were then submitted to the following
treatments: with urea (CH4 N2 O), dimethyl sulfoxide ((CH3 )2 SO), sulfuric acid (H2 SO4 ) and/or hydrofluoric acid (HF), in
order to better understand the behavior of the poorly soluble fraction. After the treatment, each NOR was characterized
by gravimetry, UV–Vis spectrophotometry, elemental analysis and Fourier-transform infrared spectroscopy (FTIR), beyond
assays aiming to appraise the adsorption of copper ions. Finally, the NOR that showed the best retention of copper was
tested in a leachate containing copper and other metal ions, released from an e-waste, in order to assess its potential
application for environmental remediation.

2. Materials and methods

2.1. Collection and preparation of soil samples

Soil samples with high amount of organic matter (28.98%) were collected in the Taquaral district, city of Ribeirão Preto,
State of São Paulo, Brazil. Once collected, samples were dried at room temperature (∼24 ◦ C), up to a constant mass and
then passed through 2.0 mm mesh sieves (Li et al., 2015).

2.2. Comparative extraction of the natural organic residues (NOR)

Comparative extractions of the soluble fraction of HS were carried out, based on the methodologies most used by
researchers in the field of HS extraction, involving non-exhaustive and exhaustive processes (Huey et al., 2010; IHSS,
2020; Swift, 1996; Zaccone et al., 2009). Table 1 lists the NOR samples obtained, as well as the extracting agent used in
each case, the presence or not of inert atmosphere, and the subsequent treatment, where applicable.
All extractions were made in the proportion of 1:10 soil:extraction solution, under stirring, for 4 h, at room temperature
(∼24 ◦ C) (Rosa et al., 2000; Swift, 1996). After each extraction, the suspension formed between the soil and the extraction
solution was kept at rest, for approximately 24 h (Cerqueira et al., 2012; Zaccone et al., 2009).
In non-exhaustive extractions, the poorly soluble fraction from each sample was thoroughly rinsed with distilled water,
in order to remove any residual alkalinity. Then, the soluble fraction was dried at 60 ◦ C, up to a constant mass (Chang
et al., 2014; Goveia et al., 2013; Jesus et al., 2011; Song et al., 2011; Wang and Xing, 2005).
In exhaustive extractions, the poorly soluble fraction was thoroughly washed with the extraction solution (Chang et al.,
2014; Song et al., 2008). After that, as detailed in Table 1, it was made a treatment with dimethylsulfoxide (DMSO):
((CH3 )2 SO) + 6% (v/v) sulfuric acid (H2 SO4 98%) 94:6 (v/v), in a proportion of 1:10 (m/v) NOR:extracting solution, for a
period of 14 h, under stirring. Both DMSO and H2 SO4 act on the NOR structure, helping to remove the recalcitrant organic
matrix (Song et al., 2008; Chang et al., 2014). The treatment with 10% (v/v) HF/1:10 (NOR:HF), for about 30 s, followed
by 12 h of rest, favors the rupture of chemical bonds throughout the organic matter, as well as in clay and silicates, so
that minerals may be solubilized during the process (Schmidt et al., 1997; Song et al., 2011; Tatzber et al., 2007).
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Table 1
The different NOR obtained and details on the conditions adopted in each extraction.

NaOH: sodium hydroxide; KOH: potassium hydroxide; Na4 P2 O7 : sodium pyrophosphate; DMSO: dimethyl sulfoxide; H2 SO4 : sulfuric acid; HF:
hydrofluoric acid.
(*) NOR samples: NOR-EE1: exhaustive extraction with NaOH; NOR-EE2: exhaustive extraction with KOH; NOR-EE3: exhaustive extraction with
Na4 P2 O7 ; NOR-EE4: exhaustive extraction with NaOH under N2 atmosphere; NOR-EE5: exhaustive extraction with NaOH, Urea + NaOH and DMSO
+ H2 SO4 ; NOR-EE6: exhaustive extraction with KOH, Urea + NaOH and DMSO + H2 SO4 ; NOR-EE7: exhaustive extraction with Na4 P2 O7 , Urea +
NaOH and DMSO + H2 SO4 ; NOR-EE8: exhaustive extraction with NaOH under N2 atmosphere, Urea + NaOH and DMSO + H2 SO4 ; NOR-n-EE1:
non-exhaustive extraction with NaOH; NOR-n-EE2: non-exhaustive extraction with KOH; NOR-n-EE3: non-exhaustive extraction with Na4 P2 O7 ; NOR-
n-EE4: non-exhaustive extraction with NaOH under N2 atmosphere; NOR-n-EE5: non-exhaustive extraction with NaOH, Urea + NaOH, DMSO +
H2 SO4 and HF; NOR-n-EE6: non-exhaustive extraction with KOH, Urea + NaOH, DMSO + H2 SO4 and HF; NOR-n-EE7: non-exhaustive extraction
with Na4 P2 O7 , Urea + NaOH, DMSO + H2 SO4 and HF; NOR-n-EE8: non-exhaustive extraction with NaOH under N2 atmosphere, Urea + NaOH, DMSO
+ H2 SO4 and HF.

2.3. NOR characterization

Organic matter and ashes contents were determined by gravimetry, from 0.5 g of NOR, treated in a muffle furnace, at
750 ◦ C, for 4 h (Griffith and Schnitzer, 1975). To determine the E4 /E6 ratio, spectrophotometric analyzes were performed
in the ultraviolet–visible (UV–Vis) region (Q798U2VS, Quimis), at 465 and 665 nm, by dissolving 2.0 mg of sample in 10
mL of 0.05 mol L−1 sodium bicarbonate (NaHCO3 ) (Chen et al., 1977).
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

The elemental composition of the samples was determined with respect to the percentages of carbon, hydrogen and
nitrogen, in an elemental analyzer (2400 Series II CHNS/O, Perkin Elmer), with 2.0 to 3.0 mg of samples, combusted at
1000 ◦ C (Xu et al., 2013).
The characterization of chemical groups in different NOR samples was based on infrared absorption bands, by Fourier-
transform infrared spectroscopy (FTIR), in a spectrometer equipped with a data acquisition system (Nicolet IR 200 FT-IR,
Thermo Scientific). Samples were homogenized in a mortar, with potassium bromide (KBr), previously dried during 24 h at
105 ◦ C, in the proportion of 1:100 (m/m) sample:KBr, and then compressed into pellets, until they remained translucent.
The scanning was taken from 400 to 4000 cm−1 , using the transmission mode, with a resolution of 4 cm−1 and 32 scans
(adapted from Tivet et al., 2013).

2.4. Interactions between NOR and Cu2+ : influence of the extraction method

2.4.1. Kinetic study of the interaction NOR/Cu2+

The kinetic studies were conducted at room temperature (∼24 ◦ C) and the pH value was chosen close to the
environmental conditions, at pH 5.0, considering that this pH value could contribute to the availability of functional groups
and charges that influence on metal adsorption by organic and inorganic constituents present in the NOR. Studies have
shown that the availability of copper species in the environment and the concomitant increase in toxicity are favored at
pH 5.0. At this pH, there is a predominance of the species in the Cu2+ form (Beiyuan et al., 2016; Chen et al., 2022).
The influence of contact time on NOR/copper interaction was evaluated from 5 to 360 min. To this end, a mass of
400 mg of NOR was mixed with 200 mL of 10 mg L−1 standard copper solution, in a tangential ultrafiltration system,
equipped with a membrane of 1 kDa (Millipore™), which allows to disrupt complexes involving the copper ions adsorbed
in the NOR and those free in solution (Botero et al., 2010, 2013; Burba et al., 2001). Thus, the amount of free copper was
quantified (Li et al., 2013) and the percentage of copper retained by different NOR was determined from Eq. (1)
C0 − C
%of retention = ∗100 (1)
C0
where C0 is the initial concentration of copper (mg L−1 ) and C is the final concentration of free metal in the filtered (mg
L−1 ).

2.4.2. Use of NOR to retain metals from an e-waste leachate

In order to appraise the applicability of NOR for environmental remediation purposes, it was used an e-waste from the
leaching of a ferric chloride (FeCl3 ) solution, which is commonly used in corrosive baths, during the etching process of
printed circuit boards. Copper is the major conductive metal on printed circuits boards and FeCl3 promotes corrosion of
the copper that will not compose electronic connections. This procedure is widely adopted due to its low cost, being the
bath solution recycled sometimes and then discarded, when the corrosion becomes ineffective or too slow. Consequently,
the resulting effluent carries considerable concentrations of copper and iron, thus requiring great care and attention on
its disposal (Cakir, 2006). Over the board, the CuCl2 formed is solubilized, leading to an effluent containing considerable
concentrations of Cu2+ . Importantly, the concentration of copper in the leachate was so high that a dilution of 1:100
(v/v) was necessary in the assays. Beyond copper, the identification of iron (Fe), manganese (Mn) and chromium (Cr) was
also made. In this assay, 0.05 g of NOR was placed in contact with 15 mL of the diluted effluent. Aliquots were collected
at different times (from 5 to 360 min) and then vacuum filtered through a 0.45 µM cellulose ester membrane (MF-
Millipore™). The assays were performed in replicates. The pH of the solution was 2.8. Metals in solution were quantified
by microwave plasma atomic emission spectroscopy (MP-AES 4200, Agilent Technologies).
The mass of retained copper in NOR was calculated from the mass of adsorbed metal per unit mass of NOR, according
to Eq. (2)
C0 − C
q= V (2)
mNOR
where q is the adsorption capacity for copper, in µg per g of NOR; C0 is the initial concentration of copper in the effluent
(µg L−1 ); C is the concentration of free copper in solution (µg L−1 ) after adding the NOR; V is the volume of leachate;
and m is the mass of NOR (g) (Won et al., 2008).

2.5. Determination of metals by microwave plasma atomic emission spectrometry

The concentrations of copper, iron, manganese and chromium in samples were quantified in a microwave plasma
atomic emission spectrometer (MP-AES 4200, Agilent Technologies) (three technical replicates) (Li et al., 2013). The
calibration curve to quantify such metal ions was obtained from a standard solution at 50 mg L−1 , with a concentration
range from 0.5 to 10 mg L−1 . The pH was adjusted to 5.0, by adding 0.1 mol L−1 NaOH or HNO3 . Analytical calibrations were
®
made by using multielement standard solution (Agilent Technologies), except for Fe (Sigma-Aldrich ). The wavelengths
were 324.754 nm to Cu, 425.433 nm to Cr, 403.076 nm to Mn and 371.993 nm to Fe.
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Table 2
Characterization of NOR obtained from different extractions. Percentages of organic matter, ashes, carbon, hydrogen, nitrogen and the E4 /E6 ,
carbon/hydrogen and carbon/nitrogen ratios.
Samples % Organic matter % Ashes E4 /E6 %C %H %N C/H C/N
Original soil 28.98 71.02 – 10.34 1.59 0.26 0.54 47.77
Exhaustive extractions
NOR-EE1 0.53 99.47 nd nd nd nd nd nd
NOR-EE2 0.47 99.53 nd nd nd nd nd nd
NOR-EE3 0.44 99.56 nd nd nd nd nd nd
NOR-EE4 0.48 99.52 nd nd nd nd nd nd
NOR-EE5 0.42 99.58 nd nd nd nd nd nd
NOR-EE6 0.41 99.58 nd nd nd nd nd nd
NOR-EE7 0.25 99.75 nd nd nd nd nd nd
NOR-EE8 0.41 99.58 nd nd nd nd nd nd
Non-exhaustive extractions
NOR-n-EE1 7.92 92.08 1.12 3.00 0.49 0.12 0.50 31.12
NOR-n-EE2 14.66 85.34 1.09 4.30 0.79 0.12 0.44 43.75
NOR-n-EE3 10.09 89.91 0.91 4.47 0.71 0.17 0.52 31.00
NOR-n-EE4 11.84 88.16 1.13 4.19 0.66 0.17 0.51 29.00
NOR-n-EE5 0.60 99.40 nd nd nd nd nd nd
NOR-n-EE6 0.43 99.57 nd nd nd nd nd nd
NOR-n-EE7 0.48 99.52 nd nd nd nd nd nd
NOR-n-EE8 0.32 99.68 nd nd nd nd nd nd

C: carbon; H: hydrogen; N: nitrogen; C/H: carbon and hydrogen ratio; C/N: carbon and nitrogen ratio; nd: not detected.
a
NOR samples: NOR-EE1: exhaustive extraction with NaOH; NOR-EE2: exhaustive extraction with KOH; NOR-EE3: exhaustive extraction with Na4 P2 O7 ;
NOR-EE4: exhaustive extraction with NaOH under N2 atmosphere; NOR-EE5: exhaustive extraction with NaOH, Urea + NaOH and DMSO + H2 SO4 ;
NOR-EE6: exhaustive extraction with KOH, Urea + NaOH and DMSO + H2 SO4 ; NOR-EE7: exhaustive extraction with Na4 P2 O7 , Urea + NaOH and
DMSO + H2 SO4 ; NOR-EE8: exhaustive extraction with NaOH under N2 atmosphere, Urea + NaOH and DMSO + H2 SO4 ; NOR-n-EE1: non-exhaustive
extraction with NaOH; NOR-n-EE2: non-exhaustive extraction with KOH; NOR-n-EE3: non-exhaustive extraction with Na4 P2 O7 ; NOR-n-EE4: non-
exhaustive extraction with NaOH under N2 atmosphere; NOR-n-EE5: non-exhaustive extraction with NaOH, Urea + NaOH, DMSO + H2 SO4 and HF;
NOR-n-EE6: non-exhaustive extraction with KOH, Urea + NaOH, DMSO + H2 SO4 and HF; NOR-n-EE7: non-exhaustive extraction with Na4 P2 O7 , Urea
+ NaOH, DMSO + H2 SO4 and HF; NOR-n-EE8: non-exhaustive extraction with NaOH under N2 atmosphere, Urea + NaOH, DMSO + H2 SO4 and HF.

2.6. Scanning transmission electron microscopy (STEM)

Morphological analyses of NOR sample were performed by scanning electron microscopy (SEM). The sample was
analyzed before interaction with e-waste leachate solutions. The micrograph was obtained using Quanta scanning electron
microscopes, model 650 FEG (10 mm of working distance and 10 kV voltage). The NOR sample was precoated with a gold
film, using Bal-Tec SCD 005 Coater equipment for 60 s and 40 mA, generating a film with an average thickness of 16 nm.
The analyses were performed at the Electronic Microscopy Laboratory (LME) of the National Nanotechnology Laboratory
(LNNano), in Campinas/SP (Quanta).

3. Results and discussion

The comparative extractions of different NOR provided a detailed understanding on such processes, allowing to select
procedures that, besides not requiring high amounts of reagents, lead to organic residues with better properties for copper
retention.

3.1. Characterization of NOR samples

In relation to the original soil, there was a reduction in the organic matter content in all resulting NOR samples after the
extractions. Every NOR derived of exhaustive extractions and those from non-exhaustive with more than one extraction
solution (NOR-n-EE5, NOR-n-EE6, NOR-n-EE7 and NOR-n-EE8) had almost all the organic matter removed: from 28.98%, in
the original soil, to values between 0.25% and 0.60%, approximately (Table 2). Conversely, the samples from non-exhaustive
extractions with just one extraction solution (NOR-n-EE1, NOR-n-EE2, NOR-n-EE3 and NOR-n-EE4), maintained the organic
matter levels between 7.92% and 14.66%, which corresponds to 96% more organic matter than that remaining from the
more exhaustive procedures (Table 2). This result reiterates that harder extractions lead to an increased ashes content,
with a small amount of residual organic matter.
The E4 /E6 ratio (quotient between the absorbances at 465 nm and 665 nm) allows estimating the degree of structural
condensation. In this case, only the samples from non-exhaustive procedures, with just one extraction solution (NOR-
n-EE1 to n-EE4) presented quantifiable values of this parameter (Table 2). A low E4 /E6 ratio indicates a high degree of
structural condensation, which may be directly related to the humification degree, indicating a greater number of aromatic
units. Conversely, higher E4 /E6 ratio values indicate less condensed structures, which are related to a lower humification
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Fig. 1. Spectroscopic analysis of the natural organic residues (NOR). Fourier Transform Infrared (FTIR) spectra of the original soil and of the NOR
obtained from different extractions.

degree (Chen et al., 1977; Stevenson, 1994). Thus, in spite of the similar values found for these four NOR samples, the
NOR-n-EE3, extracted with Na4 P2 O7 , showed a higher structural condensation when compared to the others, since it has
the lowest E4 /E6 value (0.91) (Table 2). Interestingly, the use of Na4 P2 O7 may have influenced the result, leading to less
chemical changes in the material, due to the formation of poorly soluble precipitates, jointly with a reduction in the
auto-oxidation of the extracted humic material (Francioso et al., 1998; Zaccone et al., 2009).
The elemental analysis of the NOR aimed to get information on the distribution of carbon (C), hydrogen (H) and nitrogen
(N), in order to complement the data from other analytical techniques. Only the NOR obtained from non-exhaustive
methods with just one extraction solution (NOR-n-EE1 to n-EE4), presented quantifiable values, being the contents in
all the other samples below the limit of detection (Table 2). This result makes clear how the extraction influences the
levels of C, H and N, when comparing to the original soil.
Elemental ratios (C/H and C/N) have been widely used to provide information on the degrees of aromaticity and
decomposition of organic matter (Han et al., 2012; Li et al., 2015; Romão et al., 2007). Although the C/H ratios of the
NOR obtained remained close, if compared to the original soil, it is evident that the samples NOR-n-EE1, NOR-n-EE3 and
NOR-n-EE4 (obtained from non-exhaustive methods) had higher degrees of aromaticity than the other samples, and also
very close to the original soil (Table 2. The C/N ratios, in turn, showed a variation in the values obtained for the NOR,
when compared to the original soil. Furthermore, the sample NOR-n-EE2, obtained through a non-exhaustive extraction
with KOH, presented the highest value (43.75) among all the samples (Table 2). This value may be related to a reduction
in the availability of nitrogen, due to its incorporation in more stable fractions of the NOR, which confers a higher degree
of humification to the sample (Stevenson, 1994).
From the infrared spectra of the different NOR, based on the literature, it was made a qualitative attribution of
absorption bands, related to aliphatic and aromatic groups, among others (Fig. 1). These groups may be associated with
mineral colloids in the soil, providing resistance to NOR against environmental transformations of the organic matter
(Chang et al., 2014; Dick et al., 2003; Han et al., 2012; Helal et al., 2011; Tatzber et al., 2007).
In general, infrared spectra of the different NOR (Fig. 1) demonstrated broad bands in the range between 3600–
3400 cm−1 , which are characteristic of O–H stretching in alcohols and/or phenols and/or carboxylic acids. Wavelengths
close to 1688–1585 cm−1 may be attributed to C==C stretching in aromatic rings and C==O in carboxylic acids, followed by
bands between 1142–773 cm−1 , which may be attributed to phenolic groups (Stevenson, 1994). Moreover, reductions
in absorption bands between 1200–880 cm−1 , possibly indicate the loss of groups related to aliphatic and aromatic
compounds, as well as fatty and carboxylic acids from NOR structures. This result reiterates the great influence of the
extraction way on the final NOR structure, taking into account the wide removal of important organic components during
all exhaustive extractions, as well as those non-exhaustive, in which was employed more than one extraction solution.
(Fig. 1).
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Fig. 2. Adsorption of copper (10 mg L−1 ) by natural organic residues (NOR). Adsorption of copper by NOR obtained from exhaustive (A and B)
and non-exhaustive (C and D) extractions: (A) exhaustive extractions with NaOH, KOH, Na4 P2 O7 and NaOH under N2 atmosphere; (B) exhaustive
extractions with NaOH, KOH, Na4 P2 O7 and NaOH under N2 atmosphere, submitted to treatments with urea + NaOH and DMSO + H2 SO4 ; (C) non-
exhaustive extractions with NaOH, KOH, Na4 P2 O7 and NaOH under N2 atmosphere; and (D) non-exhaustive extractions with NaOH, KOH, Na4 P2 O7
and NaOH under N2 atmosphere, submitted to treatments with urea + NaOH, DMSO + H2 SO4 and HF.

3.2. Interactions NOR-Cu2+ : influence of the extraction method

Since the characterization studies revealed important differences in the NOR structures, it became equally relevant to
verify how such changes might influence on their capacities for copper retention. As it may be seen, all the NOR obtained
from exhaustive methods and those obtained from non-exhaustive, with more than one extraction solution, presented
the lowest copper retentions (Fig. 2A, B and D), when comparing with the NOR obtained from non-exhaustive methods
with just one extraction solution (Fig. 2C).
The percentages of copper retention ranged from 5% to 39%, with an increase in the adsorptive capacity along the
time, for the NOR samples from exhaustive treatments (Fig. 2A and B) and those from non-exhaustive with more than
one extraction solution (Fig. 2C), with NOR-EE1 and NOR-EE2 retaining 39% and 24%, respectively (Fig. 2A). On the other
hand, samples from non-exhaustive extractions with just one extraction solution had better copper retentions, varying
from 10% to 80%, standing out NOR-n-EE3 and NOR-n-EE4, which showed the highest adsorptive capacities (Fig. 2C).
In the kinetic studies, a great variation on the time to reach equilibrium was observed, especially for the NOR from
exhaustive methods (Fig. 2A and B). Only the NOR from non-exhaustive extractions with just one solution showed
considerable values of copper retention, between 30 and 50 min (from 13 to 70%) (Fig. 2C). Kinetic studies also revealed
that the way of extraction significantly influenced the dynamics of adsorption, especially due to the loss of certain
important groups, such as aliphatics, aromatics, fatty and carboxylic acids (Fig. 1). This compromises the capacity of
NOR to complex copper ions, which is confirmed by the best adsorptive capacities of those NOR from non-exhaustive
extractions (NOR-n-EE1 to n-EE4). Interestingly, they conserved the IR bands between 1200–880 cm−1 and retained a high
percentage of copper (between 50% and 80%), whereas, for the other samples, the retention was around 39%. Therefore,
non-exhaustive methods, without any additional treatment, proved to be more adequate for copper retention purposes
(Fig. 2C), since they prevent the loss of organic matter (Fig. 1), which is pivotal to the formation of NOR-Cu2+ complexes.
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Fig. 3. Application of a natural organic residue (NOR) in the retention of copper. Mass of copper (q) from e-waste retained in NOR-n-EE4 as a
function of contact time. Mass of NOR-n-EE4 used: 0.05 g.

Table 3
Biosorption, bioleaching and phytoremediation, alternative methods applied for removal of potentially toxic metals in e-waste.
Remediation mechanism Metals Removal method Removal efficiency References
Microorganisms (Streptomyces Al, Ca, Cu, Cd, Fe, Ni, Zn, Bioleaching 66% Al Kaliyaraj et al. (2019)
albidoflavus) Ag and Pb 74% Ca
68% Cu
65% Cd
42% Fe
81% Ni
82% Zn
56% Ag
46% Pb

Plant (Eucalyptus globulus) Cd, Pb and Cu Phytoremediation 1.35 mg of Cd Luo et al. (2017)
58.47 mg of Pb 119.18
mg of Cu
Natural Organic Residue (NOR) Pb Biosorption 45% to 98% Oliveira et al. (2019)
Biochar and Activated Carbon Au Biosorption 98% Zhou et al. (2021)

Plant (Festuca arundinacea) Cd Phytoremediation 83,3% Luo et al. (2020)

Natural Organic Residue (NOR) Cu, Fe, Mn and Cr Biosorption 80% Cu (This work)
33% Fe
17% Mn
10% Cr

3.3. Using the NOR for retention of metals from e-waste

As NOR-n-EE4 showed the best copper retention (about 80%), it was tested in the removal of copper from an e-waste
leachate. In this case, the results showed an adsorption capacity of 270 µg Cu2+ g−1 , with just 10 min of contact, reaching
about 340 µg Cu2+ g−1 , after a contact of 360 min (Fig. 3), thus confirming the promising potential of using NOR as copper
adsorbents in effluents and environmental samples.
Based on the results obtained, it can be seen in Table 3 that this work contributes directly to the other studies that
have been developed so far. When considering the different alternative methods of removing potentially toxic metals,
mainly for the treatment of e-waste, it is possible to observe studies of biosorption, bioleaching, and phytoremediation.
Studies conducted by the bioleaching method show recovery of different potentially toxic metals from 40 to 80%,
phytoremediation studies showed the adsorption capacity ranging from 1.0 mg to 119.18 mg per plant for Cd, Pb and
Cu ions. Using biosorbents, it is possible to see a removal efficiency of over 90% for gold (Au) (Kaliyaraj et al., 2019; Luo
et al., 2017, 2020; Oliveira et al., 2019; Zhou et al., 2021).
A recovery of approximately 340 µg Cu2+ g−1 may be considered a very significant result, making clear the viability of
applying NOR, for example, immobilized in retention filters, aiming to complex potentially toxic metals from leachates or
to environmental remediation. Taking into account the possible presence of other metals in the effluent, such as iron from
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Fig. 4. Application of a natural organic residue (NOR) in the retention of potentially toxic metals. The percentages of copper, iron, manganese and
chromium, and overall retention for all metals retained by NOR-n-EE4 from an e-waste, were determined as a function of the contact time.

Fig. 5. Micrograph of the NOR-n-EE4.

FeCl3 , as well as other metal ions, which may also bind to complexing sites in NOR, a complementary quantification of
iron, chromium and manganese retained by NOR-n-EE4 was also made. The Fig. 4 suggests a possible competition among
the different metal ions present in the effluent, since the copper retention, in the presence of the other metal species,
was considerably lower in this case (only 16% for copper). For the other metals, the retention percentages were 10% for
chromium, 17% for manganese and 33.4% for iron, and a total retention of 76% was achieved for all metals analyzed. These
data reinforce the promising use of NOR, from non-exhaustive extractions, in the remediation of metal species released
from e-waste.

3.4. Scanning transmission electron microscopy (STEM)

Based on the NOR sample that showed the best retention of copper ions (NOR-n-EE4) in the kinetic studies, and on
its application for retention of metals from an e-waste leachate, micrographs were obtained for analyses of the structural
characteristics of the sample. From the micrographs obtained by SEM of the NOR-n-EE4 sample, it is possible to observe
heterogeneously distributed morphological characteristics, consisting of particles of different sizes, shapes and pores
(Fig. 5), which may contribute to the increase of the surface area during the adsorption processes, since adsorption is
a surface phenomenon (Manahan, 2009).
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L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

4. Conclusion

In this study, humic substances were submitted to exhaustive and non-exhaustive extractions, so that the structures
and physical chemical characteristics of the resulting natural organic residues (NOR) could be evaluated, aiming to check
their capacities to retain copper, as well as other potentially toxic metals from e-waste. In harder extractions, there was
loss of important organic groups, which are pivotal to the complexation of metals species, thus generating NOR with
lower capacities of retention. Conversely, the NOR from non-exhaustive extractions that employed just one extraction
solution presented the highest copper retention, when compared with those obtained from more exhaustive ways. Since
the sample NOR-n-EE4 showed the best copper retention, it was tested in an e-waste effluent, reaching 340 µg Cu2+ g−1
removed, after 360 min. Based on the results presented, it may be concluded that NOR from milder extractions represent
promising materials, which can be successfully used as chelating agents in the environmental remediation of copper, as
well as other potentially toxic metals from e-waste effluents.

CRediT authorship contribution statement

Luana Maria Tavares Rosa: Conceptualization, Methodology, Validation, Investigation, Formal analysis, Data curation,
Project administration, Visualization, Writing – original draft. Wander Gustavo Botero: Resources, Writing – review &
editing. Janaina Braga do Carmo: Resources, Writing – review & editing. Gabriele V.M. Gabriel: Visualization, Writing –
review & editing. Walter Ruggeri Waldman: Resources, Writing – review & editing. Alexandre D.M. Cavagis: Writing
– review & editing. Danielle Goveia: Resources, Writing – review & editing. Luciana Camargo de Oliveira: Project
administration, Supervision, Funding acquisition, Resources, Formal analysis, Writing – review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Acknowledgments

This study was partially financed by Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001; pro-equipment project (proposal no. 189683) CAPES no. 11/2014; Conselho Nacional de Desenvolvi-
mento Científico e Tecnológico (CNPq), Brazil - Process no. 309713/2015-3; to the Electronic Microscopy Laboratories
(LME) of the National Nanotechnology Laboratory (LNNano), in Campinas/SP; Postgraduate Program of Biotechnology and
Environmental Monitoring PPGBMA, UFSCar, UFAL and UNESP.

References

Almendros, G., Sanz, J., 1991. Structural study on the soil humin fraction—boron trifluoride-methanol transesterification of soil humin preparations.
Soil Biol. Biochem. 23, 1147–1154. http://dx.doi.org/10.1016/0038-0717(91)90027-H.
Andreas, R., Zhang, J., 2014. Characteristics of adsorption interactions of Cadmium(II) onto humin from peat soil in freshwater and seawater media.
Bull. Environ. Contam. Toxicol. 92, 352–357. http://dx.doi.org/10.1007/s00128-014-1205-x.
Awasthi, A.K., Zeng, X., Li, J., 2016. Environmental pollution of electronic waste recycling in India: A critical review. Environ. Pollut. 211, 259–270.
http://dx.doi.org/10.1016/j.envpol.2015.11.027.
Beiyuan, J., Tsang, D.C.W., Ok, Y.S., Zhang, W., Yang, X., Baek, K., Li, X.-D., 2016. Integrating EDDS-enhanced washing with low-cost stabilization of
metal-contaminated soil from an e-waste recycling site. Chemosphere 159, 426–432. http://dx.doi.org/10.1016/j.chemosphere.2016.06.030.
Bezerra, M.F., Lacerda, L.D., Lai, C., 2019. Trace metals and persistent organic pollutants contamination in batoids (Chondrichthyes: Batoidea): A
systematic review. Environ. Pollut. 248, 684–695. http://dx.doi.org/10.1016/j.envpol.2019.02.070.
Bilgen, S., Sarıkaya, İ., 2015. Exergy for environment, ecology and sustainable development. Renew. Sustain. Energy Rev. 51, 1115–1131. http:
//dx.doi.org/10.1016/j.rser.2015.07.015.
Botero, W.G., Oliveira, L.C., Cavagis, A.D.M., Rosa, A.H., Rocha, J.C., Santos, A., 2013. Influence of the extractant on the complexing capacity of humic
substances from peat for macro and micronutrients using continuous flow: agricultural application and environmental impacts. J. Braz. Chem.
Soc. 24, 2015–2020. http://dx.doi.org/10.5935/0103-5053.20130252.
Botero, W.G., Oliveira, L.C., Rocha, J.C., Rosa, A.H., Santos, A., 2010. Peat humic substances enriched with nutrients for agricultural applications:
Competition between nutrients and non-essential metals present in tropical soils. J. Hazard. Mater. 177, 307–311. http://dx.doi.org/10.1016/j.
jhazmat.2009.12.033.
Burba, P., Van den Bergh, J., Klockow, D., 2001. On-site characterization of humic-rich hydrocolloids and their metal loading by means of mobile
size-fractionation and exchange techniques. Fresenius J. Anal. Chem. 371, 660–669. http://dx.doi.org/10.1007/s002160101013.
Cakir, O., 2006. Copper etching with cupric chloride and regeneration of waste etchant. J. Mater Process. Technol. 175, 633 17. http://dx.doi.org/10.
1016/j.jmatprotec.2005.04.024, Achievements in Mechanical & Materials Engineering.
Camioto, F. de C., Mariano, E.B., Rebelatto, D.A. do N., 2014. Efficiency in Brazil’s industrial sectors in terms of energy and sustainable development.
Environ. Sci. Policy 37, 50–60. http://dx.doi.org/10.1016/j.envsci.2013.08.007.
Cerqueira, S. da C.A., Romão, L.P.C., Lucas, S.C.O., Fraga, L.E., Simões, M.L., Hammer, P., Lead, J.R., Mangoni, A.P., Mangrich, A.S., 2012. Spectroscopic
characterization of the reduction and removal of chromium (VI) by tropical peat and humin. Fuel 91, 141–146. http://dx.doi.org/10.1016/j.fuel.
2011.06.023.
Chang, R.R., Mylotte, R., Hayes, M.H.B., McLnerney, R., Tzou, Y.M., 2014. A comparison of the compositional differences between humic fractions
isolated by the IHSS and exhaustive extraction procedures. Naturwissenschaften 101, 197–209. http://dx.doi.org/10.1007/s00114-013-1140-4.

10
L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Chen, Y., Senesi, N., Schnitzer, M., 1977. Information provided on humic substances by E4/E6 ratios. Soil Sci. Soc. Am. J. 41, 352–358. http:
//dx.doi.org/10.2136/sssaj1977.03615995004100020037x.
Chen, W., Wang, H., Gao, Q., Chen, Y., Li, S., Yang, Y., Werner, D., Tao, S., Wang, X., 2017. Association of 16 priority polycyclic aromatic
hydrocarbons with humic acid and humin fractions in a peat soil and implications for their long-term retention. Environ. Pollut. 230, 882–890.
http://dx.doi.org/10.1016/j.envpol.2017.07.038.
Chen, H., Wang, L., Hu, B., Xu, J., Liu, X., 2022. Potential driving forces and probabilistic health risks of heavy metal accumulation in the soils from
an e-waste area, southeast China. Chemosphere 289, 133182. http://dx.doi.org/10.1016/j.chemosphere.2021.133182.
Cunha, G.C., Romão, L.P.C., Santos, M.C., Costa, A.S., Alexandre, M.R., 2012. A green strategy for desorption of trihalomethanes adsorbed by humin
and reuse of the fixed bed column. J. Hazard. Mater. 209–210, 9–17. http://dx.doi.org/10.1016/j.jhazmat.2011.12.028.
De la Rosa, G., Peralta-Videa, J.R., Gardea-Torresdey, J.L., 2003. Utilization of ICP/OES for the determination of trace metal binding to different humic
fractions. J. Hazard. Mater. 97, 207–218. http://dx.doi.org/10.1016/S0304-3894(02)00262-5.
Deblonde, T., Cossu-Leguille, C., Hartemann, P., 2011. Emerging pollutants in wastewater: A review of the literature. Int. J. Hyg. Environ. Health 214,
442–448. http://dx.doi.org/10.1016/j.ijheh.2011.08.002.
Dick, D.P., Santos, J.H.Z., Ferranti, E.M., 2003. Chemical characterization and infrared spectroscopy of soil organic matter from two southern Brazilian
soils. Rev. Bras. Ciênc. Solo 27, 29–39. http://dx.doi.org/10.1590/S0100-06832003000100004.
Du, Y., Wu, Q., Kong, D., Shi, Y., Huang, X., Luo, D., Chen, Z., Xiao, T., Leung, J.Y.S., 2020. Accumulation and translocation of heavy metals in
water hyacinth: T maximising the use of green resources to remediate sites impacted by e- waste recycling activities. Ecol. Ind. 115, 106384.
http://dx.doi.org/10.1016/j.ecolind.2020.106384.
Forti, V., Baldé, C.P., Kuehr, R., Bel, G., 2020. The Global E-Waste Monitor 2020: Quantities, Flows and the Circular Economy Potential. United Nations
University (UNU)/United Nations Institute for Training and Research (UNITAR) – co-hosted SCYCLE Programme, International Telecommunication
Union (ITU) & International Solid Waste Association (ISWA), Bonn/Geneva/Rotterdam.
Francioso, O., Ciavatta, C., Gessa, C., Tugnoli, V., Sanchez-Cortes, S., 1998. Spectroscopic characterization of pyrophosphate incorporation during
extraction of peat humic acids. Soil Sci. Soc. Am. J. 62, 181–187. http://dx.doi.org/10.2136/sssaj1998.03615995006200010024x.
Gavrilescu, M., Demnerová, K., Aamand, J., Agathos, S., Fava, F., 2015. Emerging pollutants in the environment: present and future challenges in
biomonitoring, ecological risks and bioremediation. New Biotechnol. 32, 147–156. http://dx.doi.org/10.1016/j.nbt.2014.01.001.
Goveia, D., Melo, C.A., Oliveira, L.K., Fraceto, L.F., Rocha, J.C., Filho, N.L.D., Rosa, A.H., 2013. Adsorption and release of micronutrients by humin
extracted from peat samples. J. Braz. Chem. Soc. 24, 721–730. http://dx.doi.org/10.5935/0103-5053.20130092.
Griffith, S.M., Schnitzer, M., 1975. Analytical characteristics of humic and fulvic acids extracted from tropical volcanic soils. Soil Sci. Soc. Am. J. 39,
861–867. http://dx.doi.org/10.2136/sssaj1975.03615995003900050023x.
Han, G., Jiang, T., Huang, Y., Zhang, Y., Li, G., 2012. Characteristics of humin fractions associated with inorganic minerals obtained by naoh, and NaOH
assisted with anthraquinone extraction procedures. J. Cent. South Univ. 19, 2286–2290. http://dx.doi.org/10.1007/s11771-012-1273-1.
Helal, A.A., Murad, G.A., Helal, A.A., 2011. Characterization of different humic materials by various analytical techniques. Arab. J. Chem. 4, 51–54.
http://dx.doi.org/10.1016/j.arabjc.2010.06.018.
Huey, L.J., Ahmed, H., Majid, N.M.A., 2010. Effects of extractants on the yields and selected chemical characteristics of humic acids isolated from
tropical saprists peat. Am. J. Appl. Sci. 7, 933–936. http://dx.doi.org/10.3844/ajassp.2010.933.936.
International Humic Substances Society (IHSS), 2020. Solation of IHSS soil fulvic and humic acids, n.d. IHSS. URL http://humic-substances.org/isolation-
of-ihss-soil-fulvic-and-humic-acids/ (accessed 15 March 2020).
Jesus, A.M.D., Romão, L.P.C., Araújo, B.R., Costa, A.S., Marques, J.J., 2011. Use of humin as an alternative material for adsorption/desorption of reactive
dyes. Desalination 274, 13–21. http://dx.doi.org/10.1016/j.desal.2011.01.063.
Kaliyaraj, D., Rajendran, M., Angamuthu, V., Antony, A.R., Kaari, M., Thangavel, S., Venugopal, G., Joseph, J., Manikkam, R., 2019. Bioleaching of
heavy metals from printed circuit board (PCB) by streptomyces albidoflavus TN10 isolated from insect nest. Bioresour. Bioprocess 6, 47.
http://dx.doi.org/10.1186/s40643-019-0283-3.
Lapworth, D.J., Baran, N., Stuart, M.E., Ward, R.S., 2012. Emerging organic contaminants in groundwater: A review of sources, fate and occurrence.
Environ. Pollut. 163, 287–303. http://dx.doi.org/10.1016/j.envpol.2011.12.034.
Li, C., Gao, S., Gao, Q., Wang, L., Zhang, J., Li, C., Gao, S., Gao, Q., Wang, L., Zhang, J., 2015. Characterization of bulk soil humin and its alkaline-soluble
and alkaline-insoluble fractions. Rev. Bras. Ciênc. Solo 39, 120–126. http://dx.doi.org/10.1590/01000683rbcs20150294.
Li, A., Kroeze, C., Kahil, T., Ma, L., Strokal, M., 2019. Water pollution from food production: lessons for optimistic and optimal solutions. Curr. Opin.
Environ. Sustain. 40, System dynamics and sustainability, 88ty 40, 88ity 40, 888, 8888timal solutions. Culuti..
Li, W., Simmons, P., Shrader, D., Herrman, T.J., Dai, S.Y., 2013. Microwave plasma-atomic emission spectroscopy as a tool for the determination of
copper, iron, manganese and zinc in animal feed and fertilizer. Talanta 112, 43–48. http://dx.doi.org/10.1016/j.talanta.2013.03.029.
Luo, J., Cai, L., Qi, S., Wu, J., Gu, X., 2017. A multi-technique phytoremediation approach to purify metals contaminated soil from e-waste recycling
site. J. Environ. Manage. 204, 17–22. http://dx.doi.org/10.1016/j.jenvman.2017.08.029.
Luo, J., He, W., Qi, S., Wu, J., Sophie Gu, X., 2020. A novel phytoremediation method assisted by magnetized water to decontaminate soil Cd based
on harvesting senescent and dead leaves of festuca arundinacea. J. Hazard. Mater. 383, 121115. http://dx.doi.org/10.1016/j.jhazmat.2019.121115.
Manahan, S.E., 2009. Environmental Chemistry, ninth ed. CRC Press LLC, Boca Raton.
Oliveira, L.C., Botero, W.G., Farias, T.S., Santos, J.C.C., Gabriel, G.V.M., Goveia, D., Cacuro, T.A., Waldman, W.R., 2019. Application of natural organic
residues as adsorbents to remove lead from waters. Water. Air. Soil Pollut. 230, 191. http://dx.doi.org/10.1007/s11270-019-4240-8.
Park, M., Lee, Y., Khan, A., Aleta, P., Cho, Y., Park, H., Park, Y.H., Kim, S., 2019. Metabolite tracking to elucidate the effects of environmental pollutants.
J. Hazard. Mater. 376, 112–124. http://dx.doi.org/10.1016/J.Jhazmat.2019.05.024.
Rice, J.A., 2001. Humin. Soil Sci. 166, 848–857.
Romão, L.P.C., Lead, J.R., Rocha, J.C., Oliveira, L.C. de, Rosa, A.H., Mendonça, A.G.R., Ribeiro, A. de S., 2007. Structure and properties of brazilian peat:
analysis by spectroscopy and microscopy. J. Braz. Chem. Soc. 18, 714–720. http://dx.doi.org/10.1590/S0103-50532007000400008.
Rosa, A.H., Rocha, J.C., Furlan, M., 2000. Humic substances of peat: study of the parameters that influence on the process of alkaline e extraction.
Quím. Nova 23, 472–476. http://dx.doi.org/10.1590/S0100-40422000000400008.
Schmidt, M.W.I., Knicker, H., Hatcher, P.G., Kogel-Knabner, I., 1997. Improvement of 13C and 15N CPMAS NMR spectra of bulk soils, particle
size fractions and organic material by treatment with 10% hydrofluoric acid. Eur. J. Soil Sci. 48, 319–328. http://dx.doi.org/10.1111/j.1365-
2389.1997.tb00552.x.
Shi, A., Shao, Y., Zhao, K., Fu, W., 2020. Long-term effect of E-waste dismantling activities on the heavy metals pollution in paddy soils of southeastern
China. Sci. Total Environ. 705, 135971. http://dx.doi.org/10.1016/j.scitotenv.2019.135971.
Song, G., Hayes, M.H.B., Novotny, E.H., Simpson, A.J., 2011. Isolation and fractionation of soil humin using alkaline urea and dimethylsulphoxide plus
sulphuric acid. Naturwissenschaften 98, 7–13. http://dx.doi.org/10.1007/s00114-010-0733-4.
Song, G., Novotny, E.H., Simpson, A.J., Clapp, C.E., Hayes, M.H.B., 2008. Sequential exhaustive extraction of a mollisol soil, and characterizations of humic
components, including humin, by solid and solution state NMR. Eur. J. Soil Sci. 59, 505–516. http://dx.doi.org/10.1111/j.1365-2389.2007.01006.x.
Starling, M.C.V.M., Amorim, C.C., Leão, M.M.D., 2019. Occurrence, control and fate of contaminants of emerging concern in environmentalcompartments
in Brazil. J. Hazard. Mater. 372, 17–36. http://dx.doi.org/10.1016/j.jhazmat.2018.04.043.

11
L.M.T. Rosa, W.G. Botero, J.B. do Carmo et al. Environmental Technology & Innovation 27 (2022) 102452

Stevenson, F.J., 1994. Extraction, fractionation, and general chemical composition of soil organic matter. In: Stevenson, F.J. (Ed.), Humus Chemistry,
second ed. John Wiley & Sons, New York, pp. 24–56.
Swift, R.S., 1996. Organic matter characterization. In: Sparks, D.L., Page, A.L., Helmke, P.A., Loppert, R.H., Soltanpour, P.N., Tabatabai, M.A., Johnston, C.T.,
Summner, M.E. (Eds.), Methods of Soil Analysis: Chemical Methods, Part 3. Soil Science Society of America, Madison, WI (1996), pp. 1018–1020.
Tatzber, M., Stemmer, M., Splegel, H., Katziberger, C., Haberhauer, G., Mentler, A., Gerzabek, M.H., 2007. FTIR-spectroscopic characterization of humic
acids and humin fractions obtained by advanced NaOH, Na4 P2 O7 , and Na2 CO3 extraction procedures. J. Plant Nutri. Soil Sci. 170, 522–529.
http://dx.doi.org/10.1002/jpln.200622082.
Tchounwou, P.B., Yedjou, C.G., Patlolla, A.K., Sutton, D.J., 2012. Heavy metals toxicity and the environment. EXS 101, 133–164. http://dx.doi.org/10.
1007/978-3-7643-8340-4_6.
Tivet, F., de Moraes Sá, J.C., Lal, R., Milori, D.M.B.P., Briedis, C., Letourmy, P., Pinheiro, L.A., Borszowskei, P.R., da Cruz Hartman, D., 2013. Assessing
humification and organic C compounds by laser-induced fluorescence and FTIR spectroscopies under conventional and no-till management in
Brazilian oxisols. Geoderma 207–208, 71–81. http://dx.doi.org/10.1016/j.geoderma.2013.05.001.
Tkaczyk, A., Mitrowska, K., Posyniak, A., 2020. Synthetic organic dyes as contaminants of the aquatic environment and their implications for
ecosystems: A review. Sci. Total Environ. 717, 137222. http://dx.doi.org/10.1016/j.scitotenv.2020.137222.
Trevisan, S., Francioso, O., Quaggiotti, S., Nardi, S., 2010. Humic substances biological activity at the plant-soil interface. Plant Signal Behav. 5, 635–643.
http://dx.doi.org/10.4161/psb.5.6.11211.
Wang, F., Dong, W., Zhao, Z., Wang, H., Li, W., Chen, G., Wang, F., Zhao, Y., Huang, J., Zhou, T., 2021. Heavy metal pollution in urban river sediment
of different urban functional areas and its influence on microbial community structure. Sci. Total Environ. 146383. http://dx.doi.org/10.1016/j.
scitotenv.2021.146383.
Wang, K., Xing, B., 2005. Chemical extractions affect the structure and phenanthrene sorption of soil humin. Environ. Sci. Technol. 39, 8333–8340.
http://dx.doi.org/10.1021/es050737u.
Won, S.W., Han, M.H., Yun, Y.S., 2008. Different binding mechanisms in biosorption of reactive dyes according to their reactivity. Water Res. 42,
4847–4855. http://dx.doi.org/10.1016/j.watres.2008.09.003.
Xu, X., Cao, X., Zhao, L., Wang, H., Yu, H., Gao, B., 2013. Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar.
Environ. Sci. Pollut. Res. 20, 358–368. http://dx.doi.org/10.1007/s11356-012-0873-5.
Zaccone, C., Soler-Rovira, P., Plaza, C., Cocozza, C., Miano, T.M., 2009. Variability in As, Ca, Cr, K, Mn, Sr, and Ti concentrations among humic acids
isolated from peat using NaOH, Na4 P2 O7 and NaOH + Na4 P2 O7 solutions. J. Hazard. Mater. 167, 987–994. http://dx.doi.org/10.1016/j.jhazmat.2009.
01.078.
Zhou, W., Liang, H., Lu, Y., Xu, H., Jiao, Y., 2021. Adsorption of gold from waste mobile phones by biochar and activated carbon in gold iodized
solution. Waste Manage. 120, 530–537. http://dx.doi.org/10.1016/j.wasman.2020.10.017.

12