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Discarded yerba mate as a source of cellulose fibers with promising

applications for drinking water decontamination

Article in Industrial Crops and Products · February 2024

DOI: 10.1016/j.indcrop.2024.118253

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 Industrial Crops & Products 211 (2024) 118253

Contents lists available at ScienceDirect

Industrial Crops & Products

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

Discarded yerba mate as a source of cellulose fibers with promising

applications for drinking water decontamination
Cintya Gordon-Falconí a, *, María Florencia Iannone a, Myriam Sara Zawoznik b, Alexis Debut c,
María Daniela Groppa a
a
Universidad de Buenos Aires. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Química y Fisicoquímica Biológicas (IQUIFIB). Facultad de
Farmacia y Bioquímica, Junín 956, Buenos Aires 1113, Argentina
b
Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica, Cátedra de Química Biológica Vegetal, Junín 956, Buenos Aires 1113, Argentina
c
Centro de Nanociencia y Nanotecnología, Universidad de las Fuerzas Armadas ESPE, Av. Gral Rumiñahui s/n, Sangolquí, Ecuador

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

Keywords: In recent years, the focus on environmental sustainability and circular economy has encouraged the reutilization
AgNPs of plant residues. This work aimed at evaluating the potential of discarded yerba mate (DYM) as a source of
antimicrobial activity cellulose fibers suitable to retain low biodegradability emerging contaminants, such as dyes. In addition, we
cellulose-based nanocomposite
aimed at testing whether the inclusion of silver nanoparticles within those fibers could result in a novel nano­
dye biosorbent
composite with antimicrobial properties. The raw material (DYM) and the cellulose fibers were characterized
according to TAPPI standards. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning
electron microscopy (SEM), thermogravimetric analysis (TGA), and tensile strength assessment were conducted.
The cellulose content of the DYM was 46.61%. The XRD analysis revealed an increase in cellulose crystallinity
index from 19% in the raw material to 60% after cellulose extraction treatments. Cellulose fibers adsorbed about
80–90% of the dyes tested (crystal violet, CV; methylene blue, MB; and safranin, S) at a concentration of 20 mg/
L. The adsorption efficiency of the nanocomposite was somewhat lower than that of the fibers alone, while its
ability to immobilize Escherichia coli and Staphylococcus aureus cells was higher. Due to these features, the
nanocomposite here described could be useful to obtain, in the future, a simple filtering device which could
provide safer water at domestic level to periurban settlers with no access to potable water sources.

1. Introduction residues has a significant environmental, social, and economic impact

The circular economy seeks to redirect the current model of pro­
duction and consumption of goods and services; it aims for production
processes to be circular, and for waste to be reintegrated into the pro­
duction chain as a resource. Within the circular economy, waste valo­
rization aims to eliminate and/or control waste and the pollution
derived from its generation. Therefore, it is essential to find mecha­
nisms, processes, and technologies that improve waste management,
promote its transformation, provide new uses, and extend its lifespan
(Ghisellini et al., 2016)
Considering that most carbon-based compounds originate from pe­
troleum refining processes, the recovery of biopolymers from plant
(Tuck et al., 2012).
Ilex paraguariensis or “yerba mate” is a native plant from South
America used to prepare hot or cold drinks in Argentina, Paraguay,
Uruguay, and south of Brazil. In Argentina, approximately 6 kg of yerba
mate are consumed per person and year. This generates 291 tons of
vegetable waste, according to the National Institute of Yerba Mate
(INMY, 2017), which is simply discarded or used as manure. Organic
wastes possess nutrients and other interesting compounds that could be
recycled, with economic and environmental benefits (Six et al., 2016). In
this sense, the yerba mate residue is arising as an interesting source of
cellulose for different applications: in aerogel elaboration (Oliveira
et al., 2020), to obtain lignocellulosic-based nanoparticles (Arrieta et al.,

Abbreviations: Ag-NPs, silver nanoparticles; RCel, raw cellulose; BCel, bleached cellulose; Cel-NP, cellulose-AgNPs composite; CV, crystal violet dye; DYME,
discarded yerba mate extract; DYM, discarded yerba mate; MB, methylene blue dye; NPs, nanoparticles; S, safranin dye; WS, washing solution.
* Correspondence to: Universidad de Buenos Aires. Consejo Nacional de lnvestigaciones Científicas y Técnicas. Instituto de Química y Fisicoquímica Biológicas
(IQUIFIB). Facultad de Farmacia y Bioquímica, Cátedra de Química Biológica Vegetal, Junín 956, Buenos Aires 1113, Argentina.
E-mail address: cgordon@ffyb.uba.ar (C. Gordon-Falconí).

https://doi.org/10.1016/j.indcrop.2024.118253
Received 24 July 2023; Received in revised form 19 January 2024; Accepted 5 February 2024
0926-6690/© 2024 Elsevier B.V. All rights reserved.
C. Gordon-Falconí et al.
2018), as a substrate in vermiculture (Torrendel et al., 2018), or as
biosorbents for the removal of metals from aqueous solutions (Copello
et al., 2011).
Population growth, human activities, urban expansion, and the lack
of responsive programs in the face of rapid development and global­
ization have promoted an increase in pollution levels across all ecosys­
tems, negatively impacting all natural resources. Wastewater can
contain a mixture of organic and inorganic chemicals, as well as path­
ogenic microbial agents (Abu Elella et al., 2019). Textile, food, leather,
pharmaceuticals, and printing industries generate considerable volumes
of colored effluents. A significant proportion of dyes (15–50%) are dis­
charged as wastewater. Among the dyes commonly employed in
microbiological staining, both crystal violet and safranin have notable
environmental implications. Safranin, recognized as a phenazine dye,
serves as a counterstain, contributing to water pollution concerns, as
highlighted by Hayat et al. (2011). In addition, crystal violet has the
potential to accumulate in water bodies, exhibiting carcinogenic and
genotoxic properties, as reported by Abu Elella et al. (2019) and Cha­
hinez et al. (2020). Similarly, methylene blue is considered safe within
therapeutic doses, but excessive exposure to this dye can lead to toxicity,
as noted by Ginimuge and Jyothi (2010). Reports from Chen et al.
(2011) and Deng et al. (2011) underscore the harmful effects of acute
methylene blue exposure on human health.
In 2015, the United Nations released the Sustainable Development
Goals (SDGs), 17 specific objectives aiming at laying a solid foundation
by 2030 for long-term sustainable development (United Nations, 2019).
Two of these goals are of utmost significance: access to clean water and
sanitation (goal 6) and responsible production and consumption (goal
12). In line with the SDGs and fueling the recirculation model to meet
immediate social needs in less developed countries, in this study, we
aimed at developing an extraction procedure to obtain cellulose fibers
from discarded yerba mate (i.e., previously consumed as “mate”) and a
synthesis procedure using those fibers to obtain a cellulose-silver
nanoparticles composite, which might become in the future an inex­
pensive water-remediation device, obtained mostly from an abundant
waste. We hypothesized that discarded yerba mate might serve as a
source of both the reduction power needed to obtain silver NPs and the
structural component to fix these NPs on a solid matrix capable of
removing chemical and biological pollutants from water at a domestic
level. As far as we know, this is the first report describing the green
synthesis of a cellulose-silver nanoparticle composite using discarded
yerba mate, a Latin American typical domestic waste, as a source of both
cellulose and reducing power to achieve silver reduction.
2. Materials and methods
2.1. Chemicals and reagents
To obtain cellulose fibers, discarded yerba mate was obtained as
described by Gordon-Falconí et al. (2020). Silver nitrate (AgNO3,
99.0%) and methylene blue (MB, 99.5%) were procured from Spectrum,
USA. Crystal violet (reagent grade), nitric acid (HNO3, 69%), safranin
(reagent grade), sodium hypochlorite (reagent grade), sodium hydrox­
ide (reagent grade), sodium acetate (reagent grade), and sulfuric acid
(reagent grade) were purchased from Fisher Scientific. Acetic acid (re­
agent grade) was acquired from Merck. Millipore Milli-Q water was
used.
2.2. Isolation of cellulose fibers from discarded yerba mate
About 400 g of discarded yerba mate (DYM) after its use as an
infusion was collected, oven-dried at 50 ± 5 ◦ C (Wiseven WOF-50.
Korea) for 48 h and stored at 20 ± 5 ◦ C until use.
The obtention of the cellulose fibers contained in the DYM was car­
ried out based on methodologies previously described (Borsoi et al.,
2020; Dahlem et al., 2019). Briefly, an alkaline treatment with 15%
2
Industrial Crops & Products 211 (2024) 118253
NaOH (w/v), at a ratio of 1 g/10 mL, was applied during 4 h under
shaking (150 rpm) on a heating plate (40 ± 5 ◦ C) (Thermo Scientific
CIMAREC HP131535, USA). The suspension was filtered, and the
remaining material was washed with distilled water until a constant pH
of 7 was recorded in the leaching fraction. This material is further named
“raw cellulose” (RCel). A second bleaching step was performed by
adding 0.5% (w/v) sodium hypochlorite solution (1:10) and keeping the
mixture under continuous stirring for 2 h at 30 ± 5 ◦ C. At the end of the
whitening step, the color of the fibers was observed, and, if necessary, a
second bleaching cycle was applied. After the complete bleaching, the
fibers were filtered, washed until pH = 7, and oven-dried (50–60 ◦ C).
This material is subsequently named “bleached cellulose” (BCel).
2.3. Physicochemical characterization of the DYM, RCel, and BCel
The moisture, solubility in water and NaOH, and Klason lignin in the
DYM, RCel, and BCel were determined according to the methodology
detailed in the Technical Association of the Pulp and Paper Industry
(TAPPI) standards T412 om-06*, T207 cm-99, T212 om-02, and T222
om-02 (TAPPI, 2023). The cellulose content in the DYM was determined
according to the methodology established by Kurschner and Hoffer
(1993) with slight modifications. A mixture of 1 g of DYM, 20 mL of
99.5% ethanol (v/v), and 5 mL of 69% nitric acid (v/v) was boiled for
30 min using a reflux condenser to keep the volume constant. Subse­
quently, the sample was filtered, and a second digestion was carried out.
Finally, a third digestion with 100 mL of distilled water for 60 min was
performed. The sample was then cooled in an ice bath, filtered, washed,
and dried (105 ± 3 ◦ C) until constant weight. Cellulose (%) was calcu­
lated with the equation below:
Cellulose (%) = [(Sample weight after the extraction process, g)/(Sample
weight before the extraction process, g)]*100
2.4. Synthesis of a novel cellulose-AgNPs composite
The synthesis of a novel cellulose-AgNPs composite (subsequently
referred to as Cel-NP) was achieved by mixing the cellulose fibers from
the DYM with AgNO3 plus a DYM extract, as the reducing agent. The
composition of the DYM extract was previously characterized by Fourier
transform infrared (FTIR) spectroscopy which revealed stretching vi­
brations of hydroxyl groups (O–H) with hydrogen bonding usually
related to polyphenols. The estimation of total phenol content and
protein concentration were 26.97 ± 1.97 mg GAE/g (Gordon-Falconí
et al., 2020) and 113.94 ± 0.85 mg/g (dry weight basis), respectively.
Briefly, 0.02 g of BCel was immersed in 10 mL of 1 mM AgNO3 and
0.1 mL of the DYM extract. After stirring for 30 min and applying 2
sonication cycles (30 min each) in a sonicator bath (Ultrasonic, Cole-
Parmer. Mexico), the mixture was filtered, and the residue was
washed and dried to constant weight (50 ± 5 ◦ C). In the supernatant, the
expected reduction of Ag+ to Ag0 was corroborated by UV–vis spectro­
scopic scanning, and the absorbance between 200 and 700 nm was
measured to detect the characteristic peak of these AgNPs in the range
from 380 to 440 nm, as previously described (Gordon-Falconí et al.,
2020). In addition, the hydrodynamic size distribution was analyzed in
the supernatant of the reaction for the composite synthesis using dy­
namic light scattering (DLS) instrument (LB-550, Horriba, Japan) under
the following analysis parameters: 25 ◦ C; viscosity 0.9190 mPa/s, host
medium refractive index 0.330, silver refractive index 0.280.
2.4.1. Physicochemical characterization of the cellulose fibers and the novel
cellulose-AgNPs composite
The morphology and surface properties of Cel-NP were studied
through field gun emission scanning electron microscopy (FEG-SEM,
TESCAN, MIRA 3) imaging. A back-scattered electron (BSE) detector
C. Gordon-Falconí et al.
was used to acquire some microphotographs. The chemical composition
of Cel-NP was analyzed using energy-dispersive X-ray spectrometry
(EDX, Bruker Nano GmbH, Quantax, with Kα) and Fourier transform
infrared spectroscopy (FTIR-ATR, Perkin Elmer), with a resolution of
4 cm− 1. Possible changes in cellulose functional groups due to AgNPs
adsorption were evaluated with this method.
Also, the resistance and elasticity of cellulose fibers (alone or in
combination with AgNPs) in the presence of a quasi-static force were
studied. The tensile test was performed in a rheometer (Discovery HR-2,
TA Instrument, United States) under room temperature (20 ± 3 ◦ C),
constant linear rate of 100 µm/s for a period 15 ± 5 sec. Rectangular
samples (9 ×40×3 mm, approximately) were prepared for this analysis
using the methodology proposed by Robles et al. (2021). The cellulose
fibers were vacuum filtered using a nylon membrane attached to a
Buchner funnel, forming a wet mat. This wet mat was subsequently
hot-pressed at 110◦ C. The specimens for the tensile tests were obtained
from these laminates, according to ASTM standards (ASTM Interna­
tional, 1996). The tensile stress (σ t) was calculated according to the
equation:
σt= F/A
where F is the axial load (N), and A is the cross-sectional area of the
analyzed sample (mm2).
Mass decomposition rate as a function of temperature was deter­
mined by thermogravimetry analysis (TGA-50, Shimadzu) under the
following analysis conditions: sample weight was between 8.1 and
8.3 mg, N2 atmosphere with a purge rate of 30 mL/min, rate of heating
10 ◦ C/min, and temperature range 24–700 ◦ C. Thermograms were
normalized for analysis by applying the following equation:
m (%) = [(mo-mt)/(mo)]*100
where m (%) is the percentage of lost mass, mo is the mass of the sample
at the beginning of the assay, and mt is the mass of the sample at the end
of each temperature cycle.
The crystallinity of the cellulose fibers obtained from DYM and that
of the Cel-NP composite was analyzed by studying the X-ray diffraction
(XRD) pattern in an XRD EMPYREAN diffractometer (PANalytical, X-ray
tube copper k = 1.54059 Å, Holland). The presence of characteristic
silver peaks was also evaluated, and the crystallinity index (CI) was
calculated according to Segal et al. (1959), following the equation:
where I(002) is the peak intensity around 22.0◦ (crystalline phase) and
I(am) is the peak intensity around 18.0◦ (amorphous phase).
2.5. Potential uses of the novel cellulose-AgNPs composite
2.5.1. Removal of emerging contaminants
The capacity of the bleached cellulose (BCel) and the composite (Cel-
NP) to retain water-soluble xenobiotics was studied by using the cationic
dyes methylene blue (MB), crystal violet (CV), and safranin (S) at two
different concentrations: 20 and 160 mg/L. The adsorption process was
studied in "batch" tests: 0.4 mg/mL of cellulose was subjected to constant
orbital agitation (150 rpm) in the dark at 20 ± 5 ◦ C during 150 min
(BCel) and 120 min (Cel-NP). The rate of decrease in the dye concen­
tration, estimated from the absorbance at the corresponding wavelength
peaks (MB, λmax = 664 nm; CV, λmax = 590 nm; S, λmax = 518 nm), was
determined. The pH was controlled at the beginning and end of each
test. The removal efficiency (%) and the equilibrium adsorption capacity
(Qe) for each dye were determined according to the following equations:
Efficiency (%) = [(Co-Ce)/Co]*100
Qe=[(Co-Ce)/W]*V
where Co and Ce are the initial and equilibrium concentrations of the
contaminating compounds (mg/L), respectively, V is the volume of the
solution (L), and W is the weight of the adsorbent material used (g).
3
Industrial Crops & Products 211 (2024) 118253
2.5.2. Retention and inactivation of bacterial pathogens
A gram-negative and a gram-positive bacterium, Escherichia coli
(ATCC 25922) and Staphylococcus aureus (ATCC 6538 P), were used to
test the capacity of the BCel and Cel-NP to retain and inactivate bacterial
pathogens. Both strains were obtained from the culture collection of
Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires. Bac­
teria were routinely grown in Luria-Bertani (LB) culture medium; a
concentration of 103 CFU/mL was used as the initial titer to study both
the adsorption capacity and the antimicrobial activity, in line with
previous reports (Montazer et al., 2012; Ottenhall et al., 2018).
The capacity of these cellulose-based matrices to retain bacteria was
evaluated using 7.0 ×7.0 mm sheet samples (BCel and Cel-NP), ac­
cording to methodologies previously described (Maneerung et al., 2008;
Montazer et al., 2012), with slight modifications. These sheets were
moistened with 50 µL of the corresponding bacterial suspension (E. coli
or S. aureus). After 1 and 3 h (E. coli) or 3 and 6 h (S. aureus) of being
moistened, the sheets were transferred to sterile tubes containing 200 µL
of saline solution [0.9% NaCl (w/v)], where they remained submerged
for 15 minutes. The number of viable cells released to the saline solution
was estimated using the drop count method (Herigstad et al., 2001).
Additionally, the cellulose sheets were transferred to Petri dishes con­
taining solid LB culture medium and incubated at 37 ◦ C. Bacterial
growth around the sheets was monitored at 24, 48, and 72 h.
The antimicrobial activity—conceived as that leading to both bac­
terial death (“bactericide”) or bacterial impairment to multiply at
normal rates (“bacteriostatic”)—of BCel and Cel-NP was evaluated first
according to Maneerung et al. (2008), with slight modifications. Sam­
ples (about 15 mg) of the cellulose fibers alone (BCel) or the synthesized
composite (Cel-NP) were placed into tubes containing 1 mL of saline
solution and shaken vigorously. Next, the tubes were inoculated with
0.5 mL of E. coli or S. aureus cell suspensions (103 CFU/mL) and sub­
jected to shaking (150 rpm) at 37 ◦ C. Aliquots (30 µL) of the saline so­
lution were taken after 1, 2, and 3 h (E. coli) or 3 and 6 h (S. aureus) to
determine the number of viable cells through the drop count method.
We confirmed that cellulose fibers and the nanocomposite synthesized
were free of contaminants by placing 15 mg of BCel or Cel-NP in test
tubes containing LB medium and incubating these tubes at the condi­
tions previously described. The antimicrobial effect of these materials on
E. coli was also tested through the diffusion method (Ghiuță et al., 2018).
Ampicillin (30 µg) was used as positive control in the assay.
2.6. Statistical analysis
The characterization tests and the emerging contaminants assays
were performed in triplicate in three blocks of independent experiments.
The maximum adsorption capacities of the dyes were analyzed by
analysis of variance (ANOVA); to correct the heteroscedasticity of the
data, the VARIDENT function was used in the model. General linear
models (GLM) were utilized to test the antimicrobial activity. The free
software RStudio was used to perform statistical analyses and graphical
representations (RStudio, 2020)
Table 1
Physicochemical characterization of DYM.
Parameter %
Moisture 1.18 ± 0.13
Solubility at 25 ◦ C 21.14 ± 1.87
Solubility at 100 ◦ C 21.39 ± 2.02
Solubility in NaOH 45.89 ± 1.80
Insoluble lignin (Klason lignin) 30.05 ± 1.27
Cellulose 46.61 ± 3.55
C. Gordon-Falconí et al.
3. Results and discussion
3.1. DYM as an interesting source of cellulose fibers
Table 1 shows the main parameters of the DYM after drying it at 50 ±
5 ◦ C. It may be observed that the drying process applied to this waste
was adequate to reach a moisture content low enough to prevent mi­
crobial contamination and hydrolytic or oxidative degradation (Ade­
kunle et al., 2023).
The cellulose content of this material was in line with data from
previous studies, which reported values from 30% to 54% (w/w) in
yerba mate fractions obtained during the industrialization process
(Borsoi et al., 2020). Cellulose concentration in plant materials depends
on the plant species, the plant age, the extraction and purification pro­
cess, and the surface irregularities of the fibers (Senthamaraikannan and
Kathiresan, 2018). Insoluble lignin (Klason) was also an abundant
component in the DYM; similar values were found in yerba mate sticks
recovered during yerba mate elaboration (Dahlem et al., 2019).
The water solubility of the DYM did not increase significantly under
high temperature (100 ◦ C) compared to that at 25 ◦ C, but it did under
alkaline conditions. It has been described that the alkaline treatment,
along with heat application, facilitates lignin, hemicellulose, and pectin
removal from plant wastes (Ferreira et al., 2019), while the bleaching
process allows the cellulose pulp whitening (Hintz and Lawal, 2018).
Sodium hypochlorite selectively oxidizes the residual lignin without
damaging the cellulose fibers, improving the crystallinity degree (García
et al., 2016). It should be noted that despite the important process of
extraction and dragging of soluble compounds (including antioxidant
substances, phenols, vitamins, and minerals) expected to occur during
"mate" consumption, these residues still contain valuable organic com­
pounds that could be used for biotechnological purposes (Gullón et al.,
2018). Moreover, the high and continuous availability of DYM in
Argentina represents an important advantage over other agricultural
Fig. 1. Macroscopic characteristics of discarded yerba mate (DYM) along the process of cellulose isolation. DYM (A); after NaOH treatment (B); after NaClO
treatment (C). FTIR spectra (D) and XRD diffractogram of DYM, raw cellulose (RCel), and BCel (E).
4
Industrial Crops & Products 211 (2024) 118253
residues, such as cereal husks, fruit, and vegetable by-products, whose
availability depends on crop seasonality (Saini et al., 2015).
3.2. Separation of cellulose fibers from DYM
Fig. 1 illustrates the macroscopic changes that DYM underwent along
the process of extraction/separation of cellulose fibers, which involved
the sequential exposure of the raw material (Fig. 1A) to NaOH (Fig. 1B)
and NaClO (Fig. 1C). Both steps of the process may have modified yerba
mate color due to the oxidation of compounds such as hemicellulose and
lignin. Clearly, size reduction, homogenization, and bleaching took
place after these treatments.
The increased band intensity between 3690 and 3000 cm− 1 in the
FTIR spectra of BCel (Fig. 1D) may be attributed to hydroxyl group (OH)
vibration in the cellulose molecules (Alves et al., 2015; Cui et al., 2013),
suggesting the concentration of this component after both steps. In the
BCel spectra, a decreased intensity of the bands between 2900 and
2850 cm− 1, which may correspond to symmetric and asymmetric
vibrational bands of the alkyl group (-CH3) in the aliphatic bonds of
complex carbon polymers (Arrieta et al., 2018; Borsoi et al., 2020), and
also the intensity reduction for the bands between 1700 and 1730 cm− 1,
considered indicative of acetyl and ester groups in hemicelluloses
(Mondragon et al., 2014), suggest the reduction of this component.
Similarly, after the sodium hypochlorite treatment, there were re­
ductions in the intensity of bands between 1440 and 1416 cm− 1,
attributed to -CH2 groups, and between 1370 and 1223 cm− 1, assigned
to stretching vibrations of C-H y C-C bonds in the aromatic rings and aryl
alkyl ether groups in the lignin (Borsoi et al., 2020), indicating a relative
reduction of these compounds. Finally, bands between 1174 and
1021 cm− 1 are associated with the stretching and deformation of the
C-OH and C-H bonds in the D-glucose units of cellulose, whereas the
band at 890 cm− 1 is assigned to the C-O-C bond; the intensity of these
bands demonstrates that cellulose fibers kept their chemical structure
C. Gordon-Falconí et al.
despite the treatments applied (Ahmed et al., 2021; Rac-Rumijowska
et al., 2019; W. Wang et al., 2018). As a whole, FTIR findings suggest
that the treatments applied to DYM contributed to cellulose
concentration.
In the XRD patterns of the DYM (Fig. 1E), the two broad peaks
observed at around 14◦ (110) and 22◦ (200) are indicative of typical
amorphous and crystalline compounds in plant samples, respectively, as
previously described (Ching and Ng, 2014). In the RCel and BCel, the
intensity at peak 22◦ was increased, which highlights the efficiency of
the extraction process, whose objectives are to dissolve low molecular
weight compounds and to increase the cellulose crystalline fraction. The
peaks around 14◦ and 16◦ may represent the amorphous region of the
cellulose, which would correspond to accompanying compounds such as
hemicellulose and lignin (Dahlem et al., 2019; Park et al., 2010). The
peaks at 14.9◦ (110), 16.5◦ (110), 22.6◦ (200), and 34.7◦ (004) are
characteristic of type I cellulose, the cellulose form found in nature
(Barbash et al., 2021; Evdokimova et al., 2021).
An increase in the crystallinity index (CI) was observed after each
step (Table 2), suggesting an increase in fibers’ resistance since CI and
resistance are parameters directly related. In addition, crystalline cel­
lulose is less susceptible to chemical reactions (Borsoi et al., 2020). Our
results are in accordance with those of Dahlem et al. (2019), who re­
ported crystallinity indices of 40.62% for untreated yerba mate residues
and 64.36% for residues subjected to alkaline treatments, bleaching, and
acid hydrolysis.
3.3. Morphology and mechanical properties of cellulose from DYM
Scanning electron microscopy observations revealed that cellulose
fibers obtained from DYM were predominantly arranged as helicoidal
structures (Fig. 2A). Regarding the mechanical properties, the tensile
strength of the BCel was 68.8 ± 2.6 MPa, the maximum tensile stress
97.7 ± 18.9 MPa, the deformation at the moment of fracture 1.33 ±
0.2%, and the modulus of elasticity, defined by the slope of the straight
line, equal to 105.99 ± 15.1 MPa. A representative plot stress-strain in
BCel samples is depicted in Fig. 2B. Though DYM cellulose fibers showed
higher tensile strength compared to nanocellulose extracted from wal­
nut shell (tensile strength of 7.81 ± 1.4 MPa) (Perumal et al., 2022),
they had lower tensile forces than fibers recovered from Agave americana
L. (tensile forces between 118.49 and 155.51 MPa depending on the
purification process) (Ahmed et al., 2021; Bezazi et al., 2014). Previous
reports indicated that tensile test forces depend on the plant species,
internal structure, and chemical composition of the fibers, as well as the
physico-chemical treatment used in the extraction process (Bezazi et al.,
2014; Mohanty et al., 2000).
3.4. Synthesis, morphology, and physicochemical properties of the novel
composite
The cellulose-silver nanoparticle composite was obtained through a
procedure in which AgNPs were synthesized in the presence of cellulose
fibers. AgNPs formation in the supernatant of the reaction was
confirmed by UV–vis spectroscopy through the detection of an absorp­
tion peak at 412 nm (Fig. 2C), as described in Gordon-Falconí et al.
Table 2
Changes in crystallinity index along cellulose extraction from
DYM.
Crystallinity index CI, %
DYM 19.32 ± 7.10
RCel 52.68 ± 1.78
BCel 60.43 ± 2.03
Cel-NP 60.00 ± 6.08
DYM, discarded yerba mate; RCel, raw cellulose; BCel,
bleached cellulose; Cel-NP, cellulose-AgNPs composite
5
Industrial Crops & Products 211 (2024) 118253
(2020). We highlight that the presence of cellulose fibers did not
interfere with the nanoparticles formation process, where the stoichio­
metric ratio in the reaction (AgNO3: DYM extract) and the pH of the
reducing agent behaved as key factors in the synthesis process. In this
procedure, Ag+ ions can enter the active sites of the fibers thanks to their
small ionic radius (0.1 nm), and during the process of synthesis, the
polymer can provide physical support for the slow growth of AgNPs.
The presence of AgNPs in the cellulose fibers was detected by a
change in their color from white to gray after the nanoparticle incor­
poration process. Similar results were obtained by Ahmed et al. (2018)
and Ali et al. (2018), who observed greenish and dark tones in the fibers
after incorporating nanomaterials.
The hydrodynamic diameter of the nanoparticles measured in the
supernatant after the composite formation process was somewhat
greater than that obtained in the absence of cellulose fibers, performed
in a previous study (Gordon-Falconí et al., 2020): 36.94 ± 4.3 nm [this
study] (Fig. 2D) vs. 24.32 ± 2.7 nm (Gordon-Falconí et al., 2020). The
XRD patterns of Cel-NP show four main peaks at 14.58◦ , 16.47◦ , 22.63◦ ,
and 34.52◦ (Fig. 2E). These peaks are attributed to the crystal planes
(110), (110), (200), and (004), characteristic of cellulose type I (Park
et al., 2010). Additionally, a diffraction peak at 2 θ◦ , characteristic of
silver (38.02◦ ), was identified. This peak can be attributed to the crystal
plane (111) and ensures the presence of silver nanocrystals with a cubic
crystal structure (CCS) (Biliuta and Coseri, 2019). Deeksha et al. (2021)
reported similar results after developing fabrics with antibacterial
properties based on cellulose and AgNPs. In addition, the CI of the cel­
lulose fibers did not change due to silver nanoparticle incorporation
(Table 2).
SEM photographs (Fig. 2F) shows the presence of AgNPs in the cel­
lulose fibers homogeneously distributed. Cellulose fibers could act as a
template or matrix, controlling the growth of the nanoparticles. Prob­
ably, the nanoparticles formed remain trapped in the skeleton of the
biopolymer, similar to that reported in previous findings (Xu et al.,
2018).
The EDX-SEM analysis of the fibers showed as main signals silver
(3 keV approx.), followed by carbon (C), oxygen (O), sodium (Na), and
magnesium (Mg) (Supplementary Fig. 1). The latter could derive from
the DYM extract used as the reductive agent.
The interaction between the cellulose fibers and the AgNPs was
analyzed through FTIR spectra (Fig. 2G). The characteristic peaks of the
cellulose type I were identified in the composite, and no new peaks were
identified compared with BCel, suggesting that the interaction of AgNPs
and cellulose fibers is mostly of the physical type and would be governed
by electrostatic and intermolecular interactions; this result agrees with
data previously reported by Ahmed et al. (2018), Deeksha et al. (2021),
and Muthulakshmi et al. (2017). In addition, the absence of vibration
bands at 1387 cm− 1 indicates that the removal of nitrates (NO-3) at the
end of the synthesis process was complete (Pal et al., 2017). On other
hand, the reduction in bands’ intensity associated with stretching vi­
brations of the functional groups O-H (3400 cm− 1), and C-O
(1749–1570 cm− 1) suggests that these groups would be involved in the
formation of hydrogen bonds (as reported recently by M’sakni and
Alsufyani, 2023), with the DYME-derived polyphenols composing the
capping of the AgNPs (Gordon-Falconí et al., 2020).
The thermal degradation curves of Cel-NP and BCel indicate two
stages in which mass loss occurs (Fig. 2H). In the first stage (between 45
and 100 ◦ C), a mass loss of 10% related to the evaporation of water
absorbed on the cellulose fibers was observed, in accordance with pre­
vious works (Z. Wang et al., 2018). A second stage of mass loss (85%
approx.) was observed at 360 ◦ C and 370 ◦ C for BCel and Cel-NP,
respectively. The loss of mass at this temperature is attributed to the
degradation of the cellulose polymer, which occurs by the cleavage of
the glycosidic bonds through a depolymerization process (Dorez et al.,
2014). Our results show that the presence of silver nanoparticles does
not alter the thermal stability of the cellulose fibers; this result agrees
with the findings of Xu et al. (2018). No differences were observed in the
C. Gordon-Falconí et al.
Fig. 2. Microstructural characteristics of bleached cellulose (A). Stress-strain curves of bleached cellulose and Cel-NP composite (B). Uv-vis spectra of the yerba mate
extract and free silver nanoparticles (C). Hydrodynamic diameter of the nanoparticles present in the supernatant after the Cel-NP composite formation process (D). X-
ray diffraction pattern of the Cel-NP composite (E). Back-scattered electrons (BSE) image and chemical mapping analysis showing the characteristic brightness of
silver in the Cel-NP matrix obtained (F). FTIR spectra (G) and thermogravimetric analysis (H) of bleached cellulose and Cel-NP composite. BCel: bleached cellulose;
Cel-NP: cellulose-nanoparticle composite.
residual weight of the two samples evaluated (BCel and Cel-NP). It is
worth mentioning that the results shown are within the range reported
in the literature for high-quality cellulose, which indicates that cellulose
decomposes from 350 ◦ C upward. Therefore, these results prove the
efficiency of the process proposed for the recovery of cellulose fibers
from discarded yerba mate.
To understand the effect produced by the application of a certain
force on the Cel-NP fibers, stress-strain curves were developed (Fig. 2B).
The tested samples had the following characteristics: tensile strength
201.22 ± 8.1 MPa, maximum stress at fracture 252.58 ± 13.5 MPa,
deformation at the time of fracture 1.08 ± 0.1%, and elasticity modulus
defined by a slope of 385.13 ± 25.5 MPa. These mechanical properties
were considered to be defined by the molecular structure, crystallinity,
orientation level (Wang et al., 2022), and, in this case, also by the
presence of AgNPs, which improved them. The fibers covered with silver
nanoparticles increased their tensile strength by 280% over cellulose
fibers without nanoparticles. Similar results were reported by Gang et al.
(2021), who found an increase of 135% and 234% in the tensile strength
and Young’s modulus in a polymer based on regenerated cellulose and
inorganic nanomaterials, compared with pure regenerated cellulose.
3.5. Emerging contaminants’ removal capacity: a comparative analysis
between BCel and Cel-NP
The cellulosic materials obtained from natural resources, including
plant residues such as yerba mate waste, can be used as versatile and
economic adsorbents since the discharge and dumping of toxic sub­
stances (heavy metals, inorganic and persistent organic pollutants such
as dyes, phenols, pesticides, detergents, etc.) on periurban water courses
has increased exponentially and became a serious threat for vast
populations.
Taking into consideration that cellulose fibers could be used to
manufacture water filtration systems, the study of the physicochemical
interactions between these fibers and the contaminants of interest is
required to design economically viable filtration systems (Nekouei et al.,
6
Industrial Crops & Products 211 (2024) 118253
2015). In this context, the contact time and initial dye concentration
effects on BCel and Cel-NP adsorption capacity applied to CV, MB, and S
solutions were studied (Fig. 3A and B). The three dyes are basic-charged
compounds; therefore, their interaction with cellulose functional groups
could be described through similar mechanisms. The removal percent­
ages shown by the BCel and Cel-NP used as bioadsorbents were 88.30%
and 84.02% for CV, 79.74% and 71.20% for MB, and 76.78% and
61.78% for S, respectively, all used at the same concentration: Co =
20 mg/L.
The adsorption equilibrium for CV, MB, and S solutions was reached
approximately after 30 min of contact since no significant changes in the
dye concentrations (in solution) were observed after this time when
using either adsorbent (Fig. 3A and B).
It has been described that the adsorption capacity of cellulosic
compounds is related to their purification degree, chemical structure,
fiber size, fiber porosity, pH, and surface area (Liu et al., 2015).
Adsorption processes are complex and depend on various physico­
chemical events, including internal, external, and interface mass trans­
fer, as well as mechanical phenomena such as cellulose fibers geometry,
which could generate resistance to the adsorption process (Liu and Liu,
2008).
Previous research indicates that physicochemical modifications of
cellulose structure recovered from plant residues can improve both
mechanical (elongation, strength) and physicochemical (contaminant
adsorption) properties, as well as conferring antioxidant and antimi­
crobial properties (Ramesh and Radhakrishnan, 2019). In our experi­
ment, the removal efficiency largely depended on the initial dye
concentration (Fig. 3C), probably due to the occupation of the active
sites of the polymer, its saturation, and the increase in the probability of
collision between dye molecules and cellulose, as previously reported
(Aljeboree and Alkaim, 2019). For all concentrations evaluated, BCel
efficiency for dies’ removal was higher than that of the Cel-NP. The
maximum adsorption capacities (Qe) were estimated at 248.22, 82.69,
and 86.35 mg of dye per g of BCel, and 202.44, 70.44, and 70.57 mg of
dye per g of Cel-NP (CV, MB, and S, respectively). These results suggest
C. Gordon-Falconí et al.
Fig. 3. Effect of the contact time (A and B) and the initial concentration (C) of dyes’ removal efficiency using BCel (A) or Cel-NP (B) as adsorbent materials. FTIR
spectra of the BCel and Cel-NP before and after the adsorption of CV dye (D). BCel, bleached cellulose; Cel-NP, cellulose-AgNPs composite.
that AgNPs could be occupying active adsorption sites in the cellulose
fibers. The reduction in the removal efficiency reveals the saturation of
the active sites in the cellulose fibers as far as the initial concentration of
the dyes increases.
The interactions that could take place between the functional groups
of the cellulose fibers and the dyes may be predicted from the FTIR
spectra analysis (Fig. 3D). A reduction in the transmittance peaks was
observed after the dye exposure to these materials, which confirms the
occurrence of adsorption processes, as described by Shaltout et al.
(2022). Similar results were obtained with MB and S (Supplementary
Fig. 2A-B). Furthermore, the band around 3391 cm− 1 shows changes
after adsorption, suggesting hydrogen bonds formation between the dye
molecules and cellulose hydroxyl groups (Shaltout et al., 2022). The CV
dye adsorbed on the cellulose modified the bands in the 1300 and
1600 cm− 1 regions; these bands are associated with asymmetric vibra­
tions of the -CH3 and –C– –O functional groups, respectively. According
to Ahmad and Ansari (2022), these changes in the adsorption spectra
suggest the participation of the functional groups –CH3 and –C– –O in the
adsorption process of the dye on the cellulose.
3.6. Bacteria adsorption and antimicrobial effect of the novel Cel-NP
composite
We designed a set of experiments to check if the composite obtained
could immobilize bacteria efficiently and exert antimicrobial effects. To
this aim, we selected two bacterial species: Escherichia coli, a gram-
negative rod considered an indicator of fecal contamination and
frequently found in untreated water resources (Majuru et al., 2016), and
7
Industrial Crops & Products 211 (2024) 118253
Staphylococcus aureus, a gram-positive, non-sporulating microorganism
that is relatively widespread in the environment and is recognized as the
leading cause of foodborne infections. It is also frequently found on
animals’ skin and mucous membranes (Hennekinne, 2018).
A lower number of bacteria in the washing solution (WS) compared
with the initial titers was detected: 84.59% of E. coli cells and 97.92% of
S. aureus cells remained immobilized on the BCel sheets after 1 and
3 hours of contact, respectively. In the WS of the Cel-NP composite
exposed to the E. coli suspension, the immobilization rates were higher:
91.02%, 97.16%, and 99.77% after 1, 2, and 3 h of contact, respectively.
For S. aureus, the Cel-NP composite retained 99.43% of the cells after 6 h
of contact (Fig. 4A and C).
These data evidence that cellulose fibers obtained from DYM have a
notorious capacity for immobilizing bacteria, and the incorporation into
this matrix of silver nanoparticles added a bactericidal effect.
The bacteria immobilization exerted by the cellulose fibers obtained
from DYM was verified by placing the cellulose sheets in Petri dishes
with solid LB. After 3 days, we observed bacterial growth around BCel
sheets previously exposed to E. coli, but not around Cel-NP (Fig. 4B). A
similar result was obtained for the samples previously exposed to
S. aureus (Fig. 4D). It should be remembered that cellulose fibers have
irregular surfaces, which facilitate the immobilization of bacterial cells.
Our results are comparable to those reported by Montazer et al. (2012),
who evaluated the antibacterial power of cotton fabric combined with
AgNPs. Maneerung et al. (2008) also reported antimicrobial properties
in bacterial cellulose impregnated with AgNPs.
The antimicrobial properties of the cellulose fibers and the composite
were tested by immersing these materials in bacterial cultures, and, in
C. Gordon-Falconí et al. Industrial Crops & Products 211 (2024) 118253

Fig. 4. Bacterial count reductions in Escherichia coli (A) and Staphylococcus aureus (C) titers in BCel and Cel-NP washing solutions (WS). The images show bacterial
growth around BCel sheets previously exposed to Escherichia coli (B) or Staphylococcus aureus (D) after 3 days of incubation, but not around Cel-NP. Images in B and D
are representative of various experiments. BCel, bleached cellulose; Cel-NP, cellulose-AgNPs composite.

the case of E. coli, also by the disk diffusion method. No growth was
recorded in the negative controls (data not shown). When BCel were
immersed in a culture of E. coli (103 CFU/mL), further bacterial growth
was reduced by 75.70% after 1 h (Table 3). However, 2 h later, the
bacterial titer was again in the range of 103 CFU/mL. On the contrary, no
observable growth at any time point (1, 2, or 3 h) was observed when
the Cel-NP was added to E. coli cultures. The result of the diffusion test
on solid media (Fig. 5) adds relevant information of practical signifi­
cance: Ag ions contained in the cellulosic nanocomposite seem not to
diffuse from the solid matrix, unlike in the case of free AgNPs. This is
particularly important considering the potential use of this material.
Previous studies reported reductions of 99.7% for E. coli and 99.9%
for S. aureus after 48 h of contact with cellulose of bacterial origin
previously impregnated with AgNPs (Maneerung et al., 2008). The

Table 3
Bacterial counts after different contact times in the presence of cellulose fibers
alone (BCel) or combined with AgNPs (Cel-NP).
Contact time, h BCel (CFU/mL) Cel-NP (CFU/mL) Fig. 5. Disk diffusion test on E. coli. BCel, bleached cellulose; Cel-NP, cellulose-
Escherichia coli AgNPs composite; DYME, discarded yerba mate extract. Whatman paper No. 1
0 1.27 (± 0.08) x103 1.27 (± 0.08) x103 was used to impregnate home-made paper disks (5 mm in diameter) with free
1 5.50 (± 0.07) x102 No growth AgNPs (20 µL, 50 μg of Ag-NPs/mL).
2 4.50 (± 0.05) x102 No growth
3 8.67 (± 0.06) x102 No growth
Staphylococcus aureus World Health Organization establishes that adequate domestic water
0 1.19 (± 0.07) x103 1.19 (± 0.07) x103 treatment must significantly eliminate the microbial load: it must
3 2.91 (± 0.41) x102 2.50 (± 0.45) x102 eliminate ≥ 99.99% of E. coli cells starting from a bacterial titer of ≥103
6 3.67 (± 0.29) x102 1.00 (± 0.30) x102
CFU/mL (Majuru et al., 2016; Ottenhall et al., 2018).

8
C. Gordon-Falconí et al.
Taking into account that the cell envelope of gram-positive bacteria
is formed by the plasma membrane and the cell wall, which includes a
thick peptidoglycan layer (Ottenhall et al., 2018), we used for S. aureus
contact times of 3 and 6 h. After 3 hours of contact with BCel and
Cel-NP, a 1-order decrease in the viable cell numbers was observed
(Table 3). According to Pinto et al. (2009), an antimicrobial process has
bactericidal capacity when it promotes a reduction of at least one order
of magnitude (≥log 1) with respect to the initial load. The World Health
Organization establishes that reductions of 1 (log 1), 2 (log 2), and 3 (log
3) orders of magnitude are equivalent to removals of 90.0%, 99.0%, and
99.9%, respectively (Majuru et al., 2016).
4. Conclusions
In this contribution, we describe the purification of cellulose fibers
from an abundant plant waste in Argentina and other Latin American
countries and the synthesis of a novel AgNPs-cellulose composite for
which discarded yerba mate supplied both a physical retention matrix
and the reducing power needed to produce Ag0 from Ag+ in the presence
of a silver salt. Taking into account that the yerba mate discarded after
its use as an infusion has ~46% cellulose and that 291 million kg of
yerba mate per year are consumed in Argentina, this residue should be
regarded as a relevant cellulose pool. In the cellulosic matrix here tested,
AgNPs were uniformly distributed and increased its mechanical resis­
tance, without modifying the crystallinity index or the thermal stability.
The presence of silver nanoparticles in the composite provides
bactericidal properties, which would avoid the contamination of our
envisaged domestic filter, with apparently no diffusion of Ag ions out of
it. This constitutes a central point taking into account the urgent need of
simple strategies capable of providing safer water to people from less
developed countries with limited access to potabilized water. Unfortu­
nately, in Argentina, this is a common situation for many inhabitants of
Buenos Aires periurban areas, who usually consume well-water.
Because a large number of contaminating industries are established
in these periurban areas and their effluents are usually poured into
natural water courses without any sanitization treatment, the pop­
ulations settled in the proximity of these industries are exposed to
considerable health hazards. Therefore, as a strength of this work we
highlight the simplicity of the synthesis process which may result in the
development of a simple, domestic water filtration system, able to retain
emerging contaminants and also inactivate relevant bacterial pathogens
at a home-scale level, could have an important social impact as it would
contribute to mitigate the risk of diarrhea and other health problems
linked to the consumption of contaminated, unsafe water. As a weakness
we recognize that we still need to optimize the collection and conser­
vation conditions of discarded yerba mate and are aware that its
composition may be variable, depending on the industrial processes
applied prior to its commercialization.
CRediT authorship contribution statement
Debut Alexis: Writing – review & editing, Supervision, Resources.
Groppa María Daniela: Writing – review & editing, Validation, Su­
pervision, Resources, Project administration, Funding acquisition.
Gordon-Falconi Cintya: Writing – original draft, Methodology, Inves­
tigation, Formal analysis, Data curation, Conceptualization. Iannone
María Florencia: Writing – review & editing, Visualization. Zawoznik
Myriam Sara: Writing – review & editing, Visualization, Validation,
Supervision.
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.
9
Industrial Crops & Products 211 (2024) 118253
Data Availability
Data will be made available on request.
Acknowledgment
This work was supported by the University of Buenos Aires (UBACYT
20020170100149BA) and the Nanomaterials Characterization Labora­
tory of the Nanoscience and Nanotechnology Center (CENCINAT) at the
Universidad de las Fuerzas Armadas (ESPE), Ecuador. María D. Groppa
and María F. Iannone are researchers at the Consejo Nacional de
Investigaciones Científicas y Técnicas (CONICET). Cintya Gordon-Fal­
coní is a fellow at CONICET. The authors would like to express sincere
thanks to Luis Cumbal PhD and Ing. Karla Vizuete of Nanomaterials
Characterization Laboratory of the Nanoscience and Nanotechnology
Center (CENCINAT) for their support and collaboration with the char­
acterization studies and to Guillermo Coppello PhD from IQUIMEFA
(CONICET).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.indcrop.2024.118253.
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