Chemistry Africa
https://doi.org/10.1007/s42250-024-01015-z
REVIEW
A review on Adsorption of Textile Dyes Onto an Unconventional
Biosorbent: Marine Waste of Posidonia Oceanica
Ghazza Masmoudi1
· Hatem Dhaouadi1
Received: 4 April 2024 / Accepted: 9 June 2024
© The Tunisian Chemical Society and Springer Nature Switzerland AG 2024
Abstract
Synthetic dye removal from textile wastewater is still a major occupation for water treatment specialists due to the high
pollutant load and poor biodegradability of these materials. Among several wastewater treatment methods, adsorption has
been shown to be an effective technique that can lead to complete colour removal from dyeing effluents. However, the relatively excessive cost of conventional adsorbents, particularly activated carbon, the complexity of its manufacture and the
high emissions of ­CO2, syngas and pyrolytic oils during pyrolysis, impose considerable limitations on its use, especially
in the current context of climate change. Therefore, a new generation of adsorbents has been developed based on the use
of natural, renewable, local, abundant, and low-cost materials. In this context, Posidonia oceanica, an aquatic plant from
the Mediterranean basin that is abundant as marine waste on beach shores, appeared to be an efficient biosorbent for dye
removal. Several scientific publications dealing with Posidonia oceanica have studied its use as an adsorbent support in
different forms: as a raw fibre or powder, chemically or physically treated adsorbent, cellulose nanofiber or nanocrystal and
precursor to activated carbon. Related studies have shown that all forms of Posidonia oceanica significantly adsorb various
pollutants, particularly heavy metals, and textile dyes even when compared to other biosorbents. In this review, the physical and chemical characteristics of different forms of Posidonia oceanica as well as their use as biosorbents for textile dye
elimination in batch or dynamic column mode were described, as reported in related scientific papers.
Keywords Adsorption · Dye · Waste · Posidonia oceanica
1 Introduction
Synthetic dyes are widely used in several industries, like
textile, tannery, paint and printing etc., despite their harmful effects on fauna and flora if discharged into the environment [1]. The textile industry is considered among the
largest consumers of dyes and producers of colored effluents [2]. Notably, the annual production of dyes worldwide
exceeds 700,000 tons, and the textile industry consumes
almost three-quarters of this amount and releases approximately 100 tons of dye per year, which is discharged into the
environment [3]. Synthetic dyes dumping causes coloration
of receiving water bodies, which decreases the passage of
sunlight, prevents photosynthesis and inhibits plant growth
* Ghazza Masmoudi
ghazza.massmoudi@fsm.u-monastir.tn
1
Research Laboratory of Environmental Chemistry and Clean
Processes, Faculty of Sciences of Monastir, University
of Monastir, Monastir, Tunisia
[4]. The dyes metabolites are more toxic than the dye molecules and their harmful effects appear after degradation of
the initial molecule into oxidation byproducts [1]. It have
carcinogenic, mutagenic and teratogenic properties that have
toxic impacts on plants, animals and humans [5]. Considering environmental constraints on the one hand and increasingly stringent regulations on wastewater discharge on the
other hand, the treatment of textile wastewater is a major
concern for manufacturers and environmental researchers
and organizations [6].
Conventional treatment methods such as biological processes and coagulation/flocculation applied to coloured
effluents have been shown to be not completely efficient for
dye removal because of the strong fluctuations in pollutant
concentrations and the weak biodegradability of dyes and
chemical additives [7]. Moreover, they show some drawback
such as such as being pH dependent, expensive, secondary
sludge disposal problem and high residence time [8]. Other
technologies, such as membrane filtration and chemical oxidation, have shown good efficiency in the removal of dyes;
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however, their high maintenance costs and high energy
demands present considerable limitations [9].
Among the applied processes, adsorption is considered
the most efficient technology for color removal [2]. It has
been widely used due to its simple design and operation [10].
Activated carbon is the most commonly used adsorbent due
to its high efficiency in color removal. It is prepared from
agricultural waste, livestock or industrial byproducts [11] by
the pyrolysis and activation of raw material, which results
in a porous morphology with a very large surface area that
can reach 2000 ­m2.g−1 [9]. However, given the complexity
of activated carbon preparation and regeneration, researchers
are looking for new materials that can reduce manufacturing
and operating costs and provide high adsorption capacities.
Thus, a new generation of adsorbents based on natural, lowcost and abundant materials has been developed.
The use of agricultural waste as an adsorbent material to remove dyes from wastewater has recently become
increasingly popular because it is less expensive, biodegradable, easily available and efficient [12]. Several kinds
of raw biomass have been studied, such as plant stems and
bark [13], orange peel [14], rice husk [15], coconut [16],
bamboo [17], and sugarcane [18], as well as microbiological materials such as algae, fungi and bacteria [19–21].
Many biosorption experiments on natural biomass have
shown that it can be considered an efficient alternative for
the removal of several pollutants from water, especially
dyes and heavy metals [3, 17, 20–22]. Biomass derivatives have also been studied as adsorbents, and particular
attention has been given to biomass nanoextracts since
nanotechnology has made a quantum leap in all areas,
especially in wastewater treatment, in which nanoparticles are used as high-quality separation and reactive media
in terms of reactivity and performance [23]. In the same
context, cellulose derived from biomass has been reported
to effectively adsorb several pollutants, such as synthetic
dyes and heavy metals [24–28].
Posidonia oceanica (P. oceanica) is a Sea grass abundant
on the Mediterranean coasts as leaves or balls (Fig. 1). It
occurs in shallow and coasts and it plays an important role
in the ecology of the Mediterranean basin and its protection
from sea erosion [29, 30]. P. oceanica has been used as an
indicator of the degree of marine ecosystem pollution for
several decades [22, 31]. It was investigated as a source of
lignocellulosic fibres for pulp and paper production [32], as
biostimulant to enhance plant growth, photosynthesis and
crop quality [33],and as a biosorbent for pollutant removal.
It was found to be efficient in dye removal, with an elimination rate that can reach 97% [34–36]. P. oceanica showed
also high performance in heavy metal elimination since it
can remove 97%, 98%, 88%, 85% and 70% of Pb(II), Cu(II),
Ni(II), Cd(II) and Zn(II), respectively [37]. It had also a
good retention of antibiotics like oxytetracycline [38]. P.
oceanica can be used in different forms: as a raw material
[39], chemically modified [40] or transformed into activated
carbon [41], cellulose [35], microcrystalline cellulose [42],
cellulose nanofibers (CNFs) [43] or nanocrystals (CNCs)
[44].
This review is a synthesis of research related to the
removal of several types of textile dyes by adsorption onto
multiscale P. oceanica derivatives, including raw materials, cellulose extracts (cellulose nanocrystals and cellulose
nanofibrils) and activated carbon. This investigation begin
with studying the adsorbent materials characteristics and
composition. Then, the effect of the material type and the
application method (in batch or column) on several textile
Fig.1 Balls a and plant b of
Posidonia oceanica
Leaves
Rhizome
(a)
(b)
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dyes removal was examined by comparing the results with
those using other biomasses.
2 Characterization of P. oceanica‑Based
Biosorbents
The use of an adsorbent medium must begin with a good
understanding of its physical and chemical properties. This
makes understanding and interpretation of the phenomena
occurring during the adsorption process easier. The characteristics of P. oceanica derivatives have been well represented by numerous research reviews.
2.1 Raw P. oceanica
The physical and chemical characterization of the leaves
and balls of P. oceanica has been the subject of several
studies. The physical characterization realized by Cocozza
et al. (2011) [45] of raw P. oceanica leaves collected from
the Italian coast revealed that the bulk density was 66.1 kg.
­m−3 against a particle density of 1595 kg.m−3, the total pore
space was 95.9%, and the air and water-holding capacities
were 43.2% and 52.6%, respectively. The low bulk density
compared to the particle density and the high total pore
space percentage confirm that the P. oceanica material is
a porous media.
Table 1 regroups the results corresponding to the chemical composition of the P. oceanica leaves and balls from
the literature. P. oceanica balls and leaves are doted by
high amounts of cellulosic material for both hemicellulose
(21.8% for balls and between 23.3% and 35% for leaves) and
α-cellulose (40% for balls and between 24% and 32.5% for
leaves). Lignin content is also relatively high for P. oceanica balls and leaves compared to other agricultural residues,
such as wheat straw (11–21%) [46], olive wood (15.64%)
[47] and banana pseudosteams (12.7%) [48]. The ash content
provides information on the percentage of mineral matter
in the sample, and the low percentages of ash indicate that
the material is mainly composed of organic matter, which
Table 1 Chemical composition of P. oceanica balls and leaves
P.O type/
country
Composition (%)
Reference
Hemicellulose
α-cellulose Lignin Ash
Balls/Tunisia
Leaves/Tunisia
Leaves/Italy
Leaves/Algeria
Leaves/Egypt
21.8
25.7
35
23.3
22.52
40
31.4
24
32.5
35.12
29.8
24.7
18
28.2
18.73
12
10.5
13
6.4
12.03
[49]
[50]
[51]
[42]
[52]
is likely of cellulosic origin. The differences between the
ash contents listed in the table are therefore likely related to
climate conditions and the chemical composition of the soil
since the P. oceanica samples were obtained from different
countries [43].
The detailed ash composition was determined by several
investigations, and the results are summarized in Table 2.
Khiari et al. (2010) [49] reported that silica is the predominant inorganic material in P. oceanica ash. However, this
finding could be due to sand contamination of the sample. In
addition, all the samples had relatively high salt concentrations (Cl, Na, K), which is expected considering the marine
environment in which the plant evolved. The relatively high
metal contents, particularly Ca, Fe and Mg, can be attributed to the intrinsic properties of the plant. Some elemental
contents in rhizomes were higher than those in leaves of the
Egyptian P. oceanica such as Ca, Cu, Mg and Zn, while Fe
was lower in the rhizome than leaves.
2.2 P. oceanica Cellulose Extracts
The analysis of the composition of the raw P. oceanica
showed that it is a cellulosic material that can be used as a
raw material for the production of cellulose and its derivatives [55]. In this regard, several studies on P. oceanica
extracts have investigated their ability to adsorb pollutants,
such as extracted cellulose [26, 35], cellulose nanofibers [56]
and cellulose nanocrystals [50, 51, 57].
Table 2 P. oceanica ash elemental composition
Reference
[49]
[45]
[52]
[53]
[54]
Country
Tunisia
Italy
Egypt
Spain
Egypt
Unit
%w/w
mg.kg-1
mg.kg-1
mg.kg-1
mg.kg-1
Parameter
Ca
C1
Cr
Cu
Fe
Hg
K
Mg
Na
Ni
P
Pb
S
Si
Zn
9.12
0.72
<100ppm
3.78
2.04
3.89
2.49
0.12
1.92
17.7
-
13915
49630
7
49.7
7455
0.07
4685
10989
36094
13.5
16.8
59.5
10850
10
875
4800
10
30.9
0.0068
0.0048
2.24
0.09
10.7
1.9
0.023
0.025
0.063
19172.49
35.6
85.44
372.49
1560.19
7544.34
45.95
P. oceanica
Balls
Leaves
Leaves
Leaves
Rhizome
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Cellulosic fibres have amorphous and crystalline structures with a high degree of organization. The crystallinity
rate depends on the origin of the material; cotton, flax, ramie
and banana have a high degree of crystallinity (65–70%),
but the crystallinity of regenerated cellulose is only 35–40%
[58].
To describe several types of cellulose nanoparticles based
on their dimensions, the Technical Association of the Pulp and
Paper established a standardized heuristic Industry (TAPPI)
for nanocellulose classification regarding fibre morphology
cut-offs (Fig. 2). Cellulose nanofibers (NFCs) are obtained by
delamination of the fibres by mechanical treatment at high pressure and/or enzymatic or chemical treatment. However, cellulose nanocrystals (CNCs) are obtained by acid hydrolysis [50].
Different analyses have been reported to characterize
P. oceanica cellulosic derivatives. The physicochemical
characterization of the extracted cellulose from P. oceanica
can be performed by Boehm titration to identify the acidic
functional groups and spectroscopic analysis; XRD (X-Ray
diffraction) to determine the crystallographic structure of
the material, FTIR (Fourrier-Transform infra-red) used to
monitor the vibrations of the functional groups which characterize a molecular structure and XPS ( X-ray photoelectron spectroscopy) to identify the overall electronic structure
of a material or its surface. As reported by Douissa et al.
(2013) [35], the characterization results of cellulosic fibres
extracted from P. oceanica showed that carboxylic groups
presented the most acidic functional groups, followed by
phenolic and lactonic groups. This result was validated by
the FT-IR spectrum, which presented a strong absorption
band at 3430 ­cm−1 due to the stretching of O–H groups and
another band at 2891 ­cm−1 due to C-H stretching. Moreover, the elemental surface composition determined by XPS
showed that the extracted fibres contained not only pure cellulose but also lignin and hemicellulose. These results were
confirmed by the presence of some nitrogen, chlorine and
Fig. 2 Proposed standard terminology for cellulose nanomaterials from TAPPI WI 3021 [59]
calcium atoms. In the same context, Bettaib et al. (2015)
[56] and Yang et al. (2014) [28] performed research on cellulose nanofibers extracted from P. oceanica balls and leaves
and demonstrated that the obtained cellulose nanofibers are
mainly composed of holocellulose (approximately 92% for
balls and 95% for leaves) and α-cellulose (approximately
72% for balls and 79% for leaves), with a low percentage
of ash (approximately 3% for balls and 7% for leaves) and
lignin (approximately 0.3% for balls and 1.4% for leaves).
Microcrystalline cellulose (MCC) and cellulose nanocrystals (CNCs) extracted from P. oceanica have robust potential
in wastewater treatment due to their surface characteristics
[24]. Furthermore, the microscopic and macroscopic characteristics of the extracted material surface were studied in
several works [35, 50, 51, 57]. X-ray diffraction analysis was
carried out to compare the crystallinity of the different supports by measuring the crystallinity index, which is a quantitative indicator of the crystallinity and is defined as the
ratio of the crystalline peaks to the crystalline + amorphous
ones, and the aspect ratio, which is defined as the ratio of the
primary size of the particle (length) to the secondary size
(width). Table 3 summarizes the geometrical characteristics
of the P. oceanica derivatives according to some literature
findings. Bettaieb et al. (2015) [50], Gonzalez et al. (2019)
[51] and Fortunati et al. (2015) [57] investigated the morphology of CNCs extracted from P. oceanica with lengths
of approximately 180–586 nm, widths of approximately
6.8 − 15 nm and average diameters of approximately 5–8 nm,
with an aspect ratio of approximately 35–76%. On the other
hand, the crystallinity index values presented in the table
below showed that the P. oceanica derivatives presented a
highly crystalline structure due to the presence of crystalline
cellulosic components. Therefore, the measured dimensions
and the morphological view of the extracted support from
P. oceanica plants (leaves and/or balls) can be compared to
those obtained from other plant fibres, as shown in Table 4.
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Table 3 Geometrical characteristics of the extracted cellulosic support
Cellulosic support
Width (nm)
Length (nm)
Diameter
(nm)
Aspect ratio
crystallinity
index Xc(%)
Reference
Extracted cellulose nanocrystals (CNC) from Commercial
microcrystalline cellulose
Extracted cellulose nanocrystals (CNC) from P.oceanica
Extracted cellulose nanocrystals (CNC) from P.oceanica
Extracted cellulose nanocrystals (CNC) from P.oceanica
Extracted microcrystalline cellulose (MCC) from P.oceanica
15 − 20
200 − 250
15–21
-
88–91.5
[24]
10–15
6.8–8
n.d
n.d
488–586
276- 520
180
52. ­103
8
5
8. ­103
35–58
35–76
36.7
-
50–77
60–64
74%
[51]
[50]
[57]
[42]
Table 4 Geometrical characteristics of some cellulose CNCs [50]
Starting materi- Width (nm) Length (nm) Aspect ratio Reference
als
Rise husk
Cotton
Cotton linter
Bagasse
Kenaf bast
Flax
Alfa
Eucalyptus
wood pulp
Ramie
Pea hull
Palm tree
Wheat straw
Bleached softwoof
Kraft pulp
Sisal
Sugarcane
bagasse
Tunicin
15–20
14.6
14.6 ± 3.9
4–10
12
10–30
10
6
171.6
171.6 ± 48.2
84–102
158
100–500
200
145
10–15
1.7
11–12
13
13
15
20
24
[60]
[61]
[62]
[63]
[64]
[25]
[65]
[66]
7
7–12
6.1
5
5
200
240–400
260
225
180–280
28
34
43
45
33–47
[67]
[68]
[69]
[70]
[71]
3.5
4
2–6
180
250
200–310
50
60
64
[72]
[73]
[74]
100–1000
10–20
50–200
[75]
The collected values are typical for cellulose nanocrystals,
regardless of the cellulose source and the growth conditions.
However, the aspect ratio observed for CNCs from P. oceanica was found to be greater than that of CNCs extracted
from the other mentioned annual plants.
The scanning electron microscopy (SEM) micrograph of
the cellulose extracted from P. oceanica dead leaves (Fig. 3)
obtained by Ben Douissa et al. (2013) [35] confirmed the
porous structure of the obtained materials, in which considerable numbers of heterogeneous layers and pores were
detected, suggesting that the cellulose extracted from P. oceanica seems to be efficient for pollutant adsorption. Figure 4
shows a transmission electron microscopy micrograph of
well-dispersed elongated rod-like P. oceanica nanoparticles obtained from balls and leaves by Bettaieb et al. (2015)
[50]. These authors reported that the CNCs obtained from
Fig. 3 SEM image of P. oceanica-extracted cellulose [35] ©
P. oceanica leaves holocellulose (WHPL) had average diameter of 6.8 nm and average length of 520 nm. The CNCs
obtained from P. oceanica leaves cellulose (WCPL) had
average diameter of 7 nm and average length of 338 nm. The
aspect ratios were approximately 48.3 and 76.5 for WHPL
and WCPL, respectively. In the case of P. oceanica balls,
CNCs extracted from holocellulose (WHPB) had average
diameter of 8.1 nm and average length of 290 nm. While
CNCs extracted from P. oceanica balls cellulose (WCPB)
had average diameter of 8 nm and average length of 276 nm.
The corresponding aspect ratios were approximately 35.8
and 34.6 for WHPB and WCPB, respectively.
2.3 Activated Carbon of P. oceanica
Activated carbon is one of the most commonly used adsorbents for water purification due to its high porosity and
adsorption capacity [76]. Basically, activated carbon is
prepared from different biomass types using two different
processes, physical and chemical activation, to increase the
Chemistry Africa
Fig. 4 Transmission electron
micrographs of diluted CNCs
suspensions obtained from the
leaves of holocellulose (a) and
cellulose (b) and the balls of
holocellulose (c) and cellulose
(d) [50] ©
porosity of the precursor. On the one hand, physical activation involves carbonization of the carbonaceous precursor in the first step, followed by activation of the obtained
char in the presence of activating agents such as steam or
carbon dioxide in the second step. During this process, a
large reduction in the internal carbon mass occurs, which
results in a well-developed porous structure. On the other
hand, chemical activation involves the carbonization of the
precursor in the presence of chemical agents that are used as
dehydrating agents that influence pyrolytic decomposition
and inhibit the formation of tar, thus enhancing the yield of
carbon [2, 77].
The application of commercial activated carbon in
industrial wastewater treatment might be limited due
to its high cost. Different studies have been carried out
to produce cheap and efficient activated carbon from
abundant biomass and renewable sources, such as sunflower oil cake [78], bean pods [79], cotton stalks [80,
81], macadamia nut shells [82], bituminous coal [83],
coffee ground [84, 85], coal [86], Chinese fir sawdust
[87] and P. oceanic leaves [41, 88–90]. According to
previous studies on the preparation of biomass-based
activated carbon (Table 5), the activated carbon produced
from P. oceanica leaves exhibited a high specific surface
area and good structural characteristics compared to the
properties of activated carbons derived from other lowcost materials, either physically or chemically activated.
However, the chemical activation of P. oceanica-based
activated carbon seems to improve the performance of
activated carbon since it has a better BET surface area
and total, micropore and mesopore volumes.
The use of biochar has also attracted increasing interest since it results from the heating of biomass in a limited oxygen environment without undergoing the activation step and is composed of amorphous carbon with a
highly functionalized surface, which makes it reactive to
various compounds. Cataldo et al. (2018) [91] prepared
biochar from P. oceanica leaves and studied its raw and
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Table 5 Comparison of textural
characteristics of some biomassbased activated carbons [41]
Activated carbon type
SBET ­(m2 ­g−1)
Vmicro ­(cm3 ­g−1)
Vmeso ­(cm3 ­g−1)
Vtotal ­(cm3 ­g−1)
Reference
Sunflower oil cake
Bean pods
Cotton stalk
Cotton stalk
Macadamia nut-shell
Bituminous coal
Commercial AC
Coffee ground
Coal
Coffee ground
Chinese firsawdust
Commercial AC
P. oceanica leaves
Physical activation
Chemical activation
240
258
594
794
844
857
924
925
970
1021
1079
1118
0.111
0.080
0.280
0.083
0.391
0.390
0.426
0.046
0.481
0.350
0.502
0.415
0.005
0.013
0.030
0.094
0.041
0.666
0.180
0.950
0.050
0.203
0.116
0.206
0.381
0.630
0.485
0.450
0.466
0.718
1.300
0.558
0.618
[78]
[79]
[80]
[81]
[82]
[83]
[82]
[84]
[86]
[85]
[87]
[92]
615
1483
0.021
0.494
0.118
0.456
0.160
1.022
[88]
[41]
chemically activated forms and reported that the activation step led to changes in the superficial area, pore volume and average pore width. In particular, the superficial area and pore volume increase from 4.664 to 20.936
­m 2.g −1 and from 0.015 to 0.018 c­ m 3.g −1, respectively.
Table 6 Regrouped data related to the structural characteristics of biomass-based activated carbon and P. oceanica-based activated carbon. The collected data include
the BET surface area, total pore volume, micropore volume (d < 2 nm), mesopore volume (2 nm < d < 50 nm),
micropore diameter, mesopore diameter and BJH average pore width and volume. On the one hand, it can be
noticed that P. oceanica can be transformed to a high
value-added material since it can effectively be used
as a precursor for the preparation of high-quality activated carbon. On the other hand, activated carbon made
directly from raw P. oceanica had better textural characteristics than other activated carbons especially when it
is chemically activated.
2.4 Treated P. oceanica
The adsorption properties of materials can be improved
by applying chemical, physical, or thermal treatments
to modify the adsorbent structure. Several studies have
shown that the modification of the P. oceanica structure improved its performance. For instance, Meseguer
et al. (2016) [53] reported that chemically modified P.
oceanica using HCl and formaldehyde can increase the
removal of cadmium present in a 20 ppm solution up
to 97% when only 80% of the raw P. oceanica is eliminated. Donut et al. (2017) [93] have also studied the
enhancement of the tetracycline adsorption capacity of
chemically pretreated dead leaves of P. oceanica. In this
study, the authors used the method described by Cuny
et al. (1995) [94] to chemically modify the adsorbing
support to eliminate unbound phenolic compounds by
submerging dead P. oceanica leaves in ethanol (50%
(v/v)) at 40 °C for 3 h. After washing with pure water,
the pretreated P. oceanica residues were dried at room
Table 6 Textural parameters of P. oceanica-based biochar and activated carbon
P. oceanica-based adsorbent
SBET
(m2.g−1)
Vpore
(cm3.g−1)
Vmicro
(cm3.g−1)
Vmes
(cm3.g−1)
Biochar
Activated biochar
Activated carbon
4.664
20.936
615
1148
602.46
1483
0.015
0.0174
0.16
0.74
1.022
0.021
0.704
0.494
0.118
0.456
Dmicro
(nm)
0.6/1.2
-
Dmes
(nm)
DBJH
(nm)
VBJH
(cm3.g−1)
Reference
2.1/5.5
-
13.09
4.715
0.068
[91]
[91]
[88]
[89]
[90]
[41]
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temperature. The authors concluded that the unbound
phenolic compounds in the dead P. oceanica leaves
limited their adsorption capacities. Krika et al. (2021)
[95] studied the effect of the basic modification of P.
oceanica using NaOH-surface treatment on pollutant
biosorption performance. An experimental study of the
adsorption of amoxillin from wastewater by P. oceanica
and NaOH-P. oceanica showed that NaOH modification
significantly increased the adsorption capacity, and the
modified material presented a greater adsorption capacity than that obtained for raw P. oceanica and several
materials from the literature, such as chitosan grains
[96], chemical-activated carbon from olive stones [97]
and activated carbon nanoparticles prepared from vine
wood [98].
Photiou et al. (2021) [99] studied the effect of thermal
treatment of P. oceanica leaves on pollutant removal and
material surface characteristics. In this regard, the phosphate adsorption capacity of thermally treated sea grass
residues of P. oceanica was studied and compared to that
of other thermally treated and pyrolyzed biowastes, such
as fish scales, orange peels, coffee residues, and biochar
produced from vineyard prunings and from olive kernels.
The biowastes were thermally treated at 500 °C-550°C for
1 h-2 h or pyrolyzed (under nitrogen stream) at 550 °C for
3 min. The obtained results are listed in Table 7, which
shows that the phosphate adsorption capacities of the thermally treated P. oceanica were greater than those of the
other bioresources subjected to the same treatment (99%).
In fact, the support structure of the functional surface
groups and pore volume changed after thermal activation due to the reduction in the carbon amount, the partial
decomposition of the organic matter and the damage to the
physical structure by decreasing the number of oxygen surface functional groups on the material. These results were
confirmed by SEM images of P. oceanica seagrass before
and after thermal treatment, as shown in Fig. 5, and the elemental composition of seagrass specimens obtained through
energy dispersive X-ray spectroscopy, as shown in Table 8.
Table 7 Percent removal of
phosphate from synthetic
aqueous solutions using
different biowastes. The initial
phosphate concentration in all
the samples was 100 mg/L [99]
3 Adsorption of textile dyes on P. oceanica
3.1 Raw P. oceanica
3.1.1 Batch adsorption
P. oceanica first attracted attention as a porous medium
with noticeably low bulk density [45]. Studies of its adsorbent capacity should begin with tests in batch mode. Batch
adsorption experiments are generally conducted in flasks
with constant solution volume by varying the initial dye
concentration, initial pH, temperature, or adsorbent dosage. Samples are taken at well-defined time intervals; the
adsorbent is separated from the solution by filtration or by
centrifugation. The concentration of dye was then analysed
using a UV spectrophotometer by monitoring the absorbance at the wavelength of the maximum absorbance of the
selected dye.
The selection of the correct pH is a key factor that
allows the optimization of adsorption performance. The
influence of the solution pH on the dye uptake can be
explained on the basis of the pH zero point charge (pHzpc)
called also isoelectric point of the adsorbent, it is the
value of the pH necessary to affect a net zero charge on a
solid surface in the absence of specific sorption. This is
a convenient index of a surface when the latter becomes
either positively or negatively charged as a function of
pH [100, 101]. Solution pH affects adsorption by regulating the adsorbents surface charge as well as the degree
of ionization of solution components (acidic and basic
compounds). In general, cation adsorption on any adsorbent will be favorable at pH > pHzpc, in this case, the surface of the adsorbent gets negatively charged and favours
uptake of cationic dyes due to increased electrostatic force
of attraction. At lower pH (pH < pHzpc), adsorbent surface is positively charged, cationic dye molecules will be
repulsed by the adsorbent surface causing a decrease in
dye uptake. The temperature is also a significant parameter
for the adsorption, it can displace the equilibrium of the
Biowastes
Pretreatment method
Adsorbent dose
[g.L−1]
P. removal [%]
Fish scales
Coffee residues
Coffee residues
Orange peels
Olive kernels
Vineyard prunings
P. oceanica
P. oceanica
Thermally treated at 550 °C for 2 h
Thermally treated at 550 °C for 2 h
Thermally treated at 550 °C for 2 h
Pyrolysis at 550 °C for 3 min
Pyrolysis at 550 °C for 3 min
Pyrolysis at 550 °C for 3 min
Thermally treated at 550 °C for 2 h
30
30
20
30
20
20
20
20
5.1 ± 0.3
0.0 ± 0.0
38.9 ± 3.7
13.2 ± 2.0
15.4 ± 1.1
15.4 ± 3.9
97.7 ± 0.4
99.1 ± 0.8
Chemistry Africa
Fig. 5 Scanning electron microscopy images of untreated (a-c) and thermally treated (d-f) P. oceanica seagrass [99] ©
Table 8 Elemental composition percentage of seagrass specimens obtained through energy dispersive X-ray spectroscopy. SG: Seagrass; SG-TT:
Thermally treated seagrass; SG-TT/P: Thermally treated seagrass after phosphate adsorption [99]
SG
SG-TT
SG-TT/P
C
O
Na
Mg
Al
Si
S
Cl
K
Ca
P
Fe
55.64
22.45
20.48
28.68
34.41
43.06
2.79
8.23
5.22
2.87
11.86
5.99
0.46
0.31
0.38
0.82
0.46
2.69
0.52
1.06
0.26
6.72
14.95
2.01
0.35
1.16
3.36
1.15
5.01
5.64
0.00
0.17
10.92
0.00
0.00
0.32
adsorption capacity. The decrease of adsorption capacity with increasing temperature indicates the exothermic nature of the adsorption. Similarly, the increase in
adsorption capacity with increasing temperature reveals
an endothermic character [2, 102]. The dye concentration
is closely linked to the adsorbent dose. It is therefore necessary to ensure that the applied doses don’t reach the
maximum adsorption capacity.
Batch experiments on Raw P. oceanica indicated that it
was able to remove between 73 and 98% of methylene blue
[34–36, 103], approximately 90% of Alpacide Grey metalcomplex dye [104], 90% of acid yellow 59 [105], 75% of
Astrazon red [39] and approximately 96% of crystal violet
[103]. Several dyes, particularly methylene blue (MB), have
been tested because of their widespread use in several fields,
particularly in textile dyeing, and because of their relatively
high toxicity in comparison to other dyes [106, 107]. MB
is a basic cationic dye often applied in dyeing baths under
acidic conditions, and it is used in inks, medicine, modified
nylon, modified polyester, paper, polyacrylonitrile, polyester,
silk, tannin-mordanted cotton and wool [9]. Table 9 shows
the results from the literature related to the adsorption of the
MB dye on the two types of P. oceanica (balls and leaves)
and those of adsorbents derived from other materials. It is
first of all remarkable that the adsorbent power of P. oceanica leaves is much greater than that of its fibrous basal
part, with a maximum adsorption capacity of 357 mg.g−1
against 5.56 mg.g−1. A comparison of MB adsorption on
P. oceanica leaves with that on rice husk, C. racemosa var.
cylindracea and Neem leaf powder revealed that P. oceanica
leaves had greater dye uptake than did rice husk, C. racemosa var. cylindracea and Neem leaf powder, according
to the results obtained by Allouche et Yassaa (2018) [36].
The elimination of several types of dyes by raw P. oceanica has been studied in several research papers. Table 10
shows the experimental results of the adsorption of various dyes onto raw P. oceanica. The elimination rates of all
the dyes studied are greater than 90%, which confirms the
Chemistry Africa
Table 9 Comparison of the
maximum adsorption capacities
of methylene blue dye onto P.
oceanica and other materials
adsorbent
PO type/origin
Qmax (mg.g−1)
T(°C)
pH
Reference
P. oceanica
Leaves/Algeria
Fibrous basal part of
leaves/Tunisia
Leaves/Libya
-
357
5.56
20
30
5
6
[36]
[34]
27.78
50.6
40.58
5.23
8.76
25
30
32
18
27
7
8
8
7
2–10
[103]
[16]
[15]
[112]
[113]
Coconuts shell
Rice husk
C. racemosa var. cylindracea
Neem leaves powder
(Azadirachta indica)
Table 10 Adsorption parameters for different dyes onto raw P. oceanica
Dye
Dye type
P. oceanica type
R(%)
T(°C)
pH
Qmax (mg.g−1)
Reference
Alpacide Grey
Astrazon red
Basic blue 41
Basic blue 41
Crystal violet
Direct red 75
Methyl violet
Reactive red 228
Yellow 59
Metal-complex
Basic
Basic
Basic
Basic
Direct
Basic
Reactive
Acid
Leaves sheath fibres/Tunisia
Leaves/Turkey
Leaves/Algeria
Balls/Tunisia
Leaves/Libya
Leaves/Turkey
Leaves/Tunisia
Balls/Tunisia
91%
97.6%
93.13%
96.02%
98.1%
90.3%
30
25
30
25
30
20
25
23
2
6.5
8–11
4
7
2
6
5
2–3
14.51
68.966
868.36
205
22.93
44.5
72.99
5.74
76.9
[104]
[39]
[114]
[109]
[103]
[40]
[112]
[115]
[105]
significant adsorption ability of the raw material. The maximum dye uptake values vary depending on both the nature
of the adsorbate and the nature of the adsorbent. Indeed,
the adsorption of basic blue 41 on the leaves and balls of P.
oceanica shows that the maximum adsorption capacity is
greater for the leaves than for the balls, which confirms the
results obtained for methylene blue adsorption.
According to Jindarom et al. (2007) [108], the adsorption capacities of yellow 59 and basic blue 41 on biochar
prepared from sewage sludge were 116 mg.g−1 and 588 mg.
g−1, respectively. Adsorption of the same dyes on raw P.
oceanica balls led to maximum adsorption capacities of
76.9 mg.g−1 [105] and 205 mg.g−1[109], respectively. Considering the morphological differences between biochar and
raw P. oceanica balls, it can be concluded that the values
found with the raw material are acceptable.
3.1.2 Dynamic column adsorption
After studying the feasibility of the adsorption of textile
dyes on raw P. oceanica in batch mode, it was determined
that this material can be considered an effective adsorbent support for the elimination of several types of dye.
At this stage, the study of dynamic adsorption on columns
is essential since it is the basis of the scaling up of the
process in industrial applications.
Dynamic adsorption experiments are generally conducted in vertical columns filled with biomass, operated
in downflow mode, and continuously fed with dye solution
at a controlled flow rate using a peristaltic pump. The
treated dye solution was then collected from the bottom of
the column. In these experiments, the breakthrough curves
C
( C t = f (t)) are plotted for various parameters, such as the
0
initial pH of the solution, flow rate, initial dye concentration, and bed depth. Among the significant measured
parameters, the breakthrough time represents the time at
which the dye concentration in the effluent reached a minimum fixed breakthrough value, which is in most cases less
than 10% of the initial dye concentration. The bed exhaustion time is also an important parameter that represents the
time at which the dye concentration in the effluent reaches
a maximum fixed amount of dye, which is generally more
than 90% of the initial dye concentration.
Generally, the plot of the breakthrough curves monitoring the dye elimination behavior of the column shows that
the amount of adsorbed dye decreased with increasing flow
rate and increased with increasing dye concentration and
bed height [110]. Indeed, the breakthrough time decreased
Chemistry Africa
with increasing influent dye concentration. At lower influent dye concentrations, breakthrough curves were dispersed, and breakthrough occurred more slowly. As the
influent dye concentration increased, sharper breakthrough
curves were obtained. These results demonstrate that the
change in the concentration gradient affects the saturation
rate and breakthrough time. This can be explained by the
fact that more adsorption sites were covered as the dye
concentration increased. The larger the influent concentration is, the steeper the slope of the breakthrough curve and
the smaller the breakthrough time [111].
The experimental results of dynamic dye adsorption on
columns are generally supported by mathematical models
such as the Thomas model described by Eq. (1) below [111]:
Ct
1
=
[
]
C0
1 + exp Kth (q0 x − C0 Veff )∕𝜐
(1)
where kTh is the Thomas rate constant (ml.mg−1.min−1),
which describes the rate of solute transfer from the liquid to
the solid phase; ­q0 is the equilibrium uptake (mg.g−1); x is
the amount of adsorbent in the column (g); ­Veff is the effluent
volume (L); and ­C0 is the influent dye concentration (mg.
­L−1), ­Ct is the effluent concentration at time t (mg. ­L−1), and
υ is the flow rate (mL.min−1).
The dynamic removal of various biomass types by methylene blue dye has been studied in several studies [101, 111,
116–119], and Table 11 regroups the related results.
In all the reported studies, the MB adsorption capacity
increased with increasing pH. A shorter breakthrough time
and greater MB removal efficiency were obtained at higher
bed.
heights. A comparison of the results of the dynamic
adsorption of MB dye on columns filled with different types
of biomass showed that the retention capacity of the column
filled with P. oceanica was greater (480 mg.g−1) than that
of the other materials. Dye elimination decreased by 67.4%
compared with 64.74% for Guava leaf powder and 55% for
treated olive pomace.
In another study, Mahjoub et al. (2014) [110] studied the
dynamic adsorption of Congo red (CR) dye onto a raw P.
oceanica fixed bed. They found that the removal of CR by
raw Posidonia fibres reached 80% with a dye concentration
of 10 mg. L
­ –1, a flow rate of 0.47 mL.min–1 and at a pH of
approximately 6.5. They also reported that the adsorption
behavior of CR is significantly influenced by the pH of the
solution since a lower pH corresponds to a longer breakthrough time. Similarly, for the flow rate, low values prolonged the breakthrough time. The increasing inlet CR concentration shortened the breakthrough time and increased
the equilibrium uptake. Additionally, for bed depth, they
found that as the bed height increased, the steepness of the
breakthrough curve decreased.
3.2 P. oceanica cellulose extracts
High-grade cellulose with an important α-cellulose content
and significant crystallinity index can be extracted from the
renewable marine biomass P. oceanica [120]. Cellulose
extracts are mainly used in the fields of textiles, pharmaceuticals, food and packaging [58]. However, its use for the
removal of textile dyes from aqueous effluents by adsorption
has proven to be effective according to several studies. Cellulosic fibres are compounds with a high degree of organization, and the progressive elimination of the less organized parts leads to fibrils with increasing crystallinity up to
almost 100%. The color removal abilities of different scales
of P. oceanica cellulose extracts were tested. Douissa et al.
(2013) [35] studied the elimination of MB dye by the cellulose extract of P. oceanica and reported a maximum MB
adsorption capacity of 0.955 mmol ­g−1, which corresponds
to 305.45 mg.g−1. Moreover, the maximum MB uptake
in P. oceanica leaves calculated by Allouche and Yassaa
(2018) [36] was 357 mg.g−1. In the same context, Batmaz
et al. (2014) [121] studied the removal of MB by CNCs
prepared from commercial cellulose fibres via sulfuric acid
hydrolysis, and the maximum adsorption capacity of this
material was 118 mg.g−1. Douissa et al. (2013) [35] studied
the detailed structure of cellulose extracted from P. oceanica using FTIR analysis and the acidic functional groups
by Boehm titration. The results showed that most detected
acidic functional groups were carboxylic (0.875 mmol.
g−1), followed by phenolic (0.275 mmol.g−1) then lactonic
(0.015 mmol.g−1). Authors concluded that the adsorption
of MB on this material seems to be driven by electrostatic
interaction and hydrogen bonding involving respectively
charged groups and OH groups. The dye/extracted cellulose
interaction can be explained as a competitive adsorption of
water molecules and dye cations, leading to the presence of
the dye (as monomer and dimer species) in zones of electric double layer, where dye ions are surrounded by water
molecules and not in direct contact with the fiber surfaces.
The use of CNCs produced by hydrolysis of commercial microcrystalline cellulose for MB adsorption led to a
maximum adsorption capacity of 101 mg.g−1 [122]. Cellulose nanofibrils (CNFs) prepared from kenaf cores were
also tested for MB dye removal by Chan et al. (2015) [123],
and the maximum dye uptake value was 122.2 mg.g−1. The
adsorption of MB onto activated carbon/cellulose biocomposite films was investigated by Somesta et al. (2020) [124],
and the maximum adsorption capacity (103.66 mg.g−1) was
also less than the adsorption capacity of raw P. oceanica and
its extracted cellulose. MB removal using cellulose nanofibril aerogels derived from sago pith waste was the subject of
the study of Beh et al. (2020) [125], and the maximum MB
adsorption was 222.2 mg.g−1.
Guava (Psidium
guajava) leaf
powder
Corynebacterium
glutamicum
jackfruit
(Artocarpus
heteropyllus)
leaf powder
treated olive
pomace
H = 20 cm
D = 1.5 cm
H = 20 cm
D = 1.5 cm
H = 10 cm
D = 3 cm
H = 9 cm
D = 1.2 cm
H = 13 cm
D = 1.5 cm
H = 10 cm
D = 2 cm
P. oceanica
Rice husk
Column dimensions
Adsorbent
40
300
40
45
50
200
17.5
1
50
100
8.2
7.28
Flow rate
Initial dye con(mL. ­min−1) centration (mg.
L−1)
5
1
20
10
1
Breakthrough
concentration (mg.
L−1)
> 80
400
3480
> 100
28
214.5
Breakthrough
Time (min)
Table 11 Adsorption parameters of methylene blue dye onto different column filler materials
40
398
48.5
-
-
99
Exhaustion
concentration
(mg.L−1)
> 160
490
8640
> 250
-
841.5
15.24
267
124
98.27
4.41
480
Exhaustion Column uptake
time (min) capacity (mg.
g−1)
55
90.8
70.1
64.74
-
67.44
Color
removal
(%)
2.248
0.231
0.035
0.038
0.134
0.139
Kth
(mg.mL−1.
min−1)
[119]
[118]
[117]
[101]
[111]
[116]
Reference
Chemistry Africa
Chemistry Africa
A comparison of these results indicated that CNCs produced from P. oceanica biomass and even from raw P. oceanica leaves had the greatest MB adsorption capacity.
3.3 Activated Carbon of P. oceanica
Agricultural wastes are often the best source for activated
carbon production due to their low ash content. The study of
the composition of P. oceanica showed that it is a cellulosic
material with a low ash fraction (6–13%), which makes it a
promising precursor for activated carbon production. Dural
et al. (2011) [41] prepared activated carbon from P. oceanica
leaves chemically activated using zinc chloride impregnation
at ratios up to 45%. They studied the adsorption of MB dye
onto prepared activated carbon and found that the Langmuir
isotherm equation fit the experimental results better than did
the Freundlich and Dubinin–Kaganer-Radushkevich (DKR)
models, indicating monolayer adsorption with a maximum
dye uptake of 270.3 mg.g−1. A comparison of the maximum adsorption capacity of MB with that of other low-cost
biomass-based activated carbons (Table 12) revealed that P.
oceanica activated carbon has the highest dye uptake over a
wide range of pH values, which indicates that dead P. oceanic leaves can be effectively used as a precursor for the
preparation of high-quality activated carbon.
3.4 Modified P. oceanica
The modification of P. oceanica by chemical, physical or
thermal treatments in an attempt to enhance its adsorption
capacity has been investigated in several studies, and this
approach seems to be a good alternative for improving dye
elimination efficiency. In this context, Ncibi et al. (2007)
[115] studied the protonation of P. oceanica with ­H3PO4 and
­HNO3 and reported that compared with that of raw materials, the color removal of reactive red 228 increased by up
to 80%. The modification of raw P. oceanica biosorbent
using succinic anhydride was studied by Aguir et al. (2009)
Table 12 Adsorption capacity of MB on different biomass-based activated carbons
Biomass
T(°C)
pH
Qmax (mg.g−1)
Reference
P. oceanica
Sunflower oil cake
cotton stalk
Olive seeds
Oil palm shell
Dragon fruit peel
Bamboo
Oil palm wood-based
Rice husk
35
25
25
30
50
25
30
25
3–10
6
9–10
6.5
10
-
270.3
16.43
193.5
263
243.9
195.2
183.3
90.9
9.83
[41]
[78]
[81]
[126]
[127]
[128]
[129]
[130]
[131]
[40], who reported that the same treatment enhanced the
elimination of Direct Red 75, and the adsorption capacity
increased from 37 mg.g−1 to 82 mg.g−1. These authors also
studied ­Pb2+ grafting on treated P. oceanica and reported
that modified P. oceanica saturated with P
­ b2+ was able to
−1
adsorb 147.12 mg.g Direct Red 75. Aguir and M’Henni
(2007) [109] also studied the carboxymethylation of cellulose extracted from P. oceanica and its use in basic blue 41
dye removal and used different carboxymethylate percentages and various contact times. Their results confirmed that
chemical modification enhanced the adsorption behavior
of P. oceanica extracts and demonstrated that modified P.
oceanica has very high retention capacities for removing
basic blue dye 41, whose maximum uptake ranges from
1252 to 2149 mg.g−1 at 30 °C, from 1764 to 2256.4 mg.g−1
at 40 °C, from 2080 to 2690 mg.g−1 at 60 °C, and from 2398
to 2950.88 mg.g−1 at 80 °C. In the same context, Elmorsi
et al. (2022) [54] developed an activated adsorbent from
the debris of P. oceanica rhizomes, the activation was performed using acetic acid. The removal of MB-spiked saline
and brackish water was between 51.7% and 97.2%.
Ferchichi et al. (2024) [132] developed a new adsorbent
materials using polymer grafting onto cellulosic biomaterial
of P. oceanica. They compared the adsorption properties
of phenol red anionic dye on P. oceanica surface modified
with polyaniline emeraldine salt with those of P. oceanica
grafted with polyaniline emeraldine base. They concluded
that modified material exhibited better performance than
unmodified one. In addition, they stated that the presence
of inorganic salts negatively affected the adsorption of phenol red dye because competitive adsorption between dye
and ions occurred which reduced the adsorption efficiency.
Thus, they highlighted the crucial role of the solution ionic
strength in the adsorption experiments and the need to determine a salinity optimal range in dye adsorption on modified
materials.
Safarik et al. (2016) [133] studied the magnetic modification of P. oceanica biomass using three procedures:
modification with microwave-synthesized magnetic iron
oxide nano- and microparticles [134], mechanochemical
synthesis [135] and modification with water-based magnetic fluid [136]. They found that the first method led to
better methylene blue dye uptake (143.7 mg.g−1) than the
second and third methods (102.5 mg.g−1 and 133.3 mg.
g−1, respectively). The authors stated that this behaviour is
due to the deposition of iron oxide nanoparticle aggregates
on the surface of the Posidonia biomass after magnetic
modification, providing sufficient surface area and consequently efficient dye adsorption. They also studied the
use of modified P. oceanica biomass with microwave-synthesized magnetic iron oxide nano- and microparticles as
adsorbents for the removal of 7 organic water-soluble dyes
belonging to different dye classes, and the corresponding
Chemistry Africa
Table 13 Maximum adsorption capacities of different dyes using
magnetically modified P. oceanica [133]
Dye
Qmax (mg.g−1)
Acridine orange
Bismarck brown Y
Brilliant green
Crystal violet
Methylene blue
Nile blue A sulfate
Safranin O
119.8
233.5
151.8
99.9
143.7
193.7
88.1
the way for industrial-scale application. However, it is first
necessary to further develop column tests using P. oceanica
and its derivatives which remain poorly studied. Subsequently, studies must be carried out to highlight the environmentally friendly aspect of the use of biomaterials in general
and particularly of P. oceanica, compared to conventional
adsorbents through life cycle assessment. Once this is done,
the next challenge will undoubtedly be the scaling up of the
technology.
Funding Not applicable.
Declarations
results are shown in Table 13. The values obtained for all
the studied dyes were relatively high; Bismarck brown Y
dye exhibited the highest value (233.5 mg.g−1), while the
lowest ­Qmax value was obtained for safranin O (88.1 mg.
g−1).
Recently, a novel method for rapid magnetic modification
of diamagnetic materials has been developed and applied on
P. oceanica fibers [137]. This method is based on mixing of
diamagnetic materials with suspensions of magnetite nanoand microparticles in highly volatile organic solvents under
microwave irradiation. This modification procedure is very
rapid when compared with already described procedures and
can produce similar magnetic materials which can be used
for dye removal applications.
4 Conclusion
Today, the world finds itself in a critical situation between
vertiginous industrial development and worrying environmental issues. Scientific research is therefore more oriented
towards the valorization of renewable bioresources to follow
the approach of sustainable development imposed by accentually severe environmental legislation. In this context, P.
oceanica, a Mediterranean seaweed rich in cellulosic material that has been widely studied as an adsorbent for the
elimination of textile dyes from colored effluents, has proven
to be effective at reducing the initial amount of dye by up
to 99%. The different forms of P. oceanica studied, such
as the raw form, cellulosic derivatives, activated carbon or
modified forms using chemical or physical treatments, have
shown high percentages of dye removal as well as very satisfactory maximum adsorption capacities compared to those
of other bioresources. Therefore, this marine biomass can
be valorized to produce high-quality biosorbents or nanocomposite materials with excellent performance. The present
work has summarized the existing experimental approaches
for studying the use of P. oceanica-based adsorbents, which
allowed high dye removal from colored effluents and paved
Ethical Approval Not applicable.
Informed Consent Not applicable.
Conflict of Interest Not applicable.
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