Green Algas

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com/scientificreports
OPEN Green algae Ulva lactuca‑derived

biochar‑sulfur improves
the adsorption of methylene blue
from water
Amany G. M. Shoaib 1, Huu‑Tap Van 2, Dinh‑Trinh Tran 3, Amany El Sikaily 1,
Mohamed A. Hassaan 1 & Ahmed El Nemr 1*
The present investigation explores the efficacy of green algae Ulva lactuca biochar-sulfur (GABS)
modified with H2SO4 and NaHCO3 in adsorbing methylene blue (MB) dye from aqueous solutions.
The impact of solution pH, contact duration, GABS dosage, and initial MB dye concentration on the
adsorption process are all methodically investigated in this work. To obtain a thorough understanding
of the adsorption dynamics, the study makes use of several kinetic models, including pseudo-first
order and pseudo-second order models, in addition to isotherm models like Langmuir, Freundlich,
Tempkin, and Dubinin–Radushkevich. The findings of the study reveal that the adsorption capacity at
equilibrium (qe) reaches 303.78 mg/g for a GABS dose of 0.5 g/L and an initial MB dye concentration
of 200 mg/L. Notably, the Langmuir isotherm model consistently fits the experimental data across
different GABS doses, suggesting homogeneous adsorption onto a monolayer surface. The potential
of GABS as an efficient adsorbent for the extraction of MB dye from aqueous solutions is highlighted
by this discovery. The study’s use of kinetic and isotherm models provides a robust framework for
understanding the intricacies of MB adsorption onto GABS. By elucidating the impact of various
variables on the adsorption process, the research contributes valuable insights that can inform the
design of efficient wastewater treatment solutions. The comprehensive analysis presented in this
study serves as a solid foundation for further research and development in the field of adsorption-
based water treatment technologies.
Keywords Methylene blue adsorption, Sulphuric acid-modified biochar, Green algae Ulva lactuca, Dye
removal
The discharge of dangerous chemicals and dyes into textile wastewater poses a serious threat to the environment.
Numerous treatment approaches have been investigated to tackle this p roblem1–3, which covered the oxidation of
reactive dyes with in situ electro-generated active chlorine for wastewater treatment in the textile dyeing industry.
They highlighted the sustainability challenges textile industries face in managing solid and liquid waste, lead-
ing to environmental p ollution4. Sarkar et al.5 emphasized the significant contribution of the textile industry to
industrial water pollution, with 17–20% attributed to dyeing treatments. In their evaluation of electrocoagulation
technology, Naje et al.6 addressed the poor rate of pollutant removal and the production of a significant amount
of sludge in traditional coagulation procedures. This technology is used to treat textile wastewater.
Moreover, Halepoto et al.7 discussed the use of anaerobic and aerobic processes for treating high and low
chemical oxygen demand (COD) textile wastewater, respectively. A staged forward osmosis technique was pro-
posed by Kim et al.8 and Li et al.9 for the simultaneous desalination and concentration of textile wastewater. They
recognised water pollution as a major environmental problem related to the textile industry and emphasized
using the best possible technology to reduce air and water pollutants from textile dyeing and finishing. Fur-
thermore, Bazrafshan et al.10 studied textile wastewater treatment using electrocoagulation and compared the
performances of various electrode connection modes.
1
Environment Division, National Institute of Oceanography and Fisheries (NIOF), Kayet Bey, Elanfoushy,
Alexandria, Egypt. 2Center for Advanced Technology Development, Thai Nguyen University, Tan Thinh Ward,
Thai Nguyen City 25000, Vietnam. 3VNU Key Lab. of Advanced Materials for Green Growth, University of
Science, Vietnam National University, No. 19 Le Thanh Tong Street, Hoan Kiem, Hanoi 120000, Vietnam. *email:
[email protected]; [email protected]
Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 1
Vol.:(0123456789)
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Textile wastewater treatment is a critical environmental concern, and sustainable techniques, such as adsorp-
tion engineering, have gained significant attention11–14. Among several physical and chemical wastewater treat-
ment methods that have been used in recent years to remove dyes14, adsorption is one of the most effective
techniques that has been successfully used to remove dyes from industrial wastewater. High adsorption capacity
materials have the potential to be used in adsorption procedures that remove a variety of contaminants from tex-
tile effluent, such as organic compounds, heavy metals, and d yes4,15,16. These materials can vary from traditional
activated carbon to innovative options like biochar or modified c lays17–19. The advantages of adsorption engineer-
ing in treating textile wastewater lie in its efficiency in removing various pollutants12. This includes effectively
fractioning dyes and salts using ultrafiltration m embranes20. Besides, the use of materials like red mud, eggshells,
and biochar has been explored for the removal of specific dyes from wastewater, highlighting the versatility of
adsorption processes21–23. The potential of biochar for removing organic and inorganic pollutants from industrial
effluents has been highlighted, emphasizing its versatility and effectiveness in wastewater t reatment24–27.
Furthermore, the use of engineered biochar, incorporating appropriate magnetic media, has been explored
for effective separation from the aqueous phase, enhancing its potential for practical applications in wastewater
treatment28–31. The application of biochar for water and wastewater treatment has been extensively reviewed,
showcasing its high sorption capacity for various contaminants, including hydroquinone32. Researchers have also
looked at using biochar in biofiltration systems to remove pathogens, nutrients, and pharmaceutical and personal
care items from wastewater. This shows that biochar can remove a variety of contaminants33. The influence of
nitrogen modification on adsorption capacity was demonstrated by the improved phenol adsorption displayed by
the nitrogen-doped hierarchical porous biochar made from maize stalks34. Additionally, modification methods,
including HNO3, NaOH, and N a2S, have been shown to enhance the adsorption capacity of biochar for Mn(II)
removal35. Additionally, the excellent adsorption characteristics of cationic dyes have been proven through the
use of calcium-rich biochars generated from wasted mushroom substrates, indicating the possibility of particular
modifications for targeted adsorption a pplications36.
The use of biochar derived from green algae Ulva lactuca (U. lactuca) for the adsorption of pollutants from
aqueous solutions is an innovative and eco-friendly approach in the field of environmental remediation. Green
algae, as source material for biochar, represents a sustainable and renewable resource, as it can be cultivated in
various water bodies, including those unsuitable for other u ses37–42. Algae-based biochar, especially when modi-
fied, can have a high surface area and porosity, making it highly effective for adsorbing pollutants, including
heavy metals, dyes, and organic compounds from wastewater28,43–45. Moreover, it emphasizes that the presence
of N-functional groups in algae-based biochar improved its surface chemistry and adsorption capacity46. These
findings underscore the potential of modified biochar from green algae for efficient adsorption of contaminants.
The investigation into utilizing modified biochar derived from green algae U. lactuca for the adsorption of
Methylene Blue from aqueous solutions constitutes a significant and innovative contribution to the wastewater
treatment domain. This study fills a critical void in existing literature, predominantly concentrating on conven-
tional and frequently less sustainable approaches to treating textile wastewater. The novelty of the present research
lies in its examination of a sustainable and effective alternative utilizing biochar derived from U. lactuca. In
contrast to traditional adsorbents, green algae biochar presents a renewable, cost-efficient, and environmentally
friendly solution. The modification of this biochar to augment its adsorption capacity, particularly for methyl-
ene Blue, showcases a pioneering strategy to target specific pollutants commonly found in textile wastewater.
Moreover, the utilization of green algae U. lactuca, an easily accessible and underutilized biomass, for biochar
production not only offers an efficient remedy for wastewater treatment but also contributes to managing algal
blooms and carbon sequestration. This research addresses the gap by presenting a pragmatic, scalable, and envi-
ronmentally sustainable approach, underscoring the potential of biochar modifications to fulfil specific industrial
wastewater treatment requirements. This facet has not been extensively explored in prior studies.
This study aims to employ biochar derived from the green algae U. lactuca using concentrated H 2SO4 and
NaHCO3 to adsorb MB dye from aqueous solutions. The study will evaluate factors such as initial concentra-
tion, contact time, and pH through batch experiments. Furthermore, the application of adsorption models will
be utilized to comprehend the mechanism and kinetics of the adsorption process. This approach represents an
innovative and sustainable method in industrial wastewater treatment, aiming to mitigate detrimental.
Materials and methods

Chemicals and equipment
Sulfuric acid ( H2SO4 (99%), Mwt = 98.079 g), Sodium bicarbonate N
aHCO3 (Mwt = 84 g), Sodium Hydrox-
ide (NaOH, Mwt = 39.997 g), Hydrogen Chloride (HCl , Mwt = 36.46 g). MB dye (basic blue 9; C.I. 52,015,
M.F. = C16H18N3ClSxH2O, λmax = 665 nm, M.W. = 319.86 g/mol, 97% dye content) (Fig. 1) was acquired from
Honeywell Riedel-de Haën AG, Seelze-Hannover, a JENCO-6173 pH metre, Germany. A JSOS-500 shaker, and
Figure 1. Methylene blue dye chemical structure.
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a digital UV/Visible spectrophotometer (PG instrument model T80 Doublebeam UV/visible spectrophotometer,
United Kingdom, with glass cells and a 1 cm optical path) were used in this work.
Sampling
Green algae U. lactuca were harvested from the coastal region of Alexandria, cleaned with tap and distilled water,
and then allowed to air dry for one night at room temperature before being baked for seventy-five hours at 120 °C.
then used the automatic mixer to compress it into a fine powder. Before use, the green powder was put through
a 100-mesh screen. The obtained U. lactuca samples have the following characteristics: Bulk density of 0.8179 g/
mL, Ash content of 35.12%, and moisture content of 15.3%.
Preparation of stock solution

A stock solution containing 1000 mg/L of MB dye was prepared by dissolving 1.0 g in 1000 mL distilled water
(DW). Once the concentrations needed for the standard calibration curve and adsorption studies were deter-
mined, this stock solution was diluted further.
Preparation of GABS
300 g of dried U. lactuca powder was added to 600 mL of concentrated H2SO4, followed by the addition of 70 mL
of DW. The system was then refluxed for 4 h at 300 °C, filtered, and then washed with DW and 1% NaHCO3
solution to eliminate any residual acid until the filtrate became neutral. Finally, ethanol was added to remove
any impurities and any residual deep organic materials and the mixture was dried for 24 h at 120 °C to produce
122 g (40.67% yield) of the targeted biochar. This type of carbon is called sulfonated biochar carbon GABS.
Batch adsorption procedure

A series of adsorption batch equilibrium experiments were conducted to examine the biochar’s ability to remove
MB dye including the impact of initial adsorbate concentration, contact duration, and pH on the adsorption
efficiency47,48. Batch adsorption studies were studied in a set of Erlenmeyer flasks with 100 mL of varied MB dye
solution concentrations (100, 125,150,175 and 200 mg/L) and varying doses of GABS (0.5, 0.75, 1.0, 1.25, and
1.5 g/L) at 25 °C. Up to a certain point, an isothermal shaker operating at a set 200 rpm and constant temperature
was employed.
An initial concentration (100–200 mg/L for MB dye) was created to investigate the effects of contact dura-
tion and initial adsorbate concentration on the adsorption uptake. The impact of solution pH on the adsorption
process was investigated by changing the starting pH of the solutions from 2 to 12. Furthermore, by fitting
the equilibrium data to the Langmuir, Freundlich, and Temkin models, respectively, isotherm investigations
were conducted for adsorption. The kinetics of the adsorption process were investigated in the batch kinetic
studies using the pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, and intraparticle diffusion
methods47,49,50. Upon utilising the aforementioned models to depict the kinetic data, each experiment’s qcal, qexp,
slope, and intercept were determined, along with the least-squares correlation coefficient (R2). Equation (1) was
used to predict the adsorption capacity at equilibrium (qe).
(C0 − Ce )V
qe = (1)
m
where the ability of the adsorbent to adsorb MB dye from a solution at a specific time is expressed as the adsorp-
tion capacity (qe) (mg/g). The initial concentration of MB dye is C0 (mg/L), and the concentration of MB dye
that remains after a given amount of time is Ce (mg/L). You may use Eq. (2) to find the percentage of MB dye
removed from water.
(C0 − Ce )
Removal% = × 100 (2)
C0
Determination of point of zero charge p

HZPC
To determine the p
HZPC value of prepared activated carbons, 0.1 g of activated carbon was introduced into 50 mL
of 0.1 M N
aNO3 solution with an initial pH range of 3–10 and was shaken for 24 h. After that, the sample was
separated from the solution and the solution equilibrium pH values were measured and the p HZPC value was
obtained.
Characterization
The characteristics of GABS were examined using FTIR spectroscopy, proximate analysis, XRD, EDX, SEM,
and surface area analysis. The dry GABS powder’s X-ray diffraction pattern (XRD) was obtained at an angle of
2θ using an X-ray diffractometer (Ulitama IV, Rigaku, Tokyo, Japan). Using a field emission scanning electron
microscopy (SEM; QUALITY 250) with an acceleration voltage of 15.0 kV, the size and shape of biochar were
examined. EDX was used to determine the materials’ elemental concentrations of C, N, and O. Using the mul-
tipoint N2 adsorption Brunauer–Emmett–Teller (BET) technique (BELSORP-Mini II, BEL Japan, Inc.), specific
surface area, pore size, and pore volume were determined. The functional groups on the surface of GABS were
recognized by the Fourier transfer infrared (FTIR) spectrometer (VERTEX70 and ATR unit model V-100) in
the region of 400–4000 cm−1. Using a thermogravimetric analyzer (TGA), approximate analyses of the GABS
were conducted (SDT650-Simultaneous Thermal Analyzer apparatus). The percentages of moisture, volatile
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matter, fixed carbon, and ash were computed at 100% based on the TGA results. To assess the moisture content,
GABS was heated in N2 gas from room temperature to 110 °C until dehydration was achieved. GABS underwent
breakdown at a temperature rise rate of 5 °C/min, with a temperature range of 25–1000 °C25,51,52.
Result and discussion

Characteristics of GABS
The functional groups existing on the surface of Green algae U. lactuca and the resulting GABS adsorbent were
identified Using FTIR spectroscopy. The FTIR diagrams of the U. lactuca and GABS were compared (Fig. 2a,b).
The materials’ FTIR spectra reveal modifications to their functional groups. The stretching oscillation of the
O–H present in the U. lactuca and GABS is shown by the broadband at 3253.52 cm–1 (Fig. 2a) for U. lactuca and
3339.40 and 3213.85 cm–1 (Fig. 2b) for GABS. The strong adsorption peak at 2926.03 cm–1 (Fig. 2a) suggests
the existence of –CH2 stretching groups in U. lactuca. According to Fig. 2b, these groups were broadband at
2655.87 and 2612.12 cm–1 in GABS. The tiny adsorption band at 1789.27 cm–1 is caused by the C=O stretching
of the anhydride groups in the U. lactuca (Fig. 2a). Later on, at 1707.07 cm–1, this band changed into a carboxyl
group in GABS (Fig. 2). However, when GABS was compared to raw U. lactuca, the strength increased to
1707.07 cm–1, suggesting that sulphoric acid treatment may enhance the carbonyl (C=O) group 47. The bands
located at 1626.49 cm–1 indicate that the C=O stretching oscillation of the β-ketone was almost nonexistent
in the U. lactuca (Fig. 2a). With high intensity, this oscillation moved to 1584.87 cm–1 in GABS; it might be a
stretching vibration of –C=C– in GABS (Fig. 2b). The peaks at 1418.32–1251.00 cm–1 are indicative of the U.
lactuca ‘ C–O functional group (Fig. 2a). The band at 1375.36 and 1236.24 cm–1 in GABS, which showed the
sulfonyl group (SO) stretching vibration, took the position of this group (Fig. 2b). Additionally, the development
of broad peak covered the area between 1236.00 and 940.00 cm–1 was produced by the dehydration process with
H2SO4. These peaks resulted from the production of –SO3H and SO groups in GSBS. These bands show that
the U. lactuca treatment with H2SO4 results in the creation of the GSBS. In contrast to GSBS, which had a faint
band at 767.63 cm–1, U. lactuca displayed a more pronounced increase in the –C–O–C– asymmetric stretching
functional group at 1080.35 cm–1 (Fig. 2a)25,53–55.
The N2 adsorption–desorption isotherm of the GABS was examined to determine how H 2SO4 altered the
surface properties of the GABS. The BET and BJH approaches were used to determine the specific surface area
and mesopore area, respectively. The textural characteristics of GABS, such as the average pore diameter, mon-
olayer volume, mass of mesopores, mesopore area, total volume of pores, and mesopore distribution peak, are
displayed in Fig. 3. At 6.26 m2/g, the GABS has a comparatively small BET-specific surface area. The monolayer
volume value of DABS was 1.4389 cm3 (STP) g–1. The overall volume of GABS is 2.0309 × 10–2 cm3/g. The overall
pore volume of DRB-SO was 1.8975 × 10–2 cm–1, with mean pore sizes of 12.971 nm. The mesopore distribution
peak value, meso surface area peak value, and mesopore volume peak values of the GABS adsorption study were
determined to be 1.22 nm, 2.1338 × 10–2 cm3/g, and 7.0477 m2/g, respectively. In the GABS study of adsorp-
tion, the mesopore volume, meso surface area, and mesopore distribution peak values were determined to be
4.3323 m2/g, 1.8970 × 10–2 cm3/g, and 1.66 nm, respectively.
Figure 4 displays SEM images of the GABS, demonstrating its purity and lack of contaminants. After the
strong sulfuric acid treatment, the pore structure of the GABS remained intact. The particle size distribution
shows that the particle sizes were within the range of 1800–7884 nm and the determined average particle size
distribution of the GABS was 4241 ± 1.65 nm.
Using scattered X-ray spectrometry (EDX), the chemical composition of the GABS adsorbent was investi-
gated. Table 1 displays the percentage of each element. It shows that, in addition to carbon mass percentage, which
accounts for 53.59% of the sample, there are approximately 41.70 and 1.29% of oxygen and sulphur, respectively.
Thermal gravimetric analysis (TGA) was used to evaluate the effects of structural differences on the degrada-
tion behaviour and operating temperature of the raw U. lactuca and GABS samples. The materials were cooked
between 50 and 1000 °C in a N2 environment. The analytical curves for TGA, differential thermal analysis
(DTA), and differential scanning calorimetry (DSC) for U. lactuca and GABS adsorbent are shown in Fig. 5.
The evaporation of water in the raw U. lactuca and GABS was the source of the first weight drop, which peaked
before 200 °C. As the temperature increased over 200 °C, numerous acidic oxygen functional groups broke down,
causing raw U. lactuca and GABS to lose weight. U. lactuca shows three weight losses at temperatures between 25
and 200, 200–550 and 550–950 °C with a total weight loss of 78.01%, while GABS shows also three weight losses
at temperatures between 25 and 200, 200–700 and 700–950 °C with total weight loss of 46.52%, which explains
the stability of GABS compared to the raw U. lactuca (Fig. 5a). Because of the breakdown of carbon in biomass,
the TGA curves of GABS and U. lactuca converged at temperatures greater than 433 °C and 220 °C, respectively.
The DTA graph of raw U. lactuca and GABS is illustrated in Fig. 5a. The DTA curve of the raw U. lactuca
peaked at three temperature points (Tf, 78.97, 220.44 and 709.64 °C), and the curve of GABS peaked at three
temperature points (Tf, 108.16, 433.27 and 725.52 °C) (Fig. 5a). The DTA curve demonstrating the production
of GABS adsorbents from raw U. lactuca indicates that the dehydration of raw U. lactuca yielded three distinct
degradation bands. The GABS degradation bands occurred at a higher temperature after treatment with 90%
H2SO4, demonstrating that the degree of degradation was intensely affected by treatment with H2SO4.
DSC may be used to compare materials by using thermal transitions or glass transitions. Figure 5b depicts
the DSC graph of raw U. lactuca and GABS. The glass transition temperatures (Tg) of U. lactuca occurred at
116.53, 145.82, and 170.69 °C, while GABS displays Tg values at 335.11, 353.26, and 363.76 °C. Higher transitional
temperatures transformed the grains into more crystalline forms that were more resistant to gelatin breakdown
and had better structural integrity.
Figure 6 displays the results of the GABS XRD, which reveal an amorphous carbon structure with aromatic
sheets orientated randomly. A broad peak is identified as the C (002) diffraction peak in the region of 2Ɵ ~ 24.9,
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Figure 2. FTIR graphs of (a) green algae U. lactuca and (b) GABS.
whereas a minor peak is situated at 2Ɵ = 42.54. About 2Ɵ ~ 15.4 (101) notable cellulosic peaks is a small peak.
This might indicate several inorganic substances, namely quartz and albite (a mineral that contains plagioclase
feldspar)56,57.
Solution pH effect on MB dye adsorption

Upon analysis of the data provided in the study on the elimination efficiency of methylene blue (MB) dye using
GABS under different pH conditions over time (Fig. 7a), several critical observations can be drawn. The general
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Figure 3. (a) Diagram of N2 adsorption–desorption, (b) diagram of the BET, (c) diagram of the BJH
adsorption, (d) diagram of the BJH desorption of the GABS.
trend indicates that as the solution pH increased from 2 to 12, the adsorption efficiency of MB dye by GABS
gradually increased over time, ranging from 5 to 180 min. Initially, at time t = 0, the removal efficiency of MB
dye by GABS was 0% across all pH levels. However, as the time of contact increased, the removal efficiency of
MB dye exhibited a significant dependence on both the contact time and the solution pH. Notably, at a lower pH
of 2, the removal efficiency started at 29.69% after 5 min and peaked at 53.80% at 150 min before experiencing
a slight decline to 47.49% at 180 min. This initial increase, followed by a decline, could suggest a saturation of
the adsorption sites on GABS or possible desorption at extended contact times. As the pH increased to 4 and 6,
there was a similar pattern of increased efficiency over time, with the highest removal efficiencies being 61.57%
at pH 4 and 61.83% at pH 6, both observed at the 180-min mark. This indicates that the GABS has a relatively
consistent adsorption capacity in the slightly acidic to neutral pH range.
Interestingly, the removal efficiency exhibited a distinct trend at higher pH values. At pH 10 and 12, there
was a rapid increase in the removal efficiency within the first 10 min, reaching 71.72% and 95.97%, respectively.
Moreover, at pH 12, the efficiency swiftly escalated to above 93.90% within 5 min. and plateaued around 98.00%
from 150 min onward. Under these conditions, the removal efficiency of MB dye by GABS was optimal, reaching
95.97% after 150 min of adsorption at pH 12. This could be indicative of the GABS having a more favourable
adsorption interaction with MB in a highly alkaline environment, possibly due to changes in the GABS’s surface
charge or the MB dye molecules’ ionization s tate55,58,59.
The observed trend of increasing methylene blue (MB) dye removal efficiency by granular activated carbon
derived from sugarcane (GABS) with increasing pH from 2 to 12 over time aligns with the general understand-
ing of adsorption processes. The literature provides insights into the adsorption properties of various carbon-
based materials, shedding light on the mechanisms underlying the observed trend. Shrestha et al.60 discussed
the adsorption properties of rice husk-derived carbon materials, including excellent methylene blue adsorption
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Figure 4. SEM image of GABS using high vacuum SEM at magnification × 500 and 15.0 kV.
GABS
Elements Mass% Atom%
C 53.59 ± 0.30 62.02 ± 0.34
O 41.70 ± 0.61 36.24 ± 0.53
S 1.29 ± 0.06 0.56 ± 0.02
Ca 3.42 ± 0.11 1.19 ± 0.04
Total 100.00 100.00
Table 1. EDX results of prepared GABS.
properties, which can provide insights into the adsorption behaviour observed in the study. Moeinian and
Mehdinia61 focused on removing MB dye from aqueous solutions using rice husk silica adsorbent, offering valu-
able information on adsorption processes. Furthermore, Kouassi et al.62 explored the removal of MB dye from
industrial effluents using corncob-activated carbon, providing insights into the adsorption behaviour of activated
carbon. Ndi Nsami and Ketcha M badcam63 also discussed the adsorption efficiency of chemically prepared acti-
vated carbon from cola nut shells for MB dye, offering further insights into the adsorption processes. These refer-
ences collectively contribute to understanding GABS’s observed pH-dependent adsorption behaviour towards
MB dye, providing a comprehensive perspective on the underlying mechanisms driving the observed trends.
The graph in Fig. 7b illustrates the p
HPZC (point of zero charge) values of GABS, which is determined to be
7.75. When the solution pH exceeds the p HPZC of the adsorbent, the surface charge of the adsorbent becomes
negative. The MB dye is classified as cationic, indicating a positive charge in s olution64,65. At lower pH values,
such as pH 2, the positive charge on the adsorbent’s surface results in electrostatic repulsion between the dye
molecules and the adsorbent, leading to reduced adsorption of MB dye. Conversely, as the pH surpasses the
isoelectric point (up to pH 12 in this instance), the surface of GABS becomes increasingly negatively charged
due to the deprotonation of acidic functional groups. There is an electrostatic attraction between the positively
charged MB dye molecules and the adsorbent, facilitating the adsorption of MB dye onto the surface of GABS.
The transition from a positive to a negative charge on the adsorbent surface as the pH increases from a low value
(e.g., pH 2) reduces electrostatic repulsion. Eventually, it leads to electrostatic attraction as the pH exceeds the
isoelectric point (7.75) and rises. Consequently, the adsorption capacity for MB dye on GABS increases with
rising pH, reaching optimal levels when the pH is well above the isoelectric point, as GABS’s highly negative
surface charge favours the adsorption of the cationic dye molecules. This phenomenon is consistent with the
principles of surface charge and electrostatic interactions in the context of adsorption processes.
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Figure 5. (a) Diagrams of TGA and TDA, and (b) diagram of DSC of the U. lactuca and GABS.
Contact time impact on MB dye adsorption

Analyzing the provided dataset on GABS’s MB dye adsorption capacity across different adsorbent concentrations
over time reveals several pertinent aspects regarding the adsorption kinetics and equilibrium states. The data
from Fig. 8 demonstrates the rapid uptake of MB dye by GABS over time, indicating a typical initial phase of the
adsorption process characterized by the abundance of available active sites. The influence of adsorbent concentra-
tion on the adsorption capacity is pronounced, with lower concentrations leading to a quick escalation in MB dye
adsorption capacity, reaching 91.91 mg/g within 5 min and continuing to rise to a maximum of 179.41 mg/g at
180 min. This suggests that at lower adsorbent concentrations, the ratio of available adsorption sites to MB mol-
ecules is high, allowing more excellent individual adsorbent saturation. However, as the dose of GABS increases,
the initial adsorption capacity decreases, indicating a dilution effect or fewer available adsorption sites per unit of
adsorbent due to aggregation or reduced surface area exposure. Despite this, all concentrations of GABS approach
a similar adsorption capacity value at the equilibrium state after 180 min, with the 1.0 g/L concentration showing
a slightly higher equilibrium capacity of 98.00 mg/g compared to the others. The trend of adsorption capacity
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Figure 6. XRD graph of fabricated GABS biochar.
Figure 7. (a) The influence of pH values on the removal of MB dye through adsorption. The experimental
conditions included a GABS dose of 1.0 g/L, initial MB dye C0 of 200 mg/L, temperature of 25 ± 2 °C, and
contact time of 180 min, (b) pHPZC analysis of GABS.
Figure 8. Contact time impact on MB dye adsorption by GABS. The experimental conditions included a pH of
12, C0 of MB dye of 200 mg/L, and temperature of 25 ± 2 °C.
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with increasing GABS dose does not strictly follow a linear relationship, suggesting diminishing returns as the
concentration increases, possibly due to the overlapping of adsorption sites and the formation of aggregates at
higher concentrations, which decreases the effective surface area available for adsorption.
The equilibrium adsorption capacity of MB by GABS increased gradually over time and reached saturation
after 90–120 min with GABS dose increasing from 0.5 to 0.75 g/L. However, the saturation state was achieved
after 20 min of adsorption for GABS concentrations ranging from 1.0 to 1.5 g/L, with a stable adsorption capacity
of 171 mg/g observed for the 0.5 g/L GABS dos after 120 min. The observed increase in the adsorption capacity
of MB dye by GABS over time, reaching saturation after varying durations at different GABS concentrations,
also aligned with the findings of several relevant studies, for instance, demonstrated that the adsorption perfor-
mance of cationic dyes, such as MB dye, by activated carbon modified with surfactants significantly influences
the adsorption capacity66. This behaviour aligns with the findings of those who discussed MB dye adsorption
and its complexes with montmorillonite, providing insights into the adsorption behaviour of cationic d yes67.
The study demonstrated the selective adsorption of cationic dyes, offering further insights into the adsorption
behaviour of cationic d yes68. Also, the work of Yamaguchi et al.69 examined the adsorption of the cationic dye
MB dye, providing valuable insights into the adsorption behaviour of cationic dyes. Furthermore, studies on the
creation of M oO3 nanowire-based membrane devices for the selective adsorption of cationic dyes from aque-
ous solutions are pertinent because they shed light on the process of selective adsorption, which advances our
knowledge of the adsorption behaviour of cationic d yes70.
The reduction in MB dye adsorption capacity and the rapid attainment of saturation with increasing the
adsorbent material (GABS) ratio can be attributed to several critical factors related to the adsorption process
and the system’s physical characteristics. Firstly, adsorption is contingent on the availability of surface area for
the adsorbate (MB dye) to interact with the adsorbent material (GABS). An increase in the ratio of adsorbent
material augments the available surface area for the adsorption process. However, there is a limit to the amount
of MB dye that can be adsorbed onto the surface area. Once all available surface sites are occupied, further
increments in the adsorbent material do not increase adsorption capacity. Secondly, as the quantity of adsorbent
material rises, there is heightened competition among the adsorbent particles to occupy the limited adsorption
sites. This intensified competition necessitates MB dye molecules to compete with each other to bond with the
restricted number of active sites on the adsorbent surface, thereby diminishing the overall adsorption capacity
and hastening saturation. Thirdly, in certain instances, increasing the quantity of adsorbent material can elongate
the diffusion path for MB molecules to reach the active sites on the adsorbent surface. Lengthier diffusion paths
can decelerate the rate at which MB dye molecules can access and bond with the adsorbent, leading to a swifter
saturation of the adsorption sites. Lastly, as the ratio of adsorbent material increases, the system may reach a
juncture where mass transfer limitations become significant. This implies that the rate at which MB dye molecules
can be conveyed from the bulk solution to the adsorbent surface becomes a constraining factor. Consequently,
the adsorption capacity saturates more rapidly as the rate of adsorption fails to match the rate at which MB dye
molecules approach the adsorbent s urface27,71.
GABS dose’s impact on adsorption capacity at different starting MB dye concentrations

The data presented in Fig. 9 provides valuable insights into the relationship between the initial concentration
of MB dye and its adsorption capacity on GABS at various adsorbent doses. This analysis offers significant illu-
mination on how the dose of GABS influences the adsorption efficiency for different C0 of MB dye. Notably, at
an initial MB dye concentration of 100 mg/L, the adsorption capacity of GABS at 0.5 g/L reached 179.41 mg/g,
indicating a high efficiency of MB dye removal per unit of adsorbent. This notable adsorption capacity can be
attributed to the abundance of active sites available for the lower concentration of MB dye, facilitating maximum
interaction between MB dye molecules and GABS. However, as the C0 of MB dye increased to 125, 150, 175, and
Figure 9. Impact of GABS dose on MB adsorption. The experimental conditions included a pH of 12, contact
time of 180 min, and temperature of 25 ± 2 °C.
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200 mg/L, the adsorption capacity of GABS at 0.5 g/L also increased, reaching a peak of 303.78 mg/g at 200 mg/L
of MB. This trend suggests that a higher C0 of MB dye may enhance the driving force for mass transfer, overcom-
ing any resistance to adsorption and leading to a higher adsorption capacity. Conversely, at higher GABS doses
ranging from 0.75 to 1.5 g/L, the adsorption capacity generally decreased with increasing adsorbent dosage. For
instance, at an initial MB dye concentration of 200 mg/L, the adsorption capacity decreased from 234.00 mg/g
at 0.75 g/L to 129.23 mg/g at 1.5 g/L.
The observation that the aggregation of adsorbent particles at higher doses reduces the effective surface area
and active sites for methylene blue (MB) dye adsorption is supported by several relevant studies. The diminished
adsorption capacity observed with increased adsorbent dosages is primarily attributed to the aggregation and
overlapping of adsorbent particles, reducing the overall available surface area for dye adsorption. In a similar
vein, the surface area may be reduced and the diffusional route length may be increased when adsorbent parti-
cles aggregate at increasing masses72. As the initial concentration of MB dye increases, the adsorption capacities
at higher doses reach a plateau, signifying the approach to the equilibrium capacity of the adsorbent 73. All of
these findings lend credence to the idea that adsorbent particle aggregation at higher dosages can decrease
the number of active sites and effective surface area available for MB adsorption, which in turn can affect the
adsorption capacity. The data underscores the adsorbent dose’s critical role in determining GABS’s adsorption
capacity. While lower doses of GABS are more efficient in adsorbing MB dye per gram, they may not be practi-
cal for treating higher concentrations of MB dye due to their lower total adsorption capacity. Conversely, higher
doses of GABS may be necessary to treat larger volumes or higher concentrations of MB dye, despite their lower
efficiency per unit mass.
Adsorption kinetic of MB dye onto GABS

The data presented in Table 2, Figs. 10 and 11 delineates the adsorption kinetics of MB dye on the GABS using
the first-order and second-order kinetic models. These models are essential for comprehending the rate of
adsorption and identifying the most suitable model for designing and predicting the behaviour of adsorption
systems in practical applications. In the first-order kinetic model (Fig. 10), the adsorption rate constant (k1) and
the calculated adsorption capacity (qe,calc.) are compared against the experimental adsorption capacity (qe,exp.).
According to the first-order model, the proportion of occupied to vacant adsorption sites is determined by the
occupancy rate of those sites. The values of k1 vary with both the dose of GABS and the initial concentration of
MB dye. For instance, at a GABS dose of 0.5 g/L and an initial MB dye concentration of 100 mg/L, the k1 value is
23.72 × 10–3 with a qe(calc.) of 132.07 mg/g, which is lower than the experimental value of 179.41 mg/g, indicating
Parameter Pseudo-first-order Pseudo-second-order

GABS dose Methylene blue (mg/L) qe (exp.) qe (calc.) k1 × 103 R2 qe (calc.) k2 × 103 h R2
100 179.41 132.07 23.72 0.963 200.00 0.23 9.12 0.991
125 245.00 28.41 27.41 0.998 243.90 3.00 178.57 1.000
0.5 g/L 150 291.81 74.92 23.49 0.990 294.12 0.86 74.63 0.999
175 293.62 59.28 16.81 0.962 294.12 0.91 78.74 0.999
200 303.78 48.02 18.65 0.918 303.03 1.20 109.89 1.000
100 128.33 79.05 30.17 0.980 135.14 0.74 13.57 0.997
125 164.38 21.56 34.08 0.980 163.93 19.58 526.32 1.000
0.75 g/L 150 196.97 36.49 18.42 0.966 200.00 4.63 185.19 1.000
175 224.59 9.40 55.27 0.929 227.27 1.56 80.65 1.000
200 234.00 72.88 10.13 0.990 232.56 0.59 31.95 0.995
100 98.00 2.13 16.12 0.715 98.04 41.62 400.00 1.000
125 123.36 2.81 54.81 0.974 123.46 65.61 1000.00 1.000
1.0 g/L 150 148.32 17.66 40.76 0.985 149.25 6.80 151.52 1.000
175 169.66 44.60 27.18 0.975 172.41 1.53 45.45 0.999
200 187.29 64.09 20.27 0.972 192.31 0.78 28.90 0.998
100 78.79 4.92 44.91 0.654 78.74 22.72 140.85 1.000
125 98.74 1.22 30.17 0.971 99.01 127.51 1250.00 1.000
1.25 g/L 150 118.85 3.05 33.62 0.870 119.05 37.14 526.32 1.000
175 138.21 18.88 36.85 0.986 138.89 5.70 109.89 1.000
200 153.27 50.65 21.19 0.951 156.25 1.03 25.19 0.998
100 65.74 2.23 38.92 0.844 65.79 50.23 217.39 1.000
125 82.33 0.52 26.25 0.917 82.64 183.01 1250.00 1.000
1.5 g/L 150 99.05 1.38 46.29 0.964 99.01 113.34 1111.11 1.000
175 115.46 13.49 45.83 0.961 116.28 10.13 136.99 1.000
200 129.23 44.38 26.71 0.982 133.33 1.45 25.84 0.999
Table 2. The calculated kinetic parameters of MB dye adsorption onto GABS.
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Figure 10. Pseudo-first-order model fitting for MB dye adsorption onto GABS.
some deviation from the model. The R2 values for the first-order model, which show the model’s goodness of fit
with the experimental data, are also presented (Table 2). While the R2 values are relatively high for all data sets,
some are below 0.95, suggesting a less accurate model fit for those conditions.
The second-order kinetic model, on the other hand, frequently offers a better match for chemisorption pro-
cesses as it posits that the adsorption rate is dependent on the availability of the adsorbate and adsorption sites
(Fig. 11). The calculated qe values are in closer agreement with the experimental data across most GABS concen-
trations, as evidenced by consistently high R2 values, indicating an excellent fit. The initial rate of adsorption (h),
which can be interpreted as a combined effect of the rate constant k2 and the square of the equilibrium capacity,
is also provided for the second-order model. These h values are notably high at lower GABS concentrations,
especially at higher initial MB dye concentrations, suggesting a more efficient adsorption process under these
conditions. The data indicates that the second-order kinetic model provides a better fit to the experimental data
than the first-order model, particularly at lower GABS concentrations where the R2 values are perfect or near-
perfect (1.000 or close to it), suggesting that the second-order kinetics are more appropriate for describing the
adsorption behaviour of MB dye onto GABS. For instance, at a GABS dose of 0.5 g/L, the second-order model
fits perfectly for initial MB dye concentrations of 125, 150, 175, and 200 mg/L with R2 values of 1.000, while the
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Figure 11. Pseudo-second-order model fitting for MB dye adsorption onto GABS.
first-order model fits well but with slightly less congruence. At higher GABS doses, such as 1.5 g/L, the second-
order model still provides a strong fit, although the first-order R2 values suggest a reasonable model agreement.
The kinetic analysis of the adsorption of MB onto GABS suggests that second-order kinetics closely describe
the process across various adsorbent doses and initial MB dye concentrations, providing valuable insights for
designing and optimizing adsorption systems for MB dye removal from wastewater. The second-order model
demonstrates a firm fit, aligning with the first-order R2 values, indicating a reasonable model agreement. This
finding is consistent with previous research that found the second-order kinetic model suitable for describing
adsorption processes, as it provides essential information about the initial extraction process and the mechanism
occurring in the final extraction s tage74. Furthermore, the literature supports the use of second-order kinetics for
modeling and predicting the behavior of adsorption systems under various operating conditions, emphasizing
this model’s applicability in understanding and optimizing adsorption processes75.
Adsorption isotherm of MB dye onto GABS

The study presented in Table 3 outlines the application of various isotherm models to describe the adsorption of
MB dye on the GABS at different concentrations (Fig. 12). Isotherm models are essential for understanding the
interaction between adsorbates and adsorbents and are crucial in designing adsorption systems.
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Isotherm Isotherm GABS dose

Model Parameters 0.5 g/L 0.75 g/L 1.0 g/L 1.25 g/L 1.5 g/L
Qm (mg/g) 303.03 238.10 200.00 166.67 135.14
Langmuir Ka 0.52 0.57 0.82 0.72 0.34
R2 1.000 1.000 0.999 0.993 0.997
1/n 0.07 0.07 0.12 0.33 0.20
Freundlich KF (mg1–1/nL1/ng–1) 229.19 189.63 139.77 76.35 91.20
R2 1.000 0.879 1.000 0.903 0.999
AT 1.14E + 01 1.24E + 01 7.19E + 00 1.88E + 00 5.19E + 00
BT 19.936 15.228 19.214 38.257 18.268
Tempkin
bT 1.24E + 02 1.63E + 02 1.29E + 02 6.48E + 01 1.36E + 02
R2 0.9999 0.8891 0.9992 0.944 0.9966
Qm (mol kg–1) 299.02 232.57 184.23 159.02 124.87
K × 106 (mol k J–1)2 0.30 0.20 0.30 0.40 0.03
Dubinin–Radushkevich
E (kJ mol–1) 1.29E + 00 1.58E + 00 1.29E + 00 1.12E + 00 4.08E + 00
R2 0.981 0.990 0.983 0.926 0.988
Table 3. The calculated isotherm and correlation constant parameters of MB dye adsorption onto GABS.
Figure 12. Isotherm model fitting for MB dye adsorption onto GABS.
Langmuir isotherm model the maximum adsorption capacity (Qm) decreases with increasing GABS dose,
indicating that lower doses of GABS have a higher capacity for adsorbing MB dye. The adsorption constant
(Ka) varies across different GABS doses, reflecting the strength of the adsorption bond. Assuming monolayer
adsorption on a homogeneous surface with no interaction between adsorbed molecules, the R2 values are about
1.000 for all GABS dosages, showing a good match to the Langmuir model.
Freundlich isotherm model the heterogeneity factor (1/n) provides insight into the adsorption intensity or
surface heterogeneity. Lower values suggest more homogeneous adsorption intensity. The Freundlich adsorp-
tion capacity (KF) decreases with increasing the GABS dose, implying reduced adsorption efficiency at higher
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adsorbent doses. The R2 values suggest that the Freundlich model fits well for most concentrations, although
the fit is not as strong for 0.75 g/L.
Tempkin isotherm model the Tempkin isotherm constant (AT) decreases notably as the GABS dose increases,
indicating a potential reduction in adsorption capacity. The Tempkin constants (BT and bT) show variation with
the GABS concentration, implying changes in the adsorption heat and surface coverage. The R2 values indicate
a good fit for the Tempkin model, except for 0.75 g/L, where the fit is less satisfactory.
Dubinin–Radushkevich (D–R) isotherm model the theoretical saturation capacity (Qm) decreases with increas-
ing the GABS dose, consistent with the Langmuir model. The D–R constant (K) suggests the nature of the
adsorption process, with variations indicating differences in adsorption energy. The mean free energy (E) of
adsorption provides insights into the adsorption type; energies less than 8 kJ/mol typically indicate physical
adsorption. The R2 values suggest that the D–R model fits reasonably well across all concentrations. Therefore,
the adsorption of MB dye onto the GABS is best described by the Langmuir model, suggesting homogenous
adsorption onto a monolayer surface. However, the Freundlich model’s applicability across most concentrations
indicates that adsorption also occurs on a heterogeneous surface with varying energies. The Tempkin model
points to a decreasing heat of adsorption with increasing GABS concentration, and the D–R model suggests that
the adsorption process is primarily physical. These models and their parameters can be invaluable in optimizing
the design and operation of adsorption systems for MB dye removal using the GABS. The selection of the best-fit
isotherm model is crucial for predicting the behaviour of the adsorption process under various conditions. It is
evident that while the Langmuir model provides a very consistent fit, the relevance of the Freundlich and D–R
models at different GABS doses highlights the complexity of the adsorption process, which may not be perfectly
monolayer or homogeneous. These insights underline the necessity to consider multiple isotherm models for
a comprehensive understanding of the adsorption mechanisms, significantly when scaling up from laboratory
to industrial applications. The pseudo-second-order kinetic model has been found to provide a good correla-
tion for the adsorption of MB onto various adsorbents, including clay, activated carbon, and biochar-coupled
magnetic material76–78. Besides, the Langmuir model has shown a consistent fit for the adsorption of MB onto
various materials, suggesting monolayer adsorption, while the Freundlich model has also been relevant at dif-
ferent concentrations, indicating heterogeneous surface e nergies79,80.
Intraparticle diffusion and film diffusion model

The data presents a comparative analysis of the intraparticle and film diffusion kinetics for the adsorption of MB
dye on the GABS at various doses (Table 4, Figs. 13, 14). These models are crucial for characterizing the mass
transfer mechanisms during the adsorption p rocess81.
Intraparticle diffusion the intraparticle diffusion rate constant (Kdif ) signifies the rate at which the MB dye
moves through the boundary layer to the adsorbent’s surface (Fig. 13). The Kdif values exhibit variability with
both the GABS dose and MB dye concentration. For instance, at the GABS dose of 0.5 g/L and an initial MB
dye concentration of 100 mg/L, Kdif is 8.881, which decreases to 3.886 as the MB dye concentration increases
to 200 mg/L. The intercept (C) represents the boundary layer thickness, with higher values suggesting a more
significant contribution of surface diffusion in adsorption. For example, C increases from 65.38 to 254.98 as the
MB dye concentration increases from 100 to 200 mg/L at a GABS dose of 0.5 g/L. The coefficient of determina-
tion (R2) suggests a good fit for the intraparticle diffusion model, with values close to 1.0000, indicating that the
model reliably represents the diffusion process across most conditions.
Film diffusion the film diffusion coefficient (KFD) reflects the mass transfer rate of MB dye across the liquid
film surrounding the GABS particles (Fig. 14). At the GABS dose of 0.5 g/L, KFD ranges from 0.0236 to 0.0187 as
the MB dye concentration increases from 100 to 200 mg/L, indicating that the film diffusion rate may decrease
with higher MB dye concentrations. Similar to the intraparticle diffusion model, the C value for film diffusion
suggests the impact of the external mass transfer resistance. For instance, at 0.5 g/L GABS dose, the C value var-
ies significantly, reaching up to 2.155 for an MB dye concentration of 125 mg/L. The R2 values are high across
all conditions, particularly for the film diffusion model, demonstrating an excellent fit and suggesting that film
diffusion is a significant factor influencing the adsorption kinetics of MB dye onto the GABS. At a GABS dose
of 1.5 g/L, the film diffusion model shows an R2 of 0.977 for an MB dye concentration of 175 mg/L, indicating
that film diffusion is a significant step in controlling adsorption. The intraparticle diffusion R2 is lower (0.820)
at the same conditions, implying that while intraparticle diffusion contributes to the process, the film diffusion
could be the rate-limiting step.
The film diffusion seems more consistent with higher R2 values across all doses and concentrations, indicat-
ing it may often be the controlling mechanism (Fig. 14). Besides, the intraparticle diffusion cannot be neglected,
especially at lower GABS doses and MB dye concentrations, where its contribution is significant. The film and
intraparticle diffusion process plays an essential role in adsorption systems.
Comparison of results with reported literature

A selection of earlier research on the removal of MB dye ions from aquatic medium is shown in Table 5. Accord-
ing to the maximum adsorption capacity (Qm) reported in this Table, at room temperature, the GABS adsorbent
has the highest Qm for MB dye among the literature reported in Table 5. For the elimination of MB dye ions at a
given concentration of 0.5 g/L of GABS adsorbent, these values were 303.03 mg/g. It is clear from this compari-
son that the GABS made from green algae was a highly effective adsorbent for taking out MB dye from aqueous
solutions.
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Intraparticle diffusion Film diffusion

GABS dose (g/L) Methylene Blue (mg/L) Kdif C R2 KFD C R2
100 8.881 65.38 0.981 0.0236 0.356 0.978
125 2.533 216.21 0.915 0.0273 2.155 0.998
0.5 150 6.063 220.47 0.974 0.0236 1.387 0.995
175 4.904 229.40 0.989 0.0161 1.589 0.991
200 3.886 254.98 0.961 0.0187 1.845 0.918
100 5.800 61.24 0.976 0.0302 0.485 0.980
125 0.201 162.02 0.777 0.0603 2.791 0.963
0.75 150 1.872 175.79 0.830 0.0358 2.175 0.989
175 3.071 185.45 0.974 0.0184 1.854 0.980
200 5.961 148.77 0.986 0.0102 1.166 0.990
100 0.136 96.11 0.719 0.0161 3.830 0.715
125 0.218 121.13 0.777 0.0473 3.951 0.984
1.0 150 1.536 130.76 0.855 0.0407 2.128 0.985
175 3.317 130.32 0.972 0.0271 1.336 0.975
200 4.689 126.77 0.982 0.0202 1.072 0.972
100 0.797 69.71 0.820 0.0450 2.774 0.654
125 0.076 97.86 0.870 0.0294 4.902 0.946
1.25 150 0.113 117.50 0.841 0.0336 3.661 0.870
175 1.737 119.20 0.891 0.0368 1.990 0.986
200 3.571 106.15 0.973 0.0237 1.023 0.965
100 0.369 61.65 0.651 0.0390 3.386 0.844
125 0.042 81.82 0.904 0.0280 5.058 0.965
1.5 150 0.074 98.22 0.676 0.0464 4.271 0.964
175 1.110 102.84 0.820 0.0488 2.041 0.977
200 3.508 89.05 0.976 0.0281 1.040 0.978
Table 4. The intended parameters for intraparticle and film diffusion models and correlation at MB dye
adsorption onto GABS.
Regeneration study
Desorption studies of the MB dye from the GABS adsorbent were carried out using 0.1 M NaOH and HCl fol-
lowed by ethanol as an elution media to examine the viability and reusability of the adsorbent for the adsorp-
tion of MB dye. In this investigation, when the regeneration cycles increased, the proportion of dye desorption
decreased (Fig. 15). Using the regenerated GABS, six cycles of adsorption/desorption have been investigated.
Throughout the cycles, the changes in adsorption and desorption were mostly almost c onstant12,65. However, after
six cycles, it decreased by about 9.9% for MB dye. It advises using GABS as a long-lasting method of removing
MB colour from water (Fig. 15).
MB dye adsorption mechanism using GABS

The most plausible process by which GABS absorbed the MB dye ions is described in Fig. 16. After the green
algae, U. lactuca source material has been dehydrated by 90% using H2SO4. FTIR examination revealed that a
range of functional groups, such as C=O, CO2H, C–O–C, O–H, SO3H, C–S, SH, and SO groups, formed on the
adsorbent’s surface (GABS). due to the positive charge on the MB dye in the presence of OH to stabilise the
newly formed bond, as well as the electrostatic contact between the sulphur and oxygen lone pair on the GABS
surface. Electrostatic interaction may be used to carry out the MB dye ions’ adsorption procedure in a high basic
media (pH 12.0).
In a strong basic environment, the surface of GABS picks up a positive charge on the MB dye, which attracts
negatively charged O H25,92. Furthermore, dye molecules are more soluble at a basic pH, which makes it easier for
them to adhere to the adsorption sites and diffuse through the BABS’s pores. The most significant process is the
ionizable organic molecules’ adsorption to the positively or negatively charged surface of the biochar through
electrostatic contact93–104.
Moreover, the pH of the solution affects the organic pollutants’ ability to adsorb in industrial e ffluent93. The
application of biochar made from food waste for the adsorption of textile colours in wastewater was investigated
by Parshetti et al.105. They discovered that dye adsorption was boosted by an alkaline pH. The significant interac-
tion between the negatively charged sites on the surface of the biochar and the positively charged dyes explained
it. According to Tsai and Chen106 and Xu et al.107, the ability of biochar to absorb materials is affected by pH. The
pH of the solution therefore influences the charged sites and the ability of organic and inorganic contaminants
from industrial effluent to adsorb on biochar.
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Figure 13. Intraparticle diffusion model fitting for MB dye adsorption onto GABS.
Conclusion
The study on the adsorption efficiency of MB dye from aqueous solutions using the GABS offers valuable insights
into the nuanced dynamics of MB dye adsorption onto the GABS. The findings highlight vital observations,
including the optimal adsorption capacity of 303.78 mg/g at the GABS dose of 0.5 g/L and the 200 mg/L MB
dye concentration. Furthermore, the Langmuir isotherm model consistently fits the adsorption data, indicating
monolayer adsorption on a homogeneous surface, with the highest adsorption capacity (Qm) of 303.03 mg/g. The
applicability of the Freundlich and Tempkin models across different GABS doses underscores the complexity of
the adsorption process, emphasizing the need for a multifaceted understanding of the adsorption phenomena,
particularly when scaling from laboratory to industrial applications. Moreover, the study demonstrates that the
pseudo-second-order kinetic model offers a better correlation than the first-order model for the adsorption
data, highlighting its suitability for predicting the system’s behaviour under various conditions. These detailed
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Figure 14. Film diffusion model fitting for MB dye adsorption onto GABS.
insights are instrumental for designing and optimizing industrial-scale adsorption systems for effective MB dye
removal from wastewater. The findings advocate for a tailored approach based on specific operational parameters,
emphasizing the importance of considering various kinetic and isotherm models to understand the adsorption
process comprehensively. The study’s comprehensive analysis of the adsorption dynamics of MB dye onto GABS
contributes to the existing body of knowledge on wastewater treatment technologies. The insights provided by
this research can inform the development of efficient and sustainable water treatment solutions, particularly
in industrial-scale applications. By elucidating the nuanced dynamics of MB dye adsorption onto GABS and
emphasizing the significance of considering various operational parameters, the study offers a valuable founda-
tion for further research and development in adsorption-based water treatment technologies.
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Biosorbents Qm (mg g –1) References

GABS 303.03 This study
Marine alga U. lactuca 40.2 82
83
Cedar sawdust 142.36
83
Crushed brick 96.61
84
Sugar beet pulp 244.76
85
Watermelon rind 231.48
86
Inactivated rosemary plant 153.17
86
Activated carbon from rosemary plant 110.67
Corn Stigmata 106.3 87
88
Orange peel 280
89
Jute stick charcoal 29.32
Azolla pinnata 80.6 90
Shorea spp. 37.8 91
Table 5. The highest amount (Qm, mg/g) of MB dye that can be adsorbed onto several documented adsorbent
materials.
Adsorpon-Desorpon cycles of MB dye

105
98.55
Ads Des
96.30
96.20
95.80
95.60
100
94.75
93.90
Adsorpon-Desorpon (%)
91.85
91.10
90.92
95
89.65
88.66
90
85
80
75
70
65
60
1 2 3 4 5 6
Number of cycles
Figure 15. Renewal study of MB dye adsorption–desorption by GABS adsorbent using dye C0 (100 ppm) and
1.5 g/L GABS dose at room temperature.
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Figure 16. The most likely process by which the produced GABS adsorbent absorbs the MB dye.
Data availability
Should any raw data files be needed in another format they are available from the corresponding author upon
reasonable request.
Received: 29 March 2024; Accepted: 10 May 2024
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Author contributions
Dr A.G.M. Shoaib, and Dr. M.A. Hassaan carried out the experiment, calculation and theoretical models. Prof.
A. El Sikaily supervised the experimental work. Dr. H.-T. Van and Dr. D.-T. Tran wrote the original manuscript.
Prof. A. El Nemr supervised the experimental work, completed the manuscript and provided financial support
for the experiment work.
Funding
Open access funding provided by The Science, Technology & Innovation Funding Authority (STDF) in coopera-
tion with The Egyptian Knowledge Bank (EKB). This work was partially funded by the Science and Technology
Development Fund (STDF) of Egypt (Projects Nos. SCSE-31235).
Competing interests
The authors declare no competing interests.
Additional information
Correspondence and requests for materials should be addressed to A.E.N.
Reprints and permissions information is available at www.nature.com/reprints.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and
institutional affiliations.
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OPEN Green algae Ulva lactuca‑derived

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 1

Materials and methods

Figure 1. Methylene blue dye chemical structure.

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Preparation of stock solution

Batch adsorption procedure

Determination of point of zero charge p

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Result and discussion

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Solution pH effect on MB dye adsorption

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Table 1. EDX results of prepared GABS.

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Contact time impact on MB dye adsorption

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Figure 6. XRD graph of fabricated GABS biochar.

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GABS dose’s impact on adsorption capacity at different starting MB dye concentrations

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 10

Adsorption kinetic of MB dye onto GABS

Parameter Pseudo-first-order Pseudo-second-order

Table 2. The calculated kinetic parameters of MB dye adsorption onto GABS.

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 11

Figure 10. Pseudo-first-order model fitting for MB dye adsorption onto GABS.

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Figure 11. Pseudo-second-order model fitting for MB dye adsorption onto GABS.

Adsorption isotherm of MB dye onto GABS

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Isotherm Isotherm GABS dose

Figure 12. Isotherm model fitting for MB dye adsorption onto GABS.

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 14

Intraparticle diffusion and film diffusion model

Comparison of results with reported literature

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 15

Intraparticle diffusion Film diffusion

MB dye adsorption mechanism using GABS

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Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 18

Biosorbents Qm (mg g­ –1) References

Shorea spp. 37.8 91

Adsorpon-Desorpon cycles of MB dye

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 19

Received: 29 March 2024; Accepted: 10 May 2024

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 20

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 21

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 22

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 23

© The Author(s) 2024

Scientific Reports | (2024) 14:11583 | https://doi.org/10.1038/s41598-024-61868-9 24

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Biosorbents Qm (mg g –1) References

Adsorpon-Desorpon cycles of MB dye