Magnetic activated carbon derived from pine fruit waste: efficient adsorbent for tetracycline (TC) and paracetamol (PC) removal from aqueous solution

doi:10.21203/rs.3.rs-3961482/v1

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Magnetic activated carbon derived from pine fruit waste: efficient adsorbent for tetracycline (TC) and paracetamol (PC) removal from aqueous solution

https://doi.org/10.21203/rs.3.rs-3961482/v1

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published 16 Jul, 2024

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This work presents a significant highly porous activated magnetic carbon nanoparticles (MPFRC-A) derived from pine fruit residue through physical activation (carbonization temperature: 110–550◦C), chemical activation (H₂SO₄ (0.1 N, 96%)), and Co-precipitation processes and then using it for removing tetracycline (TC) and paracetamol (PC) from water and evaluating via the spectrophotometer (DR6000). Functionalization of Fe₃O₄ nanoparticles on the surface of (PFR-AS) generated high saturation magnetization that causes to separate from aqueous solution by an external magnet. MPFR-AS adsorbent was evaluated by Brunauer-Emmet-Teller (BET) analyzer, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-Ray diffraction analysis (XRD) and Raman spectroscopy (RM). In the experimental sector, the effect of different items including, pH, contact time, initial concentrations, adsorbent dosage, and temperature on the adsorption processes were investigated and based on them the adsorption isotherm modules, and kinetics were studied and concluded. Results indicated that MPFR-A exhibited a large specific surface area (182.5 m2/g) and high total pore volume (0.33 cm3/g). The maximum adsorption capacity was obtained at pH = 4,5, adsorbent dose: 400 mg and initial concentration of 20 mg/L at 25°C. The study showed that experimental data were well-fitted by Langmuir isotherm model (R² > 0.98) and the maximum uptake capacities for TC was 43.75 mg/g and for PC was 41.7 mg/g.

Population growth and rapid industrialization of societies are serious problems of pollution all over the world ¹. Soil and water are directly affected by the sewage of different sectors such as chemical, pharmaceutical, agricultural, food and petrochemical industries, which creates severe risks for the environment ^2–7. Among the newly emerging pollutants, we can mention the pharmaceutical residues that are constantly released in the hospital wastewater environment ⁸. In the last few decades, several studies have shown that these pharmaceutical compounds can contaminate aquatic systems ^9,10. One of the challenging issues is that the pharmaceutical residues in wastewater are not exterminate or removed in many cases. Among the systematically used medicines, painkillers and antibiotics account for a significant share of the drugs consumed by humans and grassland animals ^11–13. For example, accordant with the World Health Organization (WHO), PC acts as a common nonsteroidal ¹⁴, anti-inflammatory ¹⁵, and antipyretic drug ¹⁶ in the first line of pain treatment by inhibiting cellular mediators involved in the initiation of pain. Based on the estimates, the global production of PC is predicted to reach 780 million dollars in 2025, among which China with proportion of 64.4% accounts for the top range of production of the global market of this medicine ¹⁷. It enters the surface and underground waters or the natural environment through unsuitable treatment of industrial effluents ¹⁸. Also, TC is an antibiotic that is mainly used to cure bacterial infections [18], mainly through its application in animal feed ¹⁹. on the other hand, in a scientific study, a significant correlation was observed between the concentration of TC in sewerage and the numeral antibiotic-resistant bacteria ^20,21. If these types of bacteria enter the human body, they can pose a serious threat by limiting the effectiveness of medical prescription because they have become resistant to the TC ^22,23. Due to misusage, unreasonable remedy procedures, and overdose, the residues of these pharmaceutical compounds are widely detected in variety of sources of surface water, which cause extremely adverse impacts on many forms of our life.

Several conventional methods of water remediation such as photocatalytic degradation ²⁴, biodegradation ²⁵, nanofiltration ²⁶, electrochemical oxidation ²⁷, reverse osmosis ²⁸, etc. have been implied but these methods need high complicated technical, and costly setup. In addition, these procedures release harmful by- products and are less effective. Among various treatment methods, the adsorption method due to its cost effective, simplicity, high effectiveness and availability of a large range of adsorbents have been applied ^29–31. One of the eco-friendly elimination of contaminants of effluents are carbonaceous sources in producing adsorbents from agricultural and food waste including wood sawdust ³², coconut shells ³³, orange peel ³⁴, oak shell ³⁵, palm-kernel shells ³⁶, wood chips ³⁷, rice husk ³⁸, corn cobs ³⁹, seeds ⁴⁰, etc. In order to activate these carbonaceous sources physical and chemical activation should be done on these agricultural residues. Physical activation of starting raw materials is carbonization of the residue waste and the consecutive activation at high temperature in a steam media. The carbonization of the already impregnated raw material with a chemical agent such as sulfuric acid, phosphoric acid, potassium hydroxide, zinc chloride, etc. is called chemical activation ^41,42. In fact, pharmaceutical compounds adsorption onto carbonaceous adsorbent pores take place through binding with functional groups that include oxygen-containing. Commonly, low specific surface area adsorbents are modified by chemical activation to improve their adsorption capacities ⁴³.The advantage of chemical activation in comparison with physical activation is that it doesn’t need high temperature and the procedure can be performed in only one step. Moreover, chemical activation process leads to higher yield and reduction in the mineral content.

In this work, a physical remedy (temperature: 110–550 ◦C) is used to transform the pine fruit residues into hard carbon powder. afterwards, a chemical activation procedure using sulfuric acid (0.1 N) and pyrolysis temperature were completed to generate highly porous activated carbon. Finally, Co-precipitation method was used to make magnetic carbon nanoparticles. For the investigation of application of this adsorbent, two different types of pharmaceutical compounds named TC, and PC were selected in aquatic system and the influences of important items in operation conditions including solution pHs, temperatures, contact times, and dosage of the adsorbent were evaluated. The properties of the adsorbent was explored via AAS, FTIR, XRD, BET, and SEM techniques and analyzed through kinetics, isotherms models, and thermodynamics.

FT-IR spectroscopy

In this study, the chemical structure of each component involved in the preparation of the adsorbent and the adsorption process was conducted using FT-IR spectroscopy, as depicted in Fig. 1. The broad peak observed at 3444 cm⁻¹ in spectrum 1a corresponds to the stretching vibration of OH bonds. This phenomenon is attributed to the presence of carboxylic acid and alcohol groups in cellulose or residual water ⁴⁴. Additionally, the peak observed in the 1576 cm⁻¹ region is associated with the stretching vibration of C = O bonds, specifically for carbonyl and carboxylic acid groups. Furthermore, the band observed at 1420 cm⁻¹ is related to the stretching vibration of C-C bonds due to the presence of aromatic rings ⁴⁴. After the pyrolysis process and subsequent activation, certain bonds were rearranged, leading to the formation of new functional groups on the surface of the MPFR-AS adsorbent. Notably, the stretching vibration of S = O bonds at 1013 cm⁻¹ provides clear evidence of sulfuric acid modification ⁴⁵. Finally, upon adsorption of TC and PC onto the adsorbent, the initial peak positions and intensities in the FTIR spectrum underwent changes, confirming the successful adsorption process ⁴⁴.

BET measurements

The BET method is employed to determine the specific surface area of materials. This technique relies on measuring the amount of nitrogen gas adsorbed within a relative pressure range of 0.1 to 1. Additionally, the pore size distribution is determined through the use of adsorption isotherms. In Fig. 2, the adsorption and desorption isotherms for two adsorbents are depicted. According to the IUPAC classification, these isotherms fall into Type IV (adsorption) and Type IV (desorption). Based on this classification, the pores exhibit a layered and sheet-like structure. Giving that Table 1, the specific surface area for carbon and m carbon adsorbents is equal to 195.5 and 182.5 m²/g, respectively. Also, in Table 4, the specifications of the absorbent surface are given. According to the data in Fig. 2, there is a distribution of the size of the holes in the absorber.

Table 1

Results of the BET measurements of adsorbent
parameter	Carbon	M carbon
a_s (m²/g)	195.5	182.5
V_m (cm³(STP) g^− 1)	96.46	94.66
V_p (cm³g^− 1)	0.42	0.33
r_p (nm)	5.06	4.21
a_p (m²/g)	117.24	115.44

SEM analysis

As observed in SEM images of MPFR-A and TC and PC adsorption (Fig. 3), before the adsorption process, the surface of the adsorbent is relatively smooth, and its pore sizes exhibit variability. However, following the adsorption of TC and PC, both the surface roughness and pore dimensions decrease. This reduction indicates the successful adsorption of pharmaceutical compounds onto the adsorbent material

XRD analysis

The observed patterns in several prior studies regarding MPFR-A indicate its amorphous nature (2θ = 15.8° to 22.8°). This amorphous character is attributed to the presence of organic materials, such as hydroxyl and carboxyl groups ⁴⁴. Upon activation and thermal decomposition, the amorphous nature transforms due to the presence of elements like graphite, calcium, and silica, resulting in a semi-crystalline structure ^44,45. Typically, the activation of the adsorbent involves acid treatment and high temperatures, leading to the breakdown of functional groups within cellulose and hemicellulose, ultimately forming graphite. The sharp peaks observed at 2θ = 29.38° and 43.12° in Fig. 4 correspond to the presence of graphite, silica, and the amorphous carbon nature, primarily due to the low graphite content ⁴⁴.

VSM analysis

The VSM analyses of MPFR-A was performed in order to demonstrate the magnetic property (Fig. 5). As can be seen, the compound have magnetic property and shows a nice increase ( 35, emu/g,).

Adsorption experiments

Several parameters affect the phenomenon of adsorption such as initial concentration of TC and PC solutions, contact time, pH, and mass of MPFR-AS. Adsorption experiments were followed by using 400 mg MPFR-AS for all solutions (35 ml) with concentrations of 10–50 mg / l for TC and PC. The glass erlenmeyer flakes were stirred at 200 rpm for 2 hours in the ambient temperature. Afterwards, the contents of the Erlenmeyer flask were separated by an external magnet. The separated liquids were analyzed via the spectrophotometer (DR6000). The obtained results reveal that the initial amount of pharmaceutical residue is one of the most noticeable factors which impact on the adsorption process. Generally, observed data in Table 2 showed a slight increase in the initial concentration of the pharmaceutical residue leads to increase in removal percentages as well, but according to limited amount of adsorbent there is a risk that the adsorbent be poisoned in high concentration. Therefore, we selected 20 mg/l in optimum section. In the following, pH, adsorbent amount, dosage of adsorbent, and contact time, were investigated to achieve reasonable data to study adsorption kinetics, and adsorption isotherms.

Table 2

Adsorption percentage in 10–50 (mg/ l) concentrations of TC and PC by MPFR-A (reported by the spectrophotometer DR6000)
Conct. of TC or PC (mg/ l)	%Adsp TC	%Adsp PC
10	78.16	73.11
20	83.15	81.18
30	85.21	88.14
40	89.13	91.17
50	91.14	91.17

The rate of TC and PC uptake on MPFR-A as adsorption capacity $q$ (mg/g) was obtained according to below equation.

$$q=\frac{\left({C}_{0}-{C}_{e}\right)\times V}{m}$$

Where, C₀ and Ce stand for the initial and equilibrium concentration respectively. V and m are defined the volume of the solution (L) and the weight of the adsorbent (g).

The pH of a solution is one of the most influential factors in the adsorption process and the mechanism of electrostatic forces. To determine the optimal pH for the adsorption of PC and TC, each drug was individually tested at a concentration of 20 mg/L, using 0.4 g/L of the adsorbent within the pH range of 8 to 3. Considering the pKa values of the drugs and the isoelectric point of the investigated adsorbent (which is 5), we observe that at pH values below the isoelectric point, the surface charge of the adsorbent becomes positive, while at pH values above the isoelectric point, the surface charge becomes negative. The results of the pH effect on adsorption capacity are illustrated in Fig. 6. Considering that the pka of TC is equal to 3.26 and PC is 9.51, for the drug PC at pH between 5 and 9 bar, it is called a pollutant and adsorbent, and the drug is absorbed by the adsorbent. For the TC, at pHs between 3 and 5, the surface charge of the adsorbent and pollutant is not named and the maximum absorption capacity occurs. As a result, the maximum absorption capacity occurs at pH 4 and 5 for TC and PC drugs. Considering that pH change affects the absorption capacity of two drugs, it can be said that electrostatic forces are involved in the absorption process.

Figure 6. The effect of pH on the absorption capacity of PC and TC (initial concentration 20 mg/l, adsorbent amount 0.4 g, volume 35 ml and ambient temperature)

Dosage of adsorbent

To check the optimal amount of adsorbent, different amounts of adsorbent 0.4, 0.6, 0.8, 1, 1.5 and 2 g/l of solution with an initial concentration of 20 mg/l, pH equal to 4 and 5 and a duration of 120 minutes were investigated. As can be seen in Fig. 7, it increases with the increase of the amount of adsorbent from 0 to 0.4 g/liter due to the adsorption sites remaining unsaturated during absorption; However, by increasing the amount of absorbent from 0.4 g to 2 g, the absorption capacity for both drugs has decreased due to the adhesion and clumping of the absorbent and the reduction of available active surface. Therefore, the adsorbent amount of 0.4 g/liter was considered as the optimal amount of adsorbent for the adsorbent in the next experiments.

Temperature

According to Fig. 8, with the increase in temperature, the speed of movement of drug molecules in the solution increases, and as a result, the energy of the random collision speed increases and causes the absorption capacity to decrease. Also, an increase in temperature breaks the bonds created between the absorbent and the pollutant and disposal occurs. According to the Fig. 8, the maximum absorption capacity is related to the ambient temperature, so the temperature of 25 degrees Celsius was chosen to continue the experiments.

Figure 8. The effect of temperature on absorption rate of PC and TC (initial concentration 20 mg/l, pH equal to 4 and 5, duration of 120 minutes and ambient temperature, amount of adsorbent 0.4 g)

Contact duration and kinetics investigation

In our study, we investigated the adsorption kinetics of TC and PC to understand the impact of contact time on their adsorption behavior. The initial solutions were prepared with a concentration of 20 mg/L, and 0.4 g/L of each adsorbent was added. To ensure that the adsorption process reached equilibrium, the samples were agitated for 2 hours in a shaker operating at 250 rpm and maintained at a temperature of 25°C. The results of this investigation shed light on the dynamic behavior of TC and PC adsorption, providing valuable insights for environmental and pharmaceutical applications.

The obtained data were fitted to pseudo-first-order, pseudo-second-order, and intraparticle diffusion models, with the results summarized in Table 3. Based on the coefficients of determination (R²) for each model, the pseudo-second-order linear model is deemed acceptable for the adsorption of TC and PC. The second-order kinetic model operates under the assumption that the rate-limiting step involves ion exchange. Additionally, the rate constants for the adsorption of TC and PC are estimated to be 0.116 g/(mg·min) and 0.096 g/(mg·min), respectively. The investigation of intraparticle diffusion kinetics provides valuable insights into the transport of solute species within porous adsorbents. Notably, the rate constant for intraparticle diffusion falls within the range of 3.21 to 3.78, while the constant C signifies the boundary layer thickness and characterizes the external mass transfer process. Furthermore, the pronounced increase in adsorption capacity during the initial stages of the process is attributed to the phenomenon of rapid mass transfer.

Table 3

Constants and coefficients related to absorption kinetic models
model	parameter	AC	TC
First-order quasi-linear	q_e (mg.g^− 1)	36.2	40.32
	K₁ (min^− 1)	0.04036	0.047
	R²	0.98	0.98
Second-order quasi-linear	q_e (mg.g^− 1)	44.41	47.94
	K₂/10^− 2 (g/(mg.min))	0.096	0.116
	R²	0.99	0.99
Intraparticle penetration	C (mg/g)	3.21	3.78
	k_ipd (mg.min ^− 0.5 g^− 1)	3.46	5.11
	R²	0.91	0.88
Elovich	α	0.26	0.20
	β	8.34	3.42
	R²	0.76	0.78

As shown in Fig. 9, in the early times, the slope of the graph is very steep (the rapid phase of external mass transfer) and as the equilibrium conditions are approached, the speed of the absorption process slows down (the slope of the graph decreases and reaches zero) until the adsorbent does not have more pollutant absorption power and the absorption graph is fixed. Also, after about 30 minutes, the absorption graph stabilizes and the absorption reaches equilibrium, however, to ensure the achievement of complete equilibrium, the studied time period was continued up to 120 minutes.

Adsorption isotherm

In the context of adsorption processes, quantifying the removal efficiency of pollutants from aqueous solutions is of paramount importance. To achieve this, we employ adsorption isotherm models, which explore the surface properties and affinity of the adsorbent toward the adsorption process. In this study, we investigated the adsorption behavior of TC and PC using the Langmuir, Freundlich, and Temkin isotherm models, as well as the three-parameter Redlich-Peterson model. The Langmuir model had the most overlap with the experimental results of TC and PC absorption. This model describes the adsorption process in terms of a monolayer at equilibrium. The maximum adsorption capacity (q_m) represents the adsorption capacity of a single layer. For TC and PC, the Langmuir model yielded high coefficients of determination (R² = 0.99). The Langmuir constants K_L characterizes the adsorbent’s affinity for the pollutant. The calculated values for TC and PC were 43.75 mg/g and 41.70 mg/g, respectively. By comparing the experimental data with the Langmuir isotherm, we observed excellent agreement between the model predictions and the measured adsorption capacities (as shown in Table 4). In summary, the Langmuir isotherm provides a robust framework for understanding the adsorption behavior of TC and PC, offering valuable insights for environmental remediation and pharmaceutical wastewater treatment.

The Freundlich isotherm, which characterizes heterogeneous surface adsorption, has been employed to investigate the interaction between the adsorbent and the pharmaceutical compounds. As shown in Table 4, the coefficient of determination (R²) for TC and PC adsorption using the Freundlich model is 0.95 and 0.91, respectively. Notably, these values are lower than those obtained from the Langmuir isotherm. This discrepancy underscores the limitations of the Freundlich model in describing the adsorption behavior of the aforementioned drugs. The parameter n in the Freundlich isotherm reflects the favorability of the adsorption process. For the range of n values between 0 and 10, the experimental data in Table 4 confirm favorable adsorption behavior. In summary, while the Freundlich isotherm provides insights into surface heterogeneity, the Langmuir model remains a more robust choice for describing the adsorption performance of TC and PC.

The Temkin isotherm model postulates that the heat of adsorption decreases linearly with coverage. Additionally, it assumes that the adsorption process is characterized by a uniform distribution of cohesive binding energies. According to the data presented in Table 4, the heat of adsorption follows a linear trend with decreasing surface coverage. The parameter A_T represents the equilibrium binding energy, corresponding to the maximum bond energy, while B_T pertains to the heat of adsorption. A low value of B_T indicates weak interactions between the adsorbate molecules and the adsorbent surface

Hill's isotherm model, in this model, it is a cooperative phenomenon where the ligand is attached in one place on the macromolecules. In this case, it may affect different binding sites on the same macromolecules. q_H is the adsorption capacity of the Hill isotherm, n_H is the Hill binding interaction coefficient, and K_H is the Hill constant.

Among the three-parameter adsorption isotherm models, the Redlich-Peterson model is frequently employed for liquid-phase adsorption of organic compounds. Based on the obtained correlation coefficients, both the Langmuir isotherm model and the Redlich-Peterson model outperformed the two-parameter models. This observation suggests that the adsorbent surface becomes more closed during surface adsorption, leading to a reduction in the influence of external factors on drug adsorption.

According to what was explained, the absorption of pharmaceutical pollutants on the researched absorbent is of single layer type. The absorbent structure is homogeneous and has the same absorption energy. Also, absorption has been done both physically and chemically. Considering that the value of β in the Redlich-Peterson equation is close to 1, the Langmuir model is more consistent with the laboratory equilibrium data. Figure 10 shows the fit of the Langmuir model curve.

Table 4

constants and coefficients of surface adsorption isotherm models for PC and TC absorption
model	parameter	PC	TC
Langmuir isotherm	q_max (mg.g^− 1)	41.7	43.75
	K_L (L.mg^− 1)	0.69	0.84
	R²	0.98	0.98
Freundlich isotherm	K_F (mg^1 − n.Lⁿ.g^− 1)	17.1	16.97
	n	2.75	2.69
	R²	0.91	0.95
Temkin isotherm	B_T (Kj.mol^− 1)	9.41	8.62
	A_T (L.mg^− 1)	6.55	8.91
	R²	0.91	0.97
Redlich-Peterson isotherm	K_RP (L.mg^− 1)	25.74	39.56
	_RPα _(L.mg⁻¹₎	0.44	1.08
	_Rpβ	1.12	0.93
	R²	0.98	0.98
Hill	q_H (mg.g^− 1)	38.41	41.68
	K_H	1.029	1.171
	n_H	1.402	1.004
	R²	0.98	0.98

Comparison studies with other adsorbents

In our study, we compared the adsorption capacity of activated magnetic carbon obtained from pine fruit waste with other existing adsorbents (see Table 5). However, due to variations in experimental conditions and physical properties of adsorbents, such as their structure, surface functional groups, and specific surface area, conducting a precise comparison remains challenging. Qualitatively, it appears that the adsorption capacity of materials derived from pine cone waste for the removal of TC and PC from aqueous environments generally outperforms other natural and synthetic adsorbents. These findings highlight the potential of utilizing waste-derived adsorbents for efficient pollutant removal in water treatment applications.

Table 5

Comparison of the adsorption efficiency of magnetic activated carbon derived from pine nut waste with others adsorbents
Adsorbents	TC	PC	Ref.
Rice husk ash	8.37	-	⁴⁶
Olive pomace	16	-	⁴⁷
Biochar (Pinus taeda)	29	-	⁴⁸
Montmorillonite	34	-	⁴⁹
Auricularia	3.2	-	⁵⁰
Poplar hydrochar	6.29	-	⁵¹
Graphene	-	18.9	⁵²
Rice husk ash	-	7.65	⁵³
Activated carbon derived from Quercus Brantii fruits	-	45.45	⁵⁴
Moringa oleifera seed pod activated carbon	-	20.28	⁵⁵
Dehydrated sewage sludge	-	0.95	⁵⁶
N-CNTs-β-CD	-	41.0	⁵⁷
magnetic activated carbon derived from pine nut waste	43.75	41.7	This Work

Recovery

Absorbent recovery for reuse is important from an economic point of view (Fig. 11). Although the price of synthesized adsorbents is higher, but due to their high absorption capacity, they can be used in smaller amounts than other mentioned adsorbents, which will bring a higher economic value. To recover the adsorbents, after each use, we add 5 cc of ethanol to the adsorbent, it is placed on the shaker for 20 minutes, then it is separated with a magnet, and in the next step, 5 cc of the buffer prepared in the ratio (1:10) is added to it and placed on the shaker for 20 minutes and finally separated by a magnet. According to Fig. 10, the synthesized adsorbent for PC and TC drugs can be used 6 times with a removal efficiency of 71.6 and 66.4%.

Figure 11. Reusability of MPFR-A

The present work shows successfully eliminated TC and PC from aqueous solutions through the utilization of activated carbon produced from pine cone waste. The carbon’s activity was evaluated through experiments involving H2SO4-treated aqueous samples. Several key parameters, including pH, initial concentration, contact time, temperature, and adsorbent dosage, were systematically investigated. The maximum adsorption capacity of the adsorbent was achieved under the following conditions: pH = 4 and 5, adsorbent dose = 400 mg and initial concentration 20 mg/L at 25°C. For TC, the maximum adsorption capacity reached 43.75 mg/g, while for PC, it was 41.7 mg/g. The experimental data closely aligned with the Langmuir isotherm model (with an R² > 0.98), indicating that the adsorption occurred on a heterogeneous surface. Notably, the adsorbent can be regenerated through sequential washing with ethanol and buffer solution, allowing for reuse. In summary, utilizing activated carbon from pine cone waste offers several advantages, including environmental compatibility, reasonable adsorption capacity, cost-effectiveness, and non-toxicity. These natural adsorbents, with their substantial surface area, hold significant promise for pharmaceutical compound removal from aqueous solutions, contributing to both economic and environmentally friendly practices in industrial settings.

Iron (III) chloride hexahydrate, Iron (III) chloride tetrahydrate, Sulfuric acid 96%, Acetic acid (glacial) 100%, PC, Aqueous ammonia (37%), TC hydrochloride, Ethanol 96%, orto-Phosphoric acid 85%, Boric acid were purchased from Merk company. Pine fruit residues were selected and collected from Chitgar forest, Tehran Province, Iran. Distilled water was purchased from Tamad kala, Iran.

Preparation of MPFR-AS

In the first step, activated carbon was synthesized using pine fruit waste. The pine residue was washed with distilled water well to remove the pollen and dried under the sun for 5 days, then put in the furnace for 8 hours at a temperature of 105 − 103°C until it dried completely, after that for the complete carbonization, the dried shells were placed in the furnace at 550°C for 20 minutes. afterwards, the samples were taken out of the oven and let them cooled down, and then they were pounded by a mortar until they were completely powdered. In order to homogenize the parts, they were sieved by a laboratory sieve and finally, the resulting powder was kept in a desiccator ⁴⁴.

In the second step, in order to generate more porosity in the obtained carbon from the previous step, it was mixed with different ratios of H₂SO₄ that were 1:1, 2:1, 3:1, and 4:1 (wt./wt.) with a glass stirrer and put in furnace at 110°C for 24 hours (soaking). Then, they washed with distilled water until reaching a stable and neutral pH, and this step was repeated several times in such a way that the above solution is poured into Falcon tubes, distilled water was added to them and mixed with a vortex machine. Finally, for complete separation, it was placed in a centrifuge at 5000 rpm for 20 minutes, and after neutralization, they were dried in an oven at a temperature of 103°C, and after cooling it was kept in a desiccator at room temperature ⁴⁴.

In the third step, Co-precipitation method was used to make magnetic carbon nanoparticles. For this purpose, FeCl₃ and FeCl₂ were dissolved in a glass flask containing 100 ml of deionized water with a molar ratio (2:1) and 1 gram of carbon obtained from the previous step was added to the above solution. The color of the solution at this stage was orange. Then aqueous ammonia (37%) was slowly added to the balloon until the solution turned completely black and its pH reached to 10. The solution was stirred at 80°C for 2 hours. This step of synthesis was done under nitrogen gas. Then, the synthesized magnetic carbon nanoparticles were separated from the balloon with an external magnet, washed and dried in a desiccator at room temperature.

Acknowledgment

Gratefully, this research was supported by the Water Research Institute, Tehran, Iran.

The authors declare that the data supporting the findings of this study are available within the Manuscript files.

contributions

Farzad Hashemzadeh: corresponding, supervision, conceptualization, data curation, formal analysis, writing-original draft.

Maryam Ariannezhad: corresponding, supervision, data curation, conceptualization, formal analysis, writing-original draft, writing-review and editing, project administration.

Seyed Hamed Derakhshandeh: data curation, funding acquisition, administration.

Statement of Compliance with Guidelines and Legislation

We confirm that our experimental research and field studies on plants, both cultivated and wild, strictly adhere to the relevant institutional, national, and international guidelines and legislation. The collection of plant material was conducted in accordance with these guidelines, ensuring ethical and responsible practices throughout our study

Author Contribution

Farzad Hashemzadeh: corresponding, supervision, conceptualization, data curation, formal analysis, writing-original draft.Maryam Ariannezhad: corresponding, supervision, data curation, conceptualization, formal analysis, writing-original draft, writing-review and editing, project administration.Seyed Hamed Derakhshandeh: data curation, funding acquisition, administration.

Zhou, H. Population growth and industrialization. Economic Inquiry 47, 249-265 (2009).
Inyinbor Adejumoke, A. et al. Water pollution: effects, prevention, and climatic impact. Water Challenges of an Urbanizing World 33, 33-47 (2018).
Halder, J. N. & Islam, M. N. Water pollution and its impact on the human health. Journal of environment and human 2, 36-46 (2015).
Quesada, H. B. et al. Surface water pollution by pharmaceuticals and an alternative of removal by low-cost adsorbents: A review. Chemosphere 222, 766-780 (2019).
Evans, A. E., Mateo-Sagasta, J., Qadir, M., Boelee, E. & Ippolito, A. Agricultural water pollution: key knowledge gaps and research needs. Current opinion in environmental sustainability 36, 20-27 (2019).
Zahoor, I. & Mushtaq, A. Water pollution from agricultural activities: A critical global review. Int. J. Chem. Biochem. Sci 23, 164-176 (2023).
Kalantari, M., Moghaddam, S. S. & Vafaei, F. Global research trends in petrochemical wastewater treatment from 2000 to 2021. Environmental Science and Pollution Research 30, 9369-9388 (2023).
Emam, T. E., Souaya, E. R., Ibrahim, M. & Mahmoud, S. A. Advanced removal of pesticides, herbicides, and pharmaceutical residues from surface water. Environmental Technology 44, 3466-3478 (2023).
Massima Mouele, E. S. et al. Removal of pharmaceutical residues from water and wastewater using dielectric barrier discharge methods—A review. International Journal of Environmental Research and Public Health 18, 1683 (2021).
Khan, N. A. et al. Recent trends in disposal and treatment technologies of emerging-pollutants-A critical review. TrAC Trends in Analytical Chemistry 122, 115744 (2020).
Tyszczuk-Rotko, K., Kozak, J. & Czech, B. Screen-printed voltammetric sensors—Tools for environmental water monitoring of painkillers. Sensors 22, 2437 (2022).
Dhanalakshmi, R., Priya, P. & Sivamurugan, V. Pharmaceutical pollutants in water: Origin, toxicity hazards, and treatment. Organic Pollutants: Toxicity and Solutions, 293-320 (2022).
Cheng, D. et al. A critical review on antibiotics and hormones in swine wastewater: Water pollution problems and control approaches. Journal of hazardous materials 387, 121682 (2020).
Peralta-Hernández, J. M. & Brillas, E. A critical review over the removal of paracetamol (acetaminophen) from synthetic waters and real wastewaters by direct, hybrid catalytic, and sequential ozonation processes. Chemosphere 313, 137411 (2023).
Rastogi, A., Tiwari, M. K. & Ghangrekar, M. M. A review on environmental occurrence, toxicity and microbial degradation of Non-Steroidal Anti-Inflammatory Drugs (NSAIDs). Journal of Environmental Management 300, 113694 (2021).
Zhu, F. et al. Determination of four antipyretic and analgesic drugs in water by solid-phase extraction coupled ultra-performance liquid chromatography-tandem mass spectrometry. Se pu= Chinese Journal of Chromatography 38, 1465-1471 (2020).
Guo, Q. & Zhang, L. Paracetamol Research and New Formulation Design. Academic Journal of Science and Technology 1, 118-120 (2022).
Graham, G. G. & Scott, K. F. Mechanism of action of paracetamol. American journal of therapeutics 12, 46-55 (2005).
Agarwal, N. Paracetamol-A contaminant of high concern: Existence in environment and adverse effects. Pharmaceut. Drug Regul. Affair J 4, 000128 (2021).
Gyesi, J. N. et al. Occurrence of pharmaceutical residues and antibiotic-resistant bacteria in water and sediments from major reservoirs (owabi and barekese dams) in Ghana. Journal of Chemistry 2022, 1-14 (2022).
Mackuľak, T. et al. Hospital wastewater—Source of specific micropollutants, antibiotic-resistant microorganisms, viruses, and their elimination. Antibiotics 10, 1070 (2021).
Tehrani, A. H. & Gilbride, K. A. A closer look at the antibiotic‐resistant bacterial community found in urban wastewater treatment systems. Microbiologyopen 7, e00589 (2018).
Novo, A., André, S., Viana, P., Nunes, O. C. & Manaia, C. M. Antibiotic resistance, antimicrobial residues and bacterial community composition in urban wastewater. Water research 47, 1875-1887 (2013).
Umar, M. & Aziz, H. A. Photocatalytic degradation of organic pollutants in water. Organic pollutants-monitoring, risk and treatment 8, 196-197 (2013).
Singh, S. & Gupta, V. K. Biodegradation and bioremediation of pollutants: perspectives strategies and applications. International Journal of Pharmacology and Biological Sciences 10, 53 (2016).
Abdel-Fatah, M. A. Nanofiltration systems and applications in wastewater treatment. Ain Shams Engineering Journal 9, 3077-3092 (2018).
Garcia-Segura, S., Ocon, J. D. & Chong, M. N. Electrochemical oxidation remediation of real wastewater effluents—A review. Process Safety and Environmental Protection 113, 48-67 (2018).
Trishitman, D., Cassano, A., Basile, A. & Rastogi, N. K. in Current trends and future developments on (bio-) membranes 207-228 (Elsevier, 2020).
Al-Muttair, A. K., Al Easawi, N. A. & Mustafa, S. A. Using Adsorption as Means to Treat Water Pollution. Journal of Biotechnology Research Center 16, 37-47 (2022).
Zhang, S. et al. Applications of water-stable metal-organic frameworks in the removal of water pollutants: A review. Environmental Pollution 291, 118076 (2021).
Rathi, B. S. & Kumar, P. S. Application of adsorption process for effective removal of emerging contaminants from water and wastewater. Environmental Pollution 280, 116995 (2021).
Meez, E., Rahdar, A. & Kyzas, G. Z. Sawdust for the removal of heavy metals from water: a review. Molecules 26, 4318 (2021).
Packialakshmi, S., Anuradha, B., Nagamani, K., Devi, J. S. & Sujatha, S. Treatment of industrial wastewater using coconut shell based activated carbon. Materials Today: Proceedings 81, 1167-1171 (2023).
Hasan, M. B., Al-Tameemi, I. M. & Abbas, M. N. Orange peels as a sustainable material for treating water polluted with antimony. Journal of Ecological Engineering 22, 25-35 (2021).
Takmil, F., Esmaeili, H., Mousavi, S. M. & Hashemi, S. A. Nano-magnetically modified activated carbon prepared by oak shell for treatment of wastewater containing fluoride ion. Advanced Powder Technology 31, 3236-3245 (2020).
Baby, R., Saifullah, B. & Hussein, M. Z. Palm Kernel Shell as an effective adsorbent for the treatment of heavy metal contaminated water. Scientific Reports 9, 18955 (2019).
Tejedor, J., Cóndor, V., Almeida-Naranjo, C., Guerrero, V. & Villamar, C. Performance of wood chips/peanut shells biofilters used to remove organic matter from domestic wastewater. Science of the Total Environment 738, 139589 (2020).
Zou, Y. & Yang, T. in Rice bran and rice bran oil 207-246 (Elsevier, 2019).
Majumder, D., Muttepwar, A. S. & Naikwade, D. S. A review: Domestic waste water treatment with corn cobs. International Journal of Innovations in Engineering Research and Technology, 1-3 (2019).
Thabede, P. M., Shooto, N. D. & Naidoo, E. B. Removal of methylene blue dye and lead ions from aqueous solution using activated carbon from black cumin seeds. South African Journal of chemical engineering 33, 39-50 (2020).
Gao, Y., Yue, Q., Gao, B. & Li, A. Insight into activated carbon from different kinds of chemical activating agents: A review. Science of the Total Environment 746, 141094 (2020).
Reza, M. S. et al. Preparation of activated carbon from biomass and its’ applications in water and gas purification, a review. Arab Journal of Basic and Applied Sciences 27, 208-238 (2020).
Moosavi, S. et al. Application of efficient magnetic particles and activated carbon for dye removal from wastewater. ACS omega 5, 20684-20697 (2020).
Hashemzadeh, F., Ariannezhad, M. & Derakhshandeh, S. H. Evaluation of Cephalexin and Amoxicillin removal from aqueous media using activated carbon produced from Aloe vera leaf waste. Chemical Physics Letters 800, 139656 (2022).
Sinha, R. K. et al. Protonated sulfuric acid: vibrational signatures of the naked ion in the near-and mid-IR. The Journal of Physical Chemistry Letters 1, 1721-1724 (2010).
Chen, Y., Wang, F., Duan, L., Yang, H. & Gao, J. Tetracycline adsorption onto rice husk ash, an agricultural waste: Its kinetic and thermodynamic studies. Journal of Molecular Liquids 222, 487-494 (2016).
Rizzi, V. et al. Removal of tetracycline from polluted water by chitosan-olive pomace adsorbing films. Science of The Total Environment 693, 133620 (2019).
Jang, H. M., Yoo, S., Choi, Y.-K., Park, S. & Kan, E. Adsorption isotherm, kinetic modeling and mechanism of tetracycline on Pinus taeda-derived activated biochar. Bioresource Technology 259, 24-31 (2018).
Figueroa, R. A., Leonard, A. & MacKay, A. A. Modeling tetracycline antibiotic sorption to clays. Environmental science & technology 38, 476-483 (2004).
Dai, Y., Li, J. & Shan, D. Adsorption of tetracycline in aqueous solution by biochar derived from waste Auricularia auricula dregs. Chemosphere 238, 124432 (2020).
Huang, H. et al. Thermal oxidation activation of hydrochar for tetracycline adsorption: the role of oxygen concentration and temperature. Bioresource technology 306, 123096 (2020).
Hernández-Martínez, A. et al. Adsorption of paracetamol onto carbon nanomaterials and degradation by ultrasonic and gamma radiation. Advanced Materials-Tech Connect Briefs 2, 217-219 (2016).
Thakur, A., Sharma, N. & Mann, A. Removal of ofloxacin hydrochloride and paracetamol from aqueous solutions: Binary mixtures and competitive adsorption. Materials Today: Proceedings 28, 1514-1519 (2020).
Nourmoradi, H., Moghadam, K. F., Jafari, A. & Kamarehie, B. Removal of acetaminophen and ibuprofen from aqueous solutions by activated carbon derived from Quercus Brantii (Oak) acorn as a low-cost biosorbent. Journal of environmental chemical engineering 6, 6807-6815 (2018).
Ogunmodede, J., Akanji, S. B. & Bello, O. S. Moringa oleifera seed pod‐based adsorbent for the removal of paracetamol from aqueous solution: A novel approach toward diversification. Environmental Progress & Sustainable Energy 40, e13615 (2021).
Kamaraj, R., Davidson, D. J., Sozhan, G. & Vasudevan, S. An in situ electrosynthesis of metal hydroxides and their application for adsorption of 4-chloro-2-methylphenoxyacetic acid (MCPA) from aqueous solution. Journal of Environmental Chemical Engineering 2, 2068-2077 (2014).
Mphahlele, K., Onyango, M. S. & Mhlanga, S. D. Adsorption of aspirin and paracetamol from aqueous solution using Fe/N-CNT/β-cyclodextrin nanocomopsites synthesized via a benign microwave assisted method. Journal of Environmental Chemical Engineering 3, 2619-2630 (2015).

No competing interests reported.

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Magnetic activated carbon derived from pine fruit waste: efficient adsorbent for tetracycline (TC) and paracetamol (PC) removal from aqueous solution

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Introduction

Characterization and discussion

VSM analysis

Comparison studies with other adsorbents

Recovery

Conclusion

Materials and methods

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Author Contribution

References

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Journal Publication

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Magnetic activated carbon derived from pine fruit waste: efficient adsorbent for tetracycline (TC) and paracetamol (PC) removal from aqueous solution

Status:

Journal Publication

Version 1

Abstract

Figures

Introduction

Characterization and discussion

VSM analysis

​

​

Comparison studies with other adsorbents

Recovery

​

Conclusion

Materials and methods

Declarations

Author Contribution

References

Additional Declarations

Status:

Journal Publication

Version 1