Potassium permanganate dye removal from synthetic wastewater using a novel, low-cost adsorbent, modified from the powder of Foeniculum vulgare seeds

In this study, Seeds powder of Foeniculum vulgare was used to prepare a novel adsorbent, the modification of the prepared adsorbent was done by each of ZnCl2, oxalic acid, and CuS, all samples have been characterized by different techniques and examined for Potassium permanganate (KMnO4) adsorption. Among the four modified and unmodified adsorbents, the sample modified by oxalic acid has the highest percentage removal for KMnO4 adsorption (%R = 89.36). The impact of KMnO4 concentration, adsorbent dose, contact temperature, contact time, and solution pH on the adsorption performance was also investigated. The experimental data of this adsorption was analyzed by different kinetic and isotherm models. As Constants of thermodynamic ΔG°, ΔH°, and ΔS° have been also evaluated. Surface area, pore volume, and pore size of the modified oxalic acid F. vulgare seeds powder adsorbent were determined as 0.6806 m2 g−1, 0.00215 cm3 g−1, and 522.063 Å, as pHZPC also was stated to be 7.2. The R2 values obtained from applying different isotherm and kinetic models (0.999 and 0.996) showed that the adsorption performance of KMnO4 follows the Langmuir and Pseudo 2nd order models. Furthermore, high adsorption capacities of 1111.11, 1250.00, and 1428.57 mg g−1 were achieved at three temperatures that were used in this study. Constants of thermodynamic ΔG°, ΔH°, and ΔS° values indicate chemical and spontaneous adsorption at the adsorbent surface. Therefore, the modified adsorbent can be used to remove KMnO4 dye from pollutant water samples.

www.nature.com/scientificreports/ to use low-cost materials within their areas and applied them as adsorbents for permanganate ions adsorption. For instance, sage 24 Neem 25 , Nitraria retusa 26 , and Ocimum basilicum 27 were used as low-cost sorbents to remove Permanganate anions from synthetic samples.
Foeniculum vulgare plant is well-known by fennel in many countries as shamr in Saudi Arabia, mainly used as food and tea flavored and considered as a flavored spice, its seeds were used as antitumor 28 , antimicrobial 29 , and antioxidant 30 . Experiments on animals and clinical trials recommend that chronic use of F. vulgare plant is not harmful and no toxicity marks were detected 31 .
Gold nanoparticles based on seeds extract of fennel F. vulgare plant was synthesized and its catalytic activity against rhodamine B and methylene blue days were examined 32 , V 2 O 5 -Fe 2 O 3 nanocomposites from stem powder of F. vulgare have been also produced and the catalytic performance of nanocomposites particles was assessed for reduction of 4-nitrophenol 33 .
Up to now, no adsorbent based on F. vulgare seeds was prepared in any form and applied to eliminate the hazardous dyes from water even permanganate ions, despite the excellent medical properties of this herb, in addition to its widespread over the world F. vulgare seeds are considered a low-cost material. Therefore, this research mainly aimed to prepare a new adsorbent from seeds of F. vulgare and to investigate the adsorbent performance toward eliminating KMnO 4 from polluted water. Thermodynamics, Kinetics, and isotherms parameters will also be studied. The performance of this adsorption will be also studied through conditions and impacts that could affect on KMnO 4 removal experiment, as the adsorption capacity of modified adsorbent for removal of KMnO 4 will be critically addressed.
To achieve all the desired goals of this work and get the best results, unmodified samples from F. vulgare seeds have been synthesized and the modification has been also carried out by zinc chloride, copper sulfide, and oxalic acid; both types of samples have been characterized and examined as adsorbents for KMnO 4 removal from water, to choose the best adsorbent, the adsorption performances have been compared, then all the KMnO 4 adsorption experimental factors and conditions of selected adsorbent were tested.

Materials and methods
Materials. Foeniculum vulgare seeds were obtained from a local market in Tabuk City, KSA. All chemicals that were used in this work were obtained from Sigma-Aldrich with a purity of (37%) for hydrochloric acid, ≥ 97% for sodium hydroxide ≥ 97% for zinc chloride, ≥ 99.99% for oxalic acid, ≥ 99:99% for copper sulfide, and ≥ 99.00% for sodium carbonate.
Preparation and modification of adsorbents. The F. vulgare seeds were washed with distilled water several times and then dried overnight, after that, the F. vulgare seeds powder (FVESP) was obtained by an electric grinder. A sample of 100 g was refluxed for 180 min with 1 L of oxalic acid (20% w/w), afterwards, the mixture was allowed to cool at room temperature. The sold part was separated by filtration, to get rid of any excess amount of oxalic acid; the solid was heated for 90 min with 250 mL of 2 M hydrochloric acid. Then, the filtration of the new mixture was done many times and rinsed with distilled water to have a clean solid, to get rid of any water present in the sample; the solid was left in the oven for 30 h at 130 °C. Finally, to ensure the homogeneity of the sample, the dry solid was grinded and sieved, and the resulted adsorbent of oxalic acid F. vulgare seeds powder labeled as (Ox-FVESP).
The same procedure was repeated with mixtures containing 100 g of FVESP with 1 L of 20% w/w acidic solution of zinc chloride, and 100 g FVESP with a mixture of 20% w/w acidic solution of zinc chloride and 50 g of copper sulfide. The resulted adsorbents of zinc chloride F. vulgare seeds powder labeled as (Zn-FVESP), and zinc chloride/copper sulfide F. vulgare seeds powder (Zn/Cu-FVESP).

Characterization of FVESP adsorbents.
To recognize the surface morphology of the modified and unmodified FVESP adsorbents SEM instrument was used at a 10 kV accelerating voltage. And to determine the surface adsorbents' functional groups, the FT-IR instrument (Nicolet iS5 of Thermo Scientific FT-IR, USA) was carried out. The surface area and porosity of each adsorbent were estimated using BET (NOVA-2200 Ver. 6.11) technology for 22 h and 77.35 K. In addition, 40 mL of 0.05 M Na 2 CO 3 solutions varying with 2, 4, 6, 8, and 10 initial values of pH i have been mixed in a 150 mL plastic container with 0.2 g of the idealistic adsorbent. After shaking all containers for 26 h 175 rpm and 27 °C conditions in a shaker incubator, filtration of each was done, then using a pH meter, the final pH (pH f ) of each solution was determined. Finally, to determine the pH ZPC value of this adsorbent, the values of (pH i − pH f ) have been calculated and graphed against the pH i values.
Adsorption experiments. The idealistic adsorbent identification. To determine the superlative as well as the most efficient adsorbent developed in the current study for KMnO 4 removal from synthetic aqueous samples, 20 mL of 100 mg L −1 KMnO 4 solution concentration was combined with 0.03 g of FVESP in a 30 mL amber bottle. A shaker incubator was used for 30 h to stir the sealed amber bottle at 27 °C and 180 rpm. After that, the mixture was filtered; The Jenway UV-6800 UV-Vis spectrophotometer was used at 525 nm to measure the balanced concentration of KMnO 4 in the filtrate. The same procedure was repeated with Ox-FVESP, Zn-FVESP, and Zn/Cu-FVESP adsorbents for the KMnO 4 adsorption. Equations (1) and (2) were used to calculate the KMnO 4 percentage removal percent %R and the quantities of KMnO 4 adsorbed at equilibrium Q e mg g −1 by both modified and unmodified adsorbents.

Experimental conditions impact.
Batch experiments have been conducted to observe and identify the most significant factors that affect KMnO 4 adsorption experiments by ideal adsorbent Ox-FVESP, such as concentration of KMnO 4 (10-1400 mg L −1 ), contact time (0-320 min), the dosage of Ox-FVESP adsorbent (0.005-0.035 g), the adsorption temperature (27-57 °C), and the pH (1.5-11.5). All of the Batch experiments have been done in 30 mL amber bottles by adding 20 mL of KMnO 4 solution to enough amounts from Ox-FVESP. A shaker incubator at 180 rpm was used to shake all sealed amber bottles for a required time, followed by filtration of each mixture, and the remaining concentrations of KMnO 4 were measured as mentioned previously.
To compute the adsorbed amount of KMnO 4 at equilibrium (Q e , mg g −1 ) by the Ox-FVESP adsorbent and time t (Q t , mg g −1 ) Eqs. (2) and (3)  where C o is the maximum initial concentration of KMnO 4 and K L is the constant of Langmuir, K F is the constant of Freundlich, and K T is the constant Temkin. q max (mg g −1 ) is the maximum capacity of adsorption. B1 and n are constants of the adsorption heat and the intensity of adsorption, respectively.

Contact time impact and Kinetic studies.
The experimental data obtained from the adsorption Batch experiments, adsorption of KMnO 4 by Ox-FVESP with a concentration of 50, 100, and 200 mg L −1 at several times from 0 to 320 min and 27 °C and 190 rpm have been analyzed by three of different kinetic models. Equations (8)-(10), Pseudo 1st order, Pseudo 2nd order, and Intraparticle diffusion, correspondingly. Then, the achieved results have been used to study each of the conducted time impact, rate, and mechanism of KMnO 4 adsorption by Ox-FVESP adsorbent. Q t (mg g −1 ): the amount of adsorbed KMnO 4 at time t, Q e : the amount of adsorbed KMnO 4 at equilibrium, K 1 (1 min −1 ): rate constants of Pseudo 1st order, K 2 : (g mg −1 min −1 ) rate constants of the 2nd order. K dif (mg g −1 min −1 ) 1/2 and C are rate constants of intraparticle diffusion.
Thermodynamic experiment. Constants of thermodynamic ΔG°, ΔH°, and ΔS° have been also evaluated from the outcomes of experimental Conditions impact part for adsorption of 500, 700, 1000, and 1200 mg L −1 KMnO 4 solutions according to Eqs. (11) and (12).  Figure 1 illustrates also that the modified Zn-FVESP, and Zn/Cu-FVESP adsorbents showed the same peaks with a slight shift, while in the case of Ox-FVESP sample, many peaks developed (Fig. 1), and these bands are 1190 cm −1 , 1320 cm −1 , and 1620 cm −1 , The appearance of these bands support the success of the chemical modification process that was carried out for the adsorbent and also confirms the variety of functional groups on the surface of Ox-FVESP, which will have an effective role in permanganate adsorption from the water later. The spectrum of FVESP, Zn-FVESP, Ox-FVESP, and Zn/Cu-FVESP SEM images are demonstrated in Fig. 2a-d, respectively. When comparing the SEM images of modified samples (b), (c), and (d) to the unmodified adsorbent (a), it can be seen that the surface of the FVESP adsorbent has been significantly transformed by modification procedure, as most of the modified adsorbents pleats have been distorted and their structures became scattered. Furthermore, several heterogeneous holes and pores have appeared on the modified adsorbents surfaces, which improve the adsorption performance. It is also recognized from Fig. 2c that the density of micropores of the modified adsorbent is more than the rest of the other samples.
The relationship between pHi and pHi-pHf is depicted in Fig. 3, which shows that pH ZPC (the solution pH when the surface of sorbent has a zero net charge) is 7.2. Meanwhile, the surface charge of the adsorbent will be positive and negative at solution pH levels lower and higher than 7.2, Al-Aoh 25 has previously found similar findings.
BET surface analyzer results for the modified and unmodified FVESP samples are listed in Table 1, Surface Area (m 2 g −1 ), Volume of Pore (cm 3 g −1 ), and Size of Pore (Å). The table shows that the Ox-FVESP sample achieved the highest surface area (0.6806 m 2 g −1 ) and size of the pore (522.063 Å) compared to the rest of the other samples, The highest values of the surface area and size of pore will positively affect the process of permanganate adsorption on the modified FVESP surface by oxalic acid and prove that the modification process has an important and obvious role.
The idealistic adsorbent identification. Figure 4 illustrates the percentage removal for KMnO 4 adsorption by four different samples that were synthesized and modified in this work, and it was as the following 80.52 for FVESP, 64.03 for Zn-FVESP, 89.36 for Ox-FVESP, and 49.08 for Zn/Cu-FVESP. The percentage removal

Experimental conditions impact.
Influence of pH solution. The adsorption performance is greatly influenced by the pH of the adsorbate solution, degree of ionization, and charge of adsorbent of the dye molecules also impacted by pH. As a result, the impact of this issue was addressed in this study (Fig. 5). It is clear from the figure that the qe (mg g −1 ) value was greatly affected by the pH values, as it was high when pH values were raised from 1.5 to 7.2, and this is due to the high attraction between the positive charges of the Ox-FVESP surface and

Impact of Ox-FVESP doses.
To specify the ideal mass of Ox-FVESP that will be required for the KMnO 4 adsorption the percent removal of KMnO 4 was plotted against Ox-FVESP doses (Fig. 6). The values of percent removal of KMnO 4 % R are improved by increasing the mass of Ox-FVESP from 0.005 to 0.020 g. This rise was caused by the improvement of the active sites on the Ox-FVESP surface, which is related to the adsorbent quantity 34 . Figure 6 shows also the percent R value does not change significantly when the mass of the adsorbent is increased from 0.020 to 0.035 g and it is assumed that the amount of dye adsorption was significantly affected by the concentration of unfilled dynamic reactive sites due to the bonding ability of the adsorption surface function 35,36 . In this study, 0.020 g of Ox-FVESP was chosen as the optimal dose. The adsorption of CR dye by Zn/Cu-TPLLP adsorbent 23 and KMnO 4 on the CuS surface showed a similar Patten 37 . Fig. 7. Figure 7 shows the relationship between the adsorption amount Q e (mg/g) and the concentration of KMnO 4 (10-1400 mg L −1 ) at 27, 42, and 57 °C temperatures. It can be observed from the figure that raising the temperature of the solution has a positive impact on the adsorption capacity of KMnO 4 by Ox-FVESP. And this refers to the decreasing of KMnO 4 viscosity with solution temperature increasing, also, the kinetic energy of the permanganate particles increases with rising the temperature; the same kinetic energy performance for permanganate ions was recorded by neem leaves powder adsorbent 25 . It is also noted from the same figure that the adsorption of permanganate is improved by raising the concentration of KMnO 4 from 10 to 1400 (mg L −1 ) at the same temperature. And this could be supported by the finding that raising the adsorbate concentration will develop the dynamic force 38 , which lowers the resistance of KMnO 4 particles mass movement between the Ox-FVESP surface and adsorbate solution. It is also clear that the adsorbent will be effective even at KMnO 4 concentrations higher than 1400 mg L −1 , and this is refer to the unfilled adsorption sites on the adsorbent surface.

Temperature impact and isotherm studies. The impact of initial solution concentration and temperature on the adsorption capacity of this work is demonstrated in
Moreover, The outcomes obtained from Batch experiments were analyzed according to the isotherm model of Langmuir (Ce against Ce/qe), isotherm model of Freundlich (ln Ce against ln qe), and isotherm model of Temkin (ln Ce against qe) Fig. 8a-c, the slopes and intercepts of these plots were used to achieve the isotherm parameters and presented in Table 2. Where the experimental results are well fitted by applying the Langmuir isotherm model and the R 2 values were the highest compared with Freundlich and Temkin models Table 2, which approves that the Langmuir model is the best fit for this adsorption. These findings also show that the adsorption of KMnO 4 is monolayer adsorption and that the Ox-FVESP adsorption sites are homogeneous. Same outputs for    (Table 2) were achieved, at three temperatures that were used in this study. This demonstrates that Ox-FVESP, as a low-cost and very effective adsorbent, will be of particular importance in the purification of wastewaters from the KMnO 4 .

Contact time impact and Kinetic studies.
To investigate the contact time impact on the KMnO 4 adsorption experiment, the contact time (t) has been graphed against Q t (mg g −1 ) (adsorption quantity at such time t) for the adsorption of (50, 100, and 200 mg L −1 ) KMnO 4 concentrations by the ideal dose of chemically modified FVESP adsorbent selected for this work (Fig. 9). Figure 9 shows that there are three adsorption regions, the higher adsorption was detected at region I (0-16 min) where the adsorption amount (Q t ) rapidly augmented, while the increase in region II (16-64 min) was regularly and after 64 min till the end of the experiment time, it was practically consistent (region III). Initially, the removal rate was high due to the availability of the abundant of functional groups 39   www.nature.com/scientificreports/ adsorption were obtained by a powder of sage leaves modified by zinc chloride 24 and for the adsorption of Cu(II) ions on the nanomaterials surface adsorbent 40 . It is also noted from the same figure that the equilibrium time occurred at the 45th minute of the experiment time. Furthermore, the experimental outcomes of this adsorption have been studied according to Pseudo-first order, pseudo-second order, and Intraparticle diffusion kinetics models Figs. 10a,b, and 11. The slopes and intercepts of these plots were used to calculate the kinetic parameters and summarized in Tables 3 and 4, the linear relationships observed by applying the pseudo-second order model in Fig. 10b, where the highest R 2 values occurred,  (Table 3) and computed values of Q e , which approve that the adsorption of this work followed the second-order kinetic model. And implying that the biosorption of KMnO 4 from the aqueous media is governed by a chemical kinetic mechanism involving electron exchange or sharing between the anionic part of the dye (MnO 4 − ) and the functional groups on the OX-FVESP adsorbent surface. Similar findings were stated for KMnO 4 adsorption by activated carbon 12 , nanoparticles prepared from copper sulfide 23 , and powder sage leaves modified by zinc chloride 24 . The dye adsorption process by modified activated carbon adsorbents followed also the pseudo-second order 41,42 .
Intra-particle diffusion plots for KMnO 4 adsorption by Ox-FVESP (Fig. 10) and R 2 values, Table 4 display that the relationship between contact time (t) and adsorption amount (Q t ) could not be linear at all, but two different areas are observed. Furthermore, all the plots do not cross the original and this approves that the adsorption of MnO 4 − ions is not affected by the Intra-particle diffusion step; migration of MnO 4 − ions via the Ox-FVESP pores will be very simple. This agrees with the SEM results, as it was clear that the Ox-FVESP surface has a lot of asymmetrical pores. Thermodynamic experiment. Equation (11) was applied to evaluate parameters of the thermodynamic ΔH°, and ΔS° at three different temperatures for solution Initial concentrations 500, 700, 1000, and 1200 mg L −1 . Then, the values of ΔG° were computed according to Eq. (12) based on the previously calculated values of ΔS° and ΔH° and illustrated in Table 5. The lowering in the randomness and the endothermic process of permanganate adsorption by Ox-FVESP adsorbent was confirmed by the positive values of each ΔS° and ΔH° (Table 5) 26 . Moreover, the ΔH° values are higher than 20.9 kJ mol −1 , ranging from 27.541 to 34.371 kJ mol −1 , which indicates the molecules of adsorbate were chemically adsorbed at the adsorbent surface sites, these results are in agreement with the previous kinetic outputs. Negative values of ΔG° suggest spontaneous adsorption in the range of temperature that is used in this study, similar findings were stated for KMnO 4 adsorption by modified Powder of Ocimum basilicum 26 and other adsorbents developed from very low-cost adsorbents 23,24 , the adsorption process by cationic polymeric adsorbent also achieved similar results 43 . Comparative study with other adsorbents. Table 6 summarized the adsorption capacities of KMnO 4 removal by Ox-FVESP at three temperatures and the capacities of other synthesized low-cost adsorbents. As presented in Table 6, Ox-FVESP adsorbent has a higher adsorption capacity than the conventional low-cost adsorbents that were previously employed to remove KMnO 4 from aqueous samples. As a result, the cost-effectiveness of Ox-FVESP, easy availability, and its high performance in adsorption of permanganate from polluted water give this adsorbent a strong opportunity over other adsorbents.  adsorption from the synthesized solutions. The surface area, volume, and size of the pore of the Ox-FVESP adsorbent were determined as 0.6806 m 2 g −1 , 0.00215 cm 3 g −1 , and 522.063 Å, respectively, as pH ZPC also was stated to be 7.2. The influence of KMnO 4 concentration, Ox-FVESP dose, pH of the solution, adsorption temperature, and adsorption time on the KMnO 4 adsorption was inspected, it can be noted from the experimental outcomes the adsorption performance of KMnO 4 was positively affected by the rising concentration of KMnO 4 from 10 to 1400 mg L −1 , Ox-FVESP dose from 0.005 to 0.020 g, contact temperature from 27 to 57 °C, and adsorption time from 0 to 64 min. While the increase of solution pH from 1.5 to 11.5 has a negative effect on the adsorption process. The calculated R 2 values of different isotherm and kinetic models (0.999 and 0.996) revealed the adsorption performance of KMnO 4 following the Langmuir and Pseudo 2nd order models. Constants of thermodynamic ΔG°, ΔH°, and ΔS° values indicate chemical and spontaneous adsorption at the adsorbent surface. Additionally, high adsorption capacities were accomplished at three temperatures that were used in this work 1111.11, 1250.00, and 1428.57 mg g −1 . Proposing that the Ox-FVESP adsorbent prepared from very low-cost material was important to explore the use in the water purification from dye at optimum conditions.

Data availability
The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request. And I state that the experimental research on plant seeds used in this study complied with the relevant institutional, national, and international guidelines and legislation.