Designing of fruit waste-derived activated carbon through CO2-consuming and microwave- assisted preparation to enhance and understand its adsorption performance towards metal, metalloid and polymer species

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The authors investigate textural, surface chemistry, and elemental parameters of precursors (chokeberry seeds, black currant seeds, orange peels), biochars (BCs) and activated carbons (ACs) obtained from them. Furthermore, the adsorption mechanisms of metalloids (arsenic, selenium), metals (copper, cadmium) and macromolecular compounds (bacterial exopolysaccharide, ionic polyacrylamides) were studied in one- and two-component systems. ACs prepared via direct and indirect activation as well as through conventional and microwave heating were compared. Microwave heating favoured surface development and, consequently, enhance ability to bind ions or macromolecules. Direct biomass activation led to higher microporosity compared to indirect, two-stage one, whilst CO 2 -consuming activation increased aromaticity and hydrophobicity of the solids. In the selected systems, polymers favoured metal/metalloid adsorption limiting their bioavailability. Earth and environmental sciences/Environmental sciences Earth and environmental sciences/Natural hazards Physical sciences/Chemistry Physical sciences/Engineering direct/indirect physical activation conventional/microwave heating adsorption polymers pollutants waste management Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction A significant amount of peel waste comes from fruit and vegetable processing in both industrial settings and household kitchens, which has a serious nutritional, economic, and environmental consequences. The waste stream from processing of fruits and vegetables alone accounts for approximately 25–30% of total production (Kumar et al., 2020 ). This waste typically includes pomace, peels, rinds, and seeds. Orange processing is one of the sectors that generate the most waste. Global orange production is estimated at roughly 60 million tonnes per year, with an annual yield of orange peel totaling 32 million tonnes (Michael-Igolima et al., 2023 ). These waste can be successfully used in various industrial areas, e.g. in cosmetics, pharmacy, and agriculture. In this last case, bio-waste is used not only as compost, but is also transformed into biochars (BCs) or activated carbons (ACs) and applied as soil conditioners. BCs and ACs can be practically produced from any material rich in organic carbon (Paraskeva et al., 2008 ). However, few researchers use fruit waste to produce carbonaceous materials and to develop new adsorbents of polymers, metals or metaloids suitable for environmental samples. So far, only Selvarajoo et al. ( 2022 ) produced BC from citrus peels at 500 ℃, which was characterized by higher heating value than sub-bituminous coal. Application of BCs and ACs is one of the ways to minimize the amount of toxic metals (including heavy metals (HMs)) and metalloids in the soil-water environment as well as to reduce their bioavailability. Metalloids, arsenic/As(V) and selenium/Se(IV), as well as metals, cadmium/Cd(II) and copper/Cu(II), pose a threat to natural ecosystems. Cd, similar to As, devoid of any physiological role, is frequently recognized as a toxic substance (Genchi et al., 2020 ; Rahaman et al. 2021 ). Cu and Se are micronutrient essential for organisms. However, their high concentrations are dangerous for plants, animals, and humans (Handy et al. 2021 ; Handrup and Ravn-Haren, 2020). The mobility of hazardous ions in the environment can additionally be limited by the use of polymeric compounds (Szewczuk-Karpisz et al. 2021 ). The main aim of the study was to develop new fruit waste-derived activated carbon via pyrolysis and CO 2 -consuming, microwave-assisted activation. The authors described changes in textural, surface chemistry and sorption characteristics of fruit waste (chokeberry seeds, black currant seeds, orange peels) as well as BCs and ACs prepared using it. The precursors and products used were characterized using various analytical methods, i.e., low-temperature nitrogen (N 2 ) adsorption/desorption, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), potentiometric titration, elemental analysis (CHNS), scanning electron microscopy etc. Their adsorption ability was determined towards Cu, Cd, As and Se ions as well as polymers (ionic polyacrylamide, bacterial polysaccharide), and, based on the obtained results, the most promising adsorbent was selected for further experiments. The adsorption mechanisms were investigated in detail in various systems, taking into account various pH values as well as the additional substance presence in the examined system (e.g., additional metal/metalloid or polymer). Experimental adsorption data were fitted to various theoretical models. To estimate strength of toxic metal or metalloid binding, desorption studies were also performed, also in the presence of macromolecular compounds. The study carried out is consistent with the trends of the circular economy, striving to reuse waste, utilize natural resources efficiently as well as reduce pollutant emissions. The authors describe a new strategy for fruit waste management towards the production of effective adsorbents of toxic metal/metalloid ions or polymer macromolecules as well as soil additives that retain their properties in various environments. 2. Materials and methods 2.1. Materials Biomass Three types of biomass (B): chokeberry ( Aronia melanocarpa ) seeds (AB), orange ( Citrus sinensis ) peels (OB) and black currant ( Ribes nigrum ) seeds (RB) were used in the study. They were transformed into BCs and ACs by simple thermochemical treatment. Before the experiments, Bs were dried at 110°C (AB and RB were dried without prior grinding, OB was cut into 3–5 mm pieces). Chokeberry and black currant seeds were delivered by GAMA Zbigniew Olejnicki, P.P.H.U, whereas orange peels by the Skworcu company. Ions/herbicides Cadmium(II) chloride (CdCl 2 , CAS 10108-64-2, Acros Organics) and sodium arsenate dibasic heptahydrate (Na 2 HAsO 4 ·7H 2 O, CAS 10048-95-0, Sigma Aldrich), copper(II) chloride (CuCl 2 , CAS 7447-39-4, Chempur), and sodium selenite (Na 2 O 3 Se, CAS 10102-18-8, Glentham Life Sciences) were used as a source of metal/metalloid ions. In turn, diuron (DCMU, C 9 H 10 Cl 2 N 2 O, CAS 330-54-1, Aldrich Chemistry) and glyphosate (GLY, C 3 H 8 NO 5 P, CAS 1071-83-6, Sigma Aldrich) were used as examples of herbicides. The concentration of stock solutions of Cd, Cu, As, and Se ions was 1000 mg/L, whereas that of diuron and glyphosate, 100 mg/L. In the case of diuron, a methanol (CH 3 OH, CAS 67-56-1, Chemsolute) solution was made due to its limited solubility in water. Polymers In the experiments, natural and synthetic polymers were used. There were: (1) exopolysaccharide (EPS) synthesized by soil bacteria Rhizobium leguminosarum bv. trifolii , (2) cationic polyacrylamide (CtPAM), anionic polyacrylamide (AnPAM). EPS was isolated courtesy of scientists from the Institute of Biological Sciences, Maria Curie-Skłodowska University in Lublin according to the procedure described elsewhere (Szewczuk-Karpisz et al., 2022 ). Anionic (AnPAM, AN945 ) and cationic (CtPAM, FO4350SH ) polyacrylamide were synthesized and delivered by SNF Floerger. The average molecular weight of AnPAM and CtPAM was 6.8 and 13 kDa, respectively. CtPAM contained 25% of the quaternary amine groups, while AnPAM contained 40% of carboxyl ones (Szewczuk-Karpisz et al. 2020 ). The polymer stock solutions had a concentration of 500 mg/L. The structures of applied organic compounds are presented in Table A.1. Others The pH value of the examined systems was adjusted with hydrochloric acid (HCl, CAS 7647-01-0, Chempur) and sodium hydroxide (NaOH, CAS 1310-73-2, Chempur). To determine AnPAM concentration, hyamine 1622 (0.004 mol/dm 3 , CAS 121-54-0, POCH) was used. Calcium chloride (CaCl 2 , CAS 10043-52-4, Chempur) with the concentration of 0.001 mol/dm 3 was applied as a supporting electrolyte. The glyphosate derivatization was performed with use of: borate buffer (Na 2 B 4 O 7 ·10H 2 O, CAS 1303 − 964, Chempur), 9-fluorenylmethylchloromethane (FMOC-Cl, CAS 28920-43-6, Glentham Life Sciences), acetonitrile (C 2 H 3 N, CAS 75-05-8, Chemsolute) and dichloromethane (CH 2 Cl 2 , CAS 75-09-2, POCH). 2.2. Methods 2.2.1. Biochar (BC) and activated carbon (AC) synthesis In order to obtain BCs, pyrolysis of dried Bs was performed at 400°C in a conventional laboratory single-zone resistance furnace (PRW75/LM, Czylok), equipped with a 75 mm diameter quartz tubular reactor or in a muffle microwave furnace (Phoenix, CEM Corporation). The pyrolysis was carried out in an atmosphere of inert gas – technical nitrogen (Linde Gaz Polska), with a flow of 200 mL/min. About 15 g of precursors were placed in nickel boats or quartz crucibles (in case of conventional or microwave furnace, respectively), and then subjected to two-stage thermal treatment: 1) heating with a temperature gradient of 5°C/min until reaching the final pyrolysis temperature, 2) annealing the sample at 400°C for a period of 45 min. Then, the pyrolysis products were cooling to the room temperature under the flow of inert gas. ACs were produced in two ways: 1) by activating the BCs or 2) by direct activation of Bs, in the appropriate type of furnace. About 10 g of BCs or precursors were placed in nickel boats (conventional heating) or quartz crucibles (microwave heating), and then put in the appropriate furnace preheated to a temperature of 700 or 800 °C for 45 min in the carbon dioxide (Linde Gaz Polska) atmosphere, with a flow of 250 mL/min. Then, the samples were cooled in nitrogen flow. After reaching room temperature, each material was ground in a planetary ball mill (Pulverisette 6 Classic Line, Fritsch). The obtained materials were marked as: (1) BCC – BC obtained in conventional furnace at 400°C, (2) BCM – BC obtained in microwave furnace at 400°C, (3) ACC – AC obtained in a conventional furnace at 800°C from BCC, (4) ACM – AC obtained in a microwave furnace at 800°C from BCM, (5) FC700 and (6) FC800 – AC obtained in a conventional furnace at 700 or 800°C directly from B, (7) FM700 and (8) FM800 – AC obtained in a microwave furnace at 700 or 800°C directly from B. If the material was prepared using chokeberry seeds, the ‘A’ prefix was assigned to it, if from orange peels, ‘O’ was added, and if from black currant seeds, ‘R’ was used. 2.2.2. Bs, BCs and ACs characteristics Low-temperature nitrogen (N 2 ) adsorption/desorption method was applied to determine textural parameters of Bs, BCs, and ACs (Quadrasorb SI, Quantachrome Instruments). Specific surface area (S BET ) was calculated using Brunauer-Emmet-Teller (BET) equation, whereas pore size distribution, by the Barett, Joyner and Halenda (BJH) method. Porosity parameters were estimated using the adsorption branch of the isotherm. Micropore volume (V mic ) was calculated using the t-plot method, and total pore volume (V t ), under relative pressure conditions p/p 0 = 0.99. Before the measurements, the samples were outgassed at 200°C for 20 h. Morphology of the tested solids was observed using scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) (Phenom ProX, PiK Instruments). The apparatus was also used to plot maps of the element distribution on the solid surface, before and after adsorption of metals and metalloids. Determination of surface functional groups was performed using Fourier transform infrared spectroscopy (Tensor27, Bruker Germany), from 128 scans in 4 cm − 1 intervals, in the range of 4000 − 400 cm − 1 . Each spectrum was corrected with a linear baseline using OMNIC (v.8.2, Thermo Scientific). To determine the point of zero charge (pH pzc ) and surface charge density (σ 0 ) of the investigated solids, the potentiometric titration with automatic burette (Titrino 702 SM, Methrom) and 0.1 M NaOH as the titrant was applied. The titration was performed at pH values of 3–10. Surface charge density was calculated using Janusz ( 1999 ) method. The form of metals and metalloids adsorbed on the solids was determined using X-ray photoelectron spectroscopy (XPS) (UHV surface analysis system (SPECS)). The elemental composition of the solids was also determined using a 2400 Series II CHNS/O Elemental Analyzer (Perkin Elemer) The ash content in the materials was established according to the DNS 1171:2002 standard. The amount of acidic and basic groups on the solid surface was determined by the Boehm back titration method (Boehm, 1994 ) using 0.1 M NaOH and HCl volumetric standards as the titrants and methyl orange as the indicator. The pH of water suspensions of each material was determined by adding a portion of 0.5 g of the solid to 25 mL of distilled water and stirring for 24 h to reach equilibrium. After the time passes, the pH of the suspensions was measured using CP-401 pH-meter (Elmetron) equipped with EPS-1 glass electrode. 2.2.3. Adsorption study Adsorption study was performed for metals, metalloids, herbicides, and polymers in both single and mixed systems. Their adsorbed amount (Γ, mg/g) was determined based on the difference in their concentration in the solution before and after the adsorption process, using the following formula: $$\:\varGamma\:=\frac{{C}_{ads}\bullet\:V}{m}$$ 1 where: C ads – the adsorbed amount of metal/metalloid ions, herbicide or polymers molecules (C ads = C 0 -C eq ) [mg/L], C 0 – the initial adsorbate concentration [mg/L], C eq – the equilibrium adsorbate concentration in the solution [mg/L], V – the system volume [L], m – the solid weight [g]. The adsorption efficiency was calculated as follows: $$\:E=\:\frac{{C}_{ads}}{{C}_{0}}\bullet\:100\%$$ 2 For Cu, Cd, polymers and herbicides, the solid weight of 0.02 g was used. In turn, for As and Se, 0.04 g of solid was applied. The solid samples were added to 10 mL of the solution containing selected adsorbate and supporting electrolyte (0.001 mol/L CaCl 2 ). The concentration of metals/metalloids, used to estimate adsorption isotherms, ranged from 10 to 250 mg/L. The adsorption kinetics were assessed for their concentration of 100 mg/L. The adsorbed amount of polymers and herbicides was determined for their initial concentration of 100 mg/L and 10 mg/L, respectively. In the mixed systems, the concentration of metals and metalloids was 10, 100 or 250 mg/L, whereas that of polymers was 100 mg/L and herbicides was 10 or 20 mg/L. Mixed adsorption tests were conducted in following combinations: metal + metal, metalloid + metalloid, metal + herbicide, metalloid + herbicide. After preparing the suspension, the pH value was adjusted to 6, and the adsorption was conducted for 24 h under continuous shaking conditions. The pH value was monitored throughout the adsorption process, and any fluctuations were corrected to maintain a value of 6. After the process completion, the concentration of metals and metalloids was determined using atomic absorption spectrometer (ContrAA 800, Analytik Jena) working in the graphite cuvette technique. The concentration of AnPAM after adsorption was determined using hyamine 1622 (Kang et al. 2013 ). CtPAM and EPS concentration was measured with total organic carbon (TOC) analyzer (Multi N/C 2000, HT 1300, Analytik Jena). The concentration of diuron was determined using high performance liquid chromatography (HPLC, Dionex Ultimate 3000, Thermo Scientific), whereas the one of glyphosate, using the method developed by Waiman et al. ( 2012 ) and Specord 200 PLUS spectrophotometer (Analytik Jena). 2.2.4. Adsorption data modeling For the adsorption of metal and metalloid ions, the equilibrium data were fitted to Langmuir, Freundlich, Langmuir-Freundlich, Temkin, Redlich-Peterson, and Dubinin-Radushkevitch models. The kinetics data were fitted to the pseudo I-order (PFO), pseudo II-order (PSO), intra-particle diffusion (IPD) and Elovich models. The Microsoft Excel Solver was used for data modelling. All equations used are shown in Table A.2. The adsorption of macromolecules is completely different than that of ions. Specific conformations including ‘loops’ and ‘tails’ are formed on the solid surface. One polymer chain can interact with several active sites (Szewczuk-Karpisz et al. 2020 ), and therefore the isotherms for polymers were not modeled. Their adsorbed amounts were presented only in the form of histograms. 2.2.5. Statistical analysis All measurements were made in triplicate. The standard deviation was calculated from the obtained data. 3. Results and discussion 3.1. Characterization of Bs, BCs and ACs According to IUPAC classification, the N 2 adsorption/desorption isotherms of the tested materials were close to type IV with hysteresis loops of H3 or H4 type (Fig. 1 a, A.1). The H3 hysteresis, visible mainly for Bs and BCs, is usually attributed to wedge-shaped pores formed by the loose stacking of flaky particles. The H4 type, observed for all ACs, corresponds with slit-shaped pores resulting from internal parallel pore structure (Xu et al., 2020 ). Among all precursors, S BET of black currant seeds was the largest (Table 1 ). Pyrolysis in a conventional furnace did not promote the development of the specific surface area, and therefore, the prepared BCs had even lower S BET than precursors. Microwave-assisted pyrolysis had an opposite effect and resulted in a higher S BET value for BC. In most cases, the obtained BCs did not contain micropores. The CO 2 activation improved specific surface area and made content of micropores higher (Fig. 1 b). The Boudouard reaction: C b + CO 2 ↔ 2CO (where: C b – the carbon in BC structure) was involved in the BC activation. CO 2 underwent dissociative chemisorption on the surface and formed the following oxides on it: C(O) and CO. Then, C(O) was desorbed, resulting in the formation the pore structure. CO, as a gaseous product, could also be adsorbed on active sites and retarded gasification (Sajjadi et al., 2018). The effect was even stronger when microwave heating was applied. During conventional heating only the surface layers of the material were exposed to high temperature and activating agent. Thanks to microwave heating, the both factors also affected deeper layers, which contributed to a significant improvement in textural parameters (Sajjadi et al., 2018). ACs obtained from AB and OB through direct activation at 800°C were characterized by the largest S BET and the highest V m /V t ratio among all tested solids. They also had the highest V t values and the smallest D parameters as well. Tab. 1. Physicochemical characterization of Bs, BCs, and ACs S BET [m 2 /g] V t [cm 3 /g] D [nm] S micro [m 2 /g] V micro [cm 3 /g] S m /S BET pH pHpzc ash [% wt.] H:C O:C (O+N):C acidic groups [mmol/g] basic groups [mmol/g] total groups content [mmol/g] AB 1 0.0015 6.3432 - - - 4.512 5 3.12 0.13 0.66 0.71 1.004 0.224 1.228 ABCC 1 0.0015 6.365 - - - 6.805 6.4 10.05 0.07 0.19 0.26 0.201 0.250 0.451 ABCM 6 0.0099 6.1754 - - - 7.648 7.7 13.34 0.04 0.18 0.25 0.699 0.971 1.670 AACC 88 0.0651 2.9484 26 0.012 0.29 8.461 7.8 13.32 0.01 0.06 0.10 0.100 1.674 1.774 AACM 250 0.1381 2.2042 211 0.104 0.84 10.208 8.4 18.00 0.01 0.06 0.11 0.398 2.226 2.624 AFC700 123 0.0866 2.811 49 0.023 0.4 7.564 8.1 13.25 0.02 0.31 0.36 0.145 0.609 0.754 AFM700 190 0.111 2.3388 151 0.074 0.79 10.112 8.6 15.57 0.02 0.37 0.44 0.450 1.635 2.085 AFC800 88 0.06 2.7318 38 0.018 0.43 9.392 9.0 14.54 0.01 0.33 0.38 0.329 0.471 0.800 AFM800 266 0.1518 2.2858 220 0.109 0.83 10.176 9.6 16.72 0.01 0.37 0.42 0.457 1.892 2.349 OB 8 0.0092 4.718 - - - 4.516 4.5 1.38 0.14 1.14 1.16 1.904 0.299 2.203 OBCC 3 0.0053 7.76 - - - 9.283 8.4 4.47 0.06 0.35 0.38 0.529 0.444 0.973 OBCM 10 0.0087 3.6366 - - - 7.746 8.7 6.73 0.05 0.32 0.35 0.484 1.248 1.732 OACC 73 0.0537 2.936 31 0.015 0.42 9.823 9.3 7.74 0.01 0.20 0.23 0.152 1.164 1.316 OACM 132 0.0807 2.434 88 0.043 0.66 10.448 10 10.84 0.01 0.25 0.28 0.000 2.071 2.071 OFC700 26 0.0192 2.9656 6 0.001 0.23 7.127 8.4 8.36 0.01 0.21 0.24 0.000 0.828 0.828 OFM700 236 0.1481 2.516 50 0.073 0.21 10.112 9.7 8.72 0.01 0.26 0.29 0.000 1.727 1.727 OFC800 263 0.1637 2.489 191 0.093 0.72 9.908 9.3 9.03 0.01 0.28 0.32 0.000 2.393 2.393 OFM800 266 0.1552 2.3328 202 0.1 0.76 10.251 10.1 10.82 0.01 0.25 0.29 0.000 2.243 2.243 RB 9 0.0083 3.662 - - - 4.672 5.3 3.24 0.16 0.60 0.67 0.897 0.174 1.071 RBCC 4 0.0057 5.776 - - - 7.397 7.7 8.04 0.09 0.14 0.20 0.100 0.224 0.323 RBCM 52 0.037 2.854 22 0.01 0.42 7.534 7.7 12.29 0.04 0.25 0.35 0.930 0.817 1.747 RACC 40 0.0327 3.304 8 0.002 0.2 8.227 8.9 14.97 0.02 0.07 0.13 0.100 0.499 0.599 RACM 249 0.483 2.378 208 0.109 0.83 9.295 9.3 19.84 0.01 0.09 0.16 0.477 1.965 2.442 RFC700 41 0.0352 3.428 12 0.011 0.29 7.167 6.6 14.22 0.02 0.30 0.37 0.025 0.396 0.421 RFM700 196 0.133 2.718 126 0.065 0.64 7.695 8.6 16.99 0.02 0.46 0.54 0.496 1.343 1.839 RFC800 88 0.063 2.836 50 0.025 0.56 8.570 8.4 16.58 0.01 0.33 0.39 0.099 0.671 0.770 RFM800 219 0.144 2.614 143 0.075 0.65 7.963 9.6 18.05 0.02 0.46 0.54 0.495 1.372 1.866 SEM was used to observe morphology of Bs, BCs, and ACs (Fig. 1 c, Fig A.2). BCs and ACs had a heterogeneous structure rich in cracks, crevices and channels. Such structures are typical for materials obtained by pyrolysis/activation of biomass at high temperatures (Tomczyk and Szewczuk-Karpisz, 2022 ). Comparing Bs, BCs, and ACs, the morphology became more and more complex due to the aggregation of mineral compounds (Suman et al., 2017 ). The acidic/basic groups content in the materials changed after pyrolysis and activation. In most cases, the solids obtained from OB had the largest number of functional groups (Table 1 ). Activation with carbon dioxide increased content of basic groups. In the case of ACs obtained directly from OB in both furnace types or indirectly in microwave furnace, the complete disappearance of acidic groups in favor of basic ones was visible. BCs produced at high temperatures (600–700°C) exhibited highly hydrophobic nature and were characterized by lower contents of H- and O-containing functional groups. This phenomenon was associated with dehydration and deoxygenation of biomass. During heating, chemical bonds in the precursor structure are being broken and rearranged, which resulted in formation of new functional moieties (Tomczyk et al., 2020 ). For example, carbonyl groups crack to CO around 400°C, whereas carboxyl groups start to decompose into CO 2 and H 2 O at 200°C due to lower thermal stability (Cui et al. 2017 ). In most cases, the water extracts of the products of OB pyrolysis/activation had the highest pH values among all tested materials. The results of potentiometric titration indicated that surface charge density and the pH pzc parameters of Bs, BCs, and ACs differed significantly (Table 1 , Fig. A.3a-c). The pH pzc value of orange peels was 4.5, which meant that at pH 6, at which the adsorption study was performed, their surface was negatively charged. BCs and ACs were positively charged during sorption experiments since their pH pzc values were higher than 8. The study on elemental composition indicated that the H:C, O:C, and (N + O):C ratios decreased after heat treatment (Table 1 ). Biomass pyrolysis and activation increased aromaticity and hydrophobicity of materials as it was indicated by lower values of the H:C and (O + N):C ratios, respectively. The decrease in the O:C ratio was equivalent to lower content of polar functional groups (Qiu et al. 2014 ). The H:C parameter was also employed to assess the level of BCs carbonization, which is closely associated with the BCs long-term stability within the environment. According European BC Certificate, the O:C ratio should be less than 0.4, and H:C, less than 0.7, when BCs are appropriate for environmental applications (Tomczyk et al. 2023 ). This criterions were fulfilled for almost all investigated carbon-rich materials. The only exceptions were two ACs prepared from black currant seeds (RFM700 and RFM800) that had the O:C ratio equal to 0.46. Spokas ( 2010 ) suggested that lower O:C molar ratios were reflected in a longer BC half-life (t 1/2 ) (in laboratory conditions). The researcher identified 3 approximate ranges for the BC t 1/2 parameter, categorized by the O:C ratio, i.e., t 1/2 > 1000 years for O:C < 0.2, 100 years < t 1/2 < 1000 years for O:C 0.2–0.6, and t 1/2 0.6. According to it, the produced BCs and ACs can be classified as those of high stability. Based on the FTIR spectra (Fig. 2 ) it was stated that physical activation of OB, regardless of the heating method, resulted in relatively minor changes in its surface chemistry. The FTIR spectra of Bs, BCs, and ACs were similar, and only intensity of specific bands was the difference between them. The FTIR spectrum of OB was composed of the following bands at: 3900 − 3500 cm − 1 (corresponding with the vibrations of free -OH bonds in alcohols, phenols, or other compounds containing hydroxyl groups that are not dissociated (Dai et al., 2023 )), 2278 cm − 1 (attributed to C ≡ N stretching vibration), 1700 − 1500 cm − 1 (stretching vibration of C = O bond in non-ionic carboxyl groups (–COOH, –COOCH 3 ), carboxylic acids, or their esters), 1600 − 1455 cm − 1 (asymmetric and symmetric stretching vibrations of ionic carboxylic groups (–COO − )), 1042 cm − 1 (the C–O stretching vibrations associated with sugars or esters (Feng et al., 2011 )). These bands were also visible for AB and RB. The FTIR spectrum of AB (Fig. A.3a) and RB (Fig. A.3b) contained bands at: 3277 cm − 1 (corresponding with –OH stretching vibrations), 2922 − 2853 cm − 1 (the C–H stretching vibrations), 1634 − 1611 cm − 1 (the C = O stretching vibration). In the case of BCs/ACs, the band at 1042 cm − 1 could be attributed to the C–O and C–O–C stretching vibrations associated with phenol, ester, and alcohol groups from cellulose degradation. The XPS results (Fig. 2 c, Table 2 ) confirmed the presence of C = C, C-H, C-O, C-N, COO − groups in OB and OB-derived BCs and ACs. It was also shown that the materials obtained in microwave furnace contained higher amount of N compared to those obtained in conventional one. Such BCs and ACs were characterized by higher content of O, which formed mainly C = O, C-O-C, C = N-O groups. The materials obtained using conventional heating were rich in C-OH moieties. Tab. 2. Content of individual forms of C, N, O, Ca, and K in OB and BCs/ACs prepared from them Sample OB OBCC OBCM OFCC800 OFCM800 C total [at. %] 77.96 86.41 81.70 84.41 76.96 C=C / C-H 43.30 68.24 57.83 67.10 52.73 C-O / C-N 20.27 11.49 17.34 22.43 15.69 C=O 11.37 4.05 3.61 5.83 4.72 COO - 3.02 2.63 2.91 4.64 3.82 N total [at. %] 1.41 0.50 2.39 1.44 2.13 N-5 (pyrrolic / pyridonic) 1.41 0.50 2.39 1.44 2.13 O total [at. %] 20.63 13.09 15.90 12.72 17.9 C=O 5.98 4.14 11.75 1.79 12.26 C-OH - 8.95 - 10.93 - C-O-C / C=N-O 14.65 - 4.15 - 5.64 COO - - - - - - Ca total [at. %] - - - 1.43 1.86 Ca 2p 3/2 - - - 0.95 1.24 Ca 2p 1/2 - - - 0.47 0.62 K total [at. %] - - - 0.01 1.14 K 2p 3/2 - - - 0.01 0.76 K 2p 1/2 - - - - 0.38 3.2. Selection of optimal precursor for production of carbon-rich materials The best material for further research was selected based on the results of adsorption tests (Fig. A.5). The highest adsorption capacities towards selected metal/metalloid ions were noted for OB- and RB-derived materials. In the case of GLY, RS-derived materials had better sorption properties than OB-derived ones, but BCs from this biomass proved unsuitable for environmental applications (their O:C ratio was too high). As a result, for further experiments aiming at the determination of the kinetics, isotherms, and mechanism of metal/metalloid adsorption, only the solids obtained from OB, i.e., OBCC, OBCM, OFC800, OFM800, and OB were selected. More detailed studies, such as those performed in the polymer presence, were carried out only on the most promising adsorbent – OFM800. For initial metal/metalloid concentration equal to 100 mg/L, its adsorption capacity was 3.7, 2.6, 28.7, and 23.4 mg/g for As, Se, Cu, and Cd, respectively. For initial herbicide concentration equal to 10 mg/L, its adsorption capacity towards DCMU was 36.57, while towards GLY, 1.26 mg/g. The production of exactly this material is the most economically justified. Orange peels are the biggest problem among all the biomasses studied due to the huge amounts of them generated every year. 3.3. Metal/metalloid adsorption mechanisms on the OB-derived materials Metal/metalloid adsorption kinetics and isotherms were determined at pH 6. Then, As(V) ions occurred as H 2 AsO 4 − (85%) and HAsO 4 2− (15%) (Lupa et al., 2023 ), Se(IV) ions, as HSeO 3 − (100%) (Lichtfouse et al., 2022 ), Cd(II) ions, as Cd 2+ (100%) (Oyetade et al., 2018 ), and Cu(II) ions, as Cu 2+ (almost 100%) (Quiroz, 2021 ). 3.3.1. Contact time effect The experimental data of Cd, Cu, As and Se adsorption kinetics with fitting to the Elovich model are presented in Fig. 3 , whereas the calculated parameters of PFO, PSO, IPD and Elovich models are presented in Table 2 . Metal/metalloid adsorption was a two-stage process, especially for ACs. This suggested strong interactions between active sites of BCs/ACs and the examined metal ions. During the first stage, there was a rapid increase in the adsorbed amount of all ions until thermodynamic equilibrium was achieved (i.e., plateau, the second stage). This state was reached after 60–120 min in the case of Cu and As adsorption on all carbonaceous materials as well as for the Se adsorption on ACs. For the Cd adsorption on BCs, the equilibrium was reached later, after 120–240 min. The adsorbed amount of all ions remained practically unchanged after 24 h, which is why exactly this time was selected for equilibrium tests. Among all theoretical kinetics models, Elovich equation best described experimental data. The correlation coefficients were high (R 2 ≥ 0.994) for the Cd, Cu, As, and Se adsorption on all studied materials (Table 3 ). The calculated theoretical qe values derived from the Elovich model were close to the observed experimental adsorption capacity. Experimental qe for the As adsorption on OFM800 was 4.01 mg/g, whereas theoretical one was 4.06 mg/g. For Se, these values were 2.59 and 2.84 mg/g, for Cd, 28.69 and 31.50 mg/g, while for Cu, 23.46 and 25.92 mg/g, respectively. The Elovich model is suitable for heterogenous adsorbents and allows to predict the mass and surface diffusion as well as activation and deactivation energy of the system (Wu et al., 2009 ; Ouyang et al., 2020). The high fitting obtained for the tested suspensions indicated that chemisorption occurs in them, wherein valence forces come into play via the sharing or exchange of electrons between the adsorbent and metal ions as well as covalent forces and ion exchange (Kończyk et al. 2022 ). Table 3 Desorption degree of metals/metalloids with and without polymers as well as complexation degree of metals/metalloids by polymers Desorption degree [%] As Se Cu Cd cycle number I II III I II III I II III I II III H 2 O 4.36 0.00 0.00 4.61 0.28 0.00 23.20 21.64 21.12 9.94 2.97 3.08 10 mg/L EPS 7.97 0.86 0.43 4.15 0.22 0.00 8.45 7.48 6.44 5.47 1.33 2.22 100 mg/L EPS 11.12 0.76 0.00 3.56 0.18 0.01 12.18 5.19 0.95 4.34 1.74 0.07 10 mg/L Ct PAM 9.28 1.01 0.00 5.11 0.26 0.01 13.92 17.14 17.51 7.74 5.93 5.22 100 mg/L Ct PAM 11.47 0.75 0.40 3.67 0.27 0.00 44.61 62.20 86.17 7.95 6.64 6.34 10 mg/L An PAM 11.10 1.23 0.05 1.19 0.27 0.04 5.96 4.43 1.16 6.37 1.46 0.16 100 mg/L An PAM 10.15 1.18 0.57 0.72 0.33 0.01 12.71 0.06 0.41 4.23 1.25 0.34 Complexation degree [%] As Se Cu Cd initial concentration of metal/metalloid 50 100 250 50 100 250 50 100 250 50 100 250 10 mg/L EPS 0.00 0.00 3.83 0.00 0.00 4.84 5.71 8.29 13.14 24.60 25.30 24.40 100 mg/L EPS 0.00 0.00 5.30 0.00 0.00 3.32 2.29 0.29 9.37 26.00 26.00 24.40 10 mg/L Ct PAM 0.00 0.00 3.42 0.00 7.28 3.78 0.00 1.43 11.71 22.80 22.80 22.40 100 mg/L Ct PAM 0.00 10.96 9.31 0.00 7.58 3.50 0.00 0.00 1.60 20.00 24.40 23.60 10 mg/L An PAM 0.00 5.59 2.78 0.00 4.88 2.48 12.00 12.57 12.23 30.00 26.00 24.80 100 mg/L An PAM 0.00 5.36 4.02 0.00 4.22 0.00 32.29 15.57 14.23 40.80 37.40 29.20 Another model with very high correlation coefficient (R 2 ≥ 0.997) was the IPD model. This model had a bit worse compliance of the experimental and theoretical values of sorption capacity than the Elovich one. The C parameter in IPD model gives the information about thickness of the boundary layer. The higher it is, the greater the thickness of the boundary layer is observed. In addition, if the C parameter is greater than 0, it indicates that intraparticle diffusion (ion diffusion in the material pores, seen as a plateau) is not the only process controlling the adsorption rate. There are also external diffusion (ion diffusion towards the external surface, seen as sudden increase at the beginning of the process) (Kończyk et al. 2022 ). Among all tested systems, the C parameter had the greatest impact on the Cu adsorption on each material, i.e., the C value was in range of 4.157–11.733. In case of Cd and As adsorption on OB, OBCC, and OBCM, the C parameter was in range of 0-0.166. In turn, for Se, it was in range of 0.565–1.094. 3.3.2. Effect of initial metal/metalloid concentration For isotherm modelling, three-parameter models (Langmuir-Freundlich (L-F), Redlich-Peterson (R-P), Dubinin-Radushkevich (D-R)), and two-parameter ones (Langmuir, Freundlich, Temkin) were applied. Figure 3 shows experimental isotherms and their fitting to L-F model, whereas Table A.3 presents all calculated isotherm parameters. The Langmuir model is valid for monolayer and uniform adsorption, when there are no interactions between the neighboring molecules/ions. On the other hand, the Freundlich model assumes that adsorption is multilayer and active sites are heterogeneous (Belhachemi and Addoun, 2011 ). The D-R model describes adsorption in porous structures, which is based on both physical and chemical forces (Kończyk et al. 2022 ). In the case of performed metal/metalloid adsorption, none of these models fit the experimental data well. L-F and R-P are a combination of the Langmuir and Freundlich models. L-F gives information about energy of adsorption (the K LF constant; it increases when adsorbate affinity to the solid is higher), the number of active sides on the adsorbent (the A m parameter) and the solid heterogenity (the m parameter) (Belhachemi and Addoun, 2011 ; Tomczyk et al., 2023 ). For the L-F model, the R 2 coefficient was higher than 0.997 for all tested systems, and thus it can be used to describe experimental data. The highest affinity to the adsorbent was noted for Cu adsorption on OFM800 (K LF = 0.318 L mg − 1 ). Lesser affinity was noted for Cu binding on OBCM and OFC800 (0.183 and 0.199 L mg − 1 , respectively). For other systems, this parameter was lower than 0.035 L mg − 1 , which was equivalent to very low ion affinity to the adsorbent surface. For Se, there was almost none affinity for the studied solids. However, it must be emphasized that the affinity of all ions increased, when the microwave muffle furnace was used in the material production. For As, the K LF parameter was 0.009 L mg − 1 for OFC800, while for OFM800, 0.025 L mg − 1 . In most cases, this was associated with a greater number of adsorbent active sites. R-P is used to the systems, where adsorption process is more complicated and involves homogeneous and heterogeneous adsorption types. The β parameter adopts values in the range from 0 to 1. When β equals 1, the aforementioned equation simplifies to the Langmuir isotherm. In turn, when it is close to 0, the Freundlich model describes the adsorption process (Belhachemi and Addoun, 2011 ; Tomczyk et al., 2023 ). For all examined systems, the R-P model also fitted the experimental data very well (R 2 ≥ 0.991). For As adsorption on OFC800 and OFM800, Se adsorption on all tested materials, Cd adsorption on OB, OFC800, and OFM800, and Cu adsorption on OBCC and OBCM, the β parameter was close to 1 and ranged of 0.619-1.000. This allowed to state that the monolayer adsorption occurred in these systems. In the remaining cases, both mono- and multilayer adsorption took place. The Temkin model assumes that the adsorption heat (the b T parameter) decreases linearly as the coverage of the adsorbent surface increases. Additionally, the adsorption distribution is characterized by uniform dispersion of binding energy (the K T parameter) (Piccin et al., 2011 ). When b T constant is less than 1.0 kcal/mol, the adsorption is physical. When b T is in the range of 1–20 kcal/mol, there is ion exchange, whereas when it exceeds 20 kcal/mol, the process is classified as chemisorption (Kończyk et al. 2022 ). The Temkin model described experimental isotherms with the R 2 coefficient equal or higher than 0.993. For As adsorption on B and BCC as well as Se adsorption on OFC800 and OFM800 samples, the b T constants of 1.247, 1.240, 1.602, and 1.042 kcal/mol, were obtained, respectively, which confirmed the ion exchange mechanism. In the remaining cases, physical adsorption occurred. The adsorbed amounts of Cd and Cu ions differed significantly, which was dictated by their various radii and electronegativity. Van der Waals atomic radius of Cu is 140 pm, while that of Cd 158 pm (National Center for Biotechnology Information). Due to the smaller size of Cu ions (compared to Cd ones), they can penetrate pores easier and in larger quantities. It seems that negatively charged As and Se ions should be adsorbed in larger quantities than Cd and Cu, due to the positive charge of the adsorbents surface at the selected pH value. However, the metalloid adsorption was significantly lower. This was probably associated with the sizes of As and Se ions, which are much larger than those of Cd and Cu ions. As and Se occur in the solution as oxyanions, and the van der Waals atomic radius of these metalloids are also larger (185 and 190 pm, respectively). In general, the amounts adsorbed were higher for the materials obtained in a microwave furnace compared to analogous samples prepared in a conventional one. There was also a clear difference between adsorption on BCs and ACs, which was caused by more developed specific surface area, better porosity and higher content of functional groups of ACs compared to BCs. The only exception was Se adsorption, during which the best adsorption properties were observed for OBCC. 3.3.3. Effect of solution pH value The solution pH value affects adsorbent surface charge, as well as alters adsorbate ionization and species. During the study, for As concentration 100 mg/L, the highest removal efficiency was observed at pH 5 (Γ = 3.94 mg/g) (Fig. A.6). For pH 6 and 7, a slight decrease in adsorption capacity was observed (it was equal to 3.69 and 3.01 mg/g, respectively). Similar effect was visible for Se, that is, its adsorbed amount was slightly reduced at higher pH values (2.78, 2.59, and 2.43 mg/g for pH 5, 6, and 7, respectively). Surface charge density of OFM800 was less positive at higher pH values and thus electrostatic attraction between oxyanions and the solid particles were weakened. On the contrary, for Cd and Cu, the adsorption capacity of OFM800 adsorbent increased at higher pH values. When the pH value increased, the solid surface became protonated and had a less positive charge. As a result, the electrostatic repulsion between cations and positively charged solid was reduced, which made their contact easier. The amounts of Cu adsorbed on the selected adsorbents were 19.94, 23.40, and 29.22 mg/g, whereas those of Cd were 22.22, 28.66, and 33.76 mg/g for pH 5, 6, and 7, respectively. 3.3.4. XPS, EDS and FTIR after adsorption studies with metals and metaloids The EDS analyses (Fig. 4 a, A.7) confirmed that Cu, Cd, As, and Se were adsorbed on the OFM800 surface. Additional peaks corresponding to metal/metalloid ions were visible in the spectra. The changes in the FTIR spectra (Fig. 2 b) after ion adsorption were not significant. The XPS results (Fig. 4 b) indicated that As was adsorbed as arsenic oxide compounds (45 eV) (Tian et al., 2017 ), whereas Se, as NaSeO 3 (59 eV) and HSeO 3 (60–61 eV) (Naveau et al., 2007 ). The peaks registered for Cd corresponded to its + 2 oxidation state (413–416 eV, 406–409 eV), namely Cd(OH) + or Cd(OH) 2 (Wang et al., 2018 ). In turn, Cu ions formed Cu 2 O (932 eV) and CuCl 2 (935 eV) on the solid surface (Biesinger, 2017 ). 3.4. Polymer adsorption mechanisms on the OB-derived materials The measured amounts of polymers adsorbed on OBCC, OBCM, OFC800 and OFM800 at different pH values are presented in Fig. 5ab. The EPS and AnPAM adsorption decreased slightly with increasing pH value. For the initial EPS concentration of 100 mg/L, its adsorbed amount was 20.75 mg/g at pH 5, 16.14 mg/g at pH 6 and 4.15 mg/g at pH 7. Carboxylic groups present in the EPS chains underwent gradual dissociation as the pH of the solution increased. According to Szewczuk-Karpisz et al. ( 2022 ), the pK a parameter of EPS was 5.1 (50% of carboxylic groups were dissociated then). At pH 7, 98.7% of the groups were dissociated, which was equivalent to more expanded conformation of the macromolecules. Such polymer chains occupied a much larger area of the solid during adsorption, and consequently, the amount of adsorbed EPS was reduced at higher pH value. The EPS and AnPAM adsorption was favoured by electrostatic attraction occurring between the negatively charged macromolecules and the positively charged surface of solid. For CtPAM, the tendency was completely different, i.e., its adsorption increased with increasing pH. This was connected with different conformation of polymer chains. AnPAM formed adsorption layer of lower thickness with ‘loops’ and ‘tails’ of short length. In turn, due to the electrostatic repulsion between positively charged CtPAM macromolecules and adsorbent particles, this polymer formed long ‘loops’ and ‘tails’, which limited its contact with the surface. As a result, more chains could fit on a unit area of the solid and the amount of adsorbed polymer was greater. 3.4.1. Polymer impact on solid surface charge The modification of OFM800 clearly influenced its surface charge density as well as the pH pzc value (Fig. A.3d). This effect was strongly dependent on the type of polymer and the content of ionizable groups in the macromolecules. Typically, dissociated carboxylic groups (-COO − ) of the polymer fragments located near the surface contribute to the reduction in absolute values of negative σ 0 parameter. Conversely, the -COO − moieties found in 'loops' and 'tails' of the adsorbed polymer chains lead to increase in the absolute values of negative σ 0 parameter (Szewczuk-Karpisz et al. 2020 ). In the analyzed systems, the latter phenomenon prevailed. In the presence of AnPAM a significant increase in the absolute values of negative surface charge was observed, and pH pzc decreased from 10.1 to 8.3. The positive groups still prevailed on the OFM800 surface – the σ 0 parameter equaled 20 µC/cm 2 at pH 5, 16.3 µC/cm 2 , pH 6, and 6.3 µC/cm 2 at pH 7. The EPS adsorption contributed to a slight reduction in the pH pzc value to 9.8 as well as in the absolute values of negative surface charge. This was also induced by the dissociated -COO − groups present in the ‘loops’ and ‘tails’ of the adsorbed polymer chains. The quaternary amine groups of CtPAM also influenced the OFM800 surface charge. Generally, when positive moieties are situated in segments of the adsorbed polymer (very close to the solid surface), they contribute to an increase in the absolute values of negative surface charge. Conversely, their placement in polymer fragments located in the by-surface layer, resulted in a reduction in the absolute values of negative surface charge (Szewczuk-Karpisz et al. 2020 ). In the case of the examined systems, the influence of CtPAM was not clear. Probably, the the number of positively charged groups in the adsorbed segments and those located within the 'loops' and 'tails' was very similar. CtPAM caused only a slight reduction in pH pzc to 9.8. 3.5. Adsorption in the mixed systems 3.5.1. Mixed systems of metal/metalloid ions and herbicide In the mixed systems containing two metal/metalloid ions or one metal/metalloid ion and one herbicide simultaneously, adsorption was different than in the single ones (Fig. 6 ). As, Se, Cd, and Cu ions were adsorbed in larger amounts after addition of DCMU and GLY. Similarly, when As and Se were present together in the system, their adsorption was enhanced. In both cases, the formation of complexes between metal and metalloid ions or two metalloid ions based on hydrogen bonds took place (Fijałkowska et al., 2019 ). The simultaneous presence of metal ions, Cd and Cu, reduced their adsorption on the solid surface, which was dictated by the competition between both cations for active sites. 3.5.2. Mixed systems of metal/metalloid ions and macromolecular compounds Modification of solids with polymers also influenced the metal/metalloid adsorption (Fig. 5 c-f), which was mainly associated with the complexation of macromolecular compounds and ions (Table 3 ). CtPAM made Se and As adsorption higher by 2.2- and 2.6-times, respectively, when initial metalloid concentration was 100 mg/L. This polymer contributed to higher absolute values of positive surface charge at pH 6, which facilitated contact between oxyanions and solid particles. In the case of Cu, CtPAM significantly reduced its adsorption (by almost 80%), which was the result of strong electrostatic repulsion between positively charged quaternary amine groups and Cu cations. Surprisingly, this phenomenon did not occur for Cd. Probably, both metals, due to differences in electronegativity (Cu = 1.90 and Cd = 1.70 in Pauling’s scale), formed different types of complexes with CtPAM, i.e., intramolecular or intermolecular one (Szewczuk-Karpisz et al., 2022 ). CtPAM is composed of fragments with quaternary amine moieties (-N(CH 3 ) 3 + ) being a source of positive charge as well as neutral amide groups. The latter have free electron pairs located on the N atom, that may participate in the formation of a covalent bond between CtPAM and cations (Zhou et al., 2011 ). Anionic polymers, EPS and AnPAM, increased adsorption of most metals and metalloids. Se adsorption in the presence of AnPAM was only one exception. In the case of metals, the adsorption was greater even by 1.6 times in the EPS presence. This was mainly associated with the introduction of additional negative groups (-COO − ) together with anionic macromolecules, with which cations could interact electrostatically. On the other hand, As oxyanions were involved in hydrogen bond formation with the polymer functional groups. The formed ion-polymer complexes were adsorbed on the solid surface and, as a result, Cd/Cu/As adsorbed amount increased. 3.6. Desorption of metal/metalloids from B and produced materials Desorption study allowed to determine the binding strength of selected metal/metalloids with and without polymers (Table 3 ). Desorption was performed in three cycles, and, as expected, it was the highest in the first cycle. Due to the weakness of the interaction between Cd/Cu cations and positively charged OFM800, their desorption was the greatest among all ions. In the first cycle, it was in the range 5.96–44.61% for Cu and 4.23–9.44% for Cd. For As/Se, that were electrostatically attracted to the surface, the desorption degree was much lower, 0.72–4.36%. The immobilization of metals/metalloids was enhanced by polymers. A clear reduction in desorption was observed for Se with AnPAM as well as Cu/Cd with EPS/AnPAM. Then, ion-polymer complexation as well as polymer adsorption on the solid surface limited the leaching of metals and metalloids and thus reduced their bioavailability. Conclusions The authors developed fruit waste-derived activated carbons produced using CO 2 -consuming microwave-assisted method of satisfied adsorption capacity towards various substances. For initial metal concentration of 100 mg/L, it adsorbed 57.32% of Cu and 46.8% Cd. Surprisingly, these values increased in the mixed systems with diuron (10 mg/L) to the values of 64.42% and 61.5%, respectively, which meant that the investigated adsorbed remained high ability to bind toxic compounds in the solutions with both organic and inorganic compounds. The selected orange peels AC had enhanced adsorption capacity also in the systems with metals/metalloids and polymers. The CtPAM presence increased Se/As adsorption, whereas the one with EPS or AnPAM, enhanced Cd/Cu/As binding. The Cu removal rate was equal to even 96.52% in the EPS presence (100 mg/L). Anionic polymers made metal/metalloid immobilization stronger limiting their bioavailability. Thus, the produced material is of high environmental importance. 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Rahaman, Md.S., Rahman, Md.M., Mise, N., Sikder, Md.T., Ichihara, G., Uddin, Md.K., Kurasaki, M., Ichihara, S., 2021. Environmental arsenic exposure and its contribution to human diseases, toxicity mechanism and management. Environ. Pollut. 289, 117940. Sajjadi, B., Chen, W.-Y., Egiebor, N.O., 2019. A comprehensive review on physical activation of biochar for energy and environmental applications. Rev. Chem. Eng. 35, 735–776. Selvarajoo, A., Wong, Y.L., Khoo, K.S., Chen, W.-H., Show, P.L., 2022. Biochar production via pyrolysis of citrus peel fruit waste as a potential usage as solid biofuel. Chemosphere 294, 133671. Spokas, K.A., 2010. Review of the stability of biochar in soils: predictability of O:C molar ratios. Carbon Management 1, 289–303. Suman, S., Panwar, D.S., Gautam, S., 2017. Surface morphology properties of biochars obtained from different biomass waste. Energ. Source. Part A 39, 1007–1012. Szewczuk-Karpisz, K., Bajda, T., Tomczyk, A., Kuśmierz, M., Komaniecka, I., 2022. Immobilization mechanism of Cd 2+ /HCrO 4 - /CrO 4 2- ions and carboxin on montmorillonite modified with Rhizobium leguminosarum bv. trifolii exopolysaccharide. J. Hazard. Mater. 428, 128228. Szewczuk-Karpisz, K., Nowicki, P., Sokołowska, Z., Pietrzak, R., 2020. Hay-based activated biochars obtained using two different heating methods as effective low-cost sorbents: Solid surface characteristics, adsorptive properties and aggregation in the mixed Cu(II)/PAM system. Chemosphere 250, 126312. Szewczuk-Karpisz, K., Tomczyk, A., Komaniecka, I., Choma, A., Adamczuk, A., Sofińska-Chmiel, W., 2021. Impact of Sinorhizobium meliloti exopolysaccharide on adsorption and aggregation in the copper(ii) ions/supporting electrolyte/kaolinite system. Materials 14, 1950. Tian, Z., Feng, Y., Guan, Y., Shao, B., Zhang, Y., Wu, D., 2017. Opposite effects of dissolved oxygen on the removal of As(III) and As(V) by carbonate structural Fe(II). Sci. Rep. 7, 17015. Tomczyk, A., Kubaczyński, A., Szewczuk-Karpisz, K., 2023. Assessment of agricultural waste biochars for remediation of degraded water-soil environment: Dissolved organic carbon release and immobilization of impurities in one- or two-adsorbate systems. Waste Manag. 155, 87–98. Tomczyk, A., Sokołowska, Z., Boguta, P., 2020. Biochar physicochemical properties: pyrolysis temperature and feedstock kind effects. Rev. Environ. Sci. Bio. 19, 191–215. Tomczyk, A., Szewczuk-Karpisz, K., 2022. Effect of Biochar Modification by Vitamin C, Hydrogen Peroxide or Silver Nanoparticles on Its Physicochemistry and Tetracycline Removal. Materials 15, 5379. Waiman, C.V., Avena, M.J., Garrido, M., Fernández Band, B., Zanini, G.P., 2012. A simple and rapid spectrophotometric method to quantify the herbicide glyphosate in aqueous media. Application to adsorption isotherms on soils and goethite. Geoderma 170, 154–158. Wang, W., He, R., Yang, T., Hu, Y., Zhang, N., Yang, C., 2018. Three-dimensional mesoporous calcium carbonate-silica frameworks thermally activated from porous fossil bryophyte: Adsorption studies for heavy metal uptake. RSC Adv. 8(45), 25754-25766. Wu, F.-C., Tseng, R.-L., Juang, R.-S., 2009. Characteristics of Elovich equation used for the analysis of adsorption kinetics in dye-chitosan systems. J. Chem. Eng. 150, 366–373. Xu, L., Zhang, J., Ding, J., Liu, T., Shi, G., Li, X., Dang, W., Cheng, Y., Guo, R., 2020. Pore Structure and Fractal Characteristics of Different Shale Lithofacies in the Dalong Formation in the Western Area of the Lower Yangtze Platform. Minerals 10, 72. Zhou, S., Xue, A., Zhao, Y., Wang, O., Chen, Y., Li, M., Xing, W., 2011. Competitive adsorption of Hg 2+ , Pb 2+ and Co 2+ ions on polyacrylamide/attapulgite. Desalination 270, 269–274. Additional Declarations No competing interests reported. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5037429","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":367655321,"identity":"07573d7d-b4ce-4f55-8d70-423268e27ca9","order_by":0,"name":"Sylwia Kukowska","email":"","orcid":"","institution":"Institute of Agrophysics, Polish Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Sylwia","middleName":"","lastName":"Kukowska","suffix":""},{"id":367655322,"identity":"7921fc16-0347-46d6-b7fd-27aca017a945","order_by":1,"name":"Piotr Nowicki","email":"","orcid":"","institution":"Adam Mickiewicz University in Poznań","correspondingAuthor":false,"prefix":"","firstName":"Piotr","middleName":"","lastName":"Nowicki","suffix":""},{"id":367655323,"identity":"40f40aca-9398-45a1-b1c8-94f16492b285","order_by":2,"name":"Katarzyna Szewczuk-Karpisz","email":"data:image/png;base64,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","orcid":"","institution":"Institute of Agrophysics, Polish Academy of Sciences","correspondingAuthor":true,"prefix":"","firstName":"Katarzyna","middleName":"","lastName":"Szewczuk-Karpisz","suffix":""}],"badges":[],"createdAt":"2024-09-05 10:27:20","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5037429/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5037429/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-85409-0","type":"published","date":"2025-01-07T15:58:03+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":69410581,"identity":"8def66b9-45b7-40b9-afe9-3e80b1320955","added_by":"auto","created_at":"2024-11-20 05:57:41","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":757220,"visible":true,"origin":"","legend":"\u003cp\u003eN\u003csub\u003e2\u003c/sub\u003e adsorption/desorption isotherms (a) pore size distribution (b) of orange peels as well as BCs and ACs produced from them, as well as SEM images (c) at 3000x magnification (OB, OBCM, and OFM800, respectively)\u003c/p\u003e","description":"","filename":"Manuscript1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/384d11aeb83293a7fd369ccc.jpg"},{"id":69410583,"identity":"050caf86-50c3-4a84-a1fd-d50b1a52b55f","added_by":"auto","created_at":"2024-11-20 05:57:41","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":704240,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of orange peels as well as BCs and ACs produced from them (a); FTIR spectra of OFM800 after adsorption of metals and metalloids (b); XPS spectra (survey, C1s, N1s, O1s) for OFM800 (c)\u003c/p\u003e","description":"","filename":"Manuscript2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/4c52cc4486c518ec03f22bb3.jpg"},{"id":69410578,"identity":"d2644626-a073-4637-b480-1e9456aa0c36","added_by":"auto","created_at":"2024-11-20 05:57:41","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":683766,"visible":true,"origin":"","legend":"\u003cp\u003eExperimental data on adsorption kinetics and isotherms of metal and metalloids on OB and OB-derived materials fitted to Elovich and Langmuir-Freundlich models, respectively\u003c/p\u003e","description":"","filename":"Manuscript3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/138b16a9c821ef3982782345.jpg"},{"id":69410579,"identity":"9386a8bf-b862-4e43-a5c4-a9b16d6b49e7","added_by":"auto","created_at":"2024-11-20 05:57:41","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":527384,"visible":true,"origin":"","legend":"\u003cp\u003eEDS (a) and XPS (b) spectra of the OFM800 material with adsorbed metals (Cd, Cu) and metalloids (As, Se)\u003c/p\u003e","description":"","filename":"Manuscript4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/73dd3e8266dc9220bdd21c68.jpg"},{"id":69411862,"identity":"87a8ef33-75a6-4327-a8a1-9ffcbdb81ae5","added_by":"auto","created_at":"2024-11-20 06:13:41","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":409746,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorbed amounts of EPS, CtPAM, and AnPAM on OBCC, OBCM, OFC800, and OFM800 at pH 6 (a) or different pH values (b); adsorbed amounts of metal/metalloids on OFM800 in the presence of polymers (at the concentration of 10 or 100 mg/L) (c-f)\u003c/p\u003e","description":"","filename":"Manuscript5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/c6a4c12d80f8c2b76f82bdbc.jpg"},{"id":69410756,"identity":"0aa3954c-e916-4568-9f13-39003873ca0e","added_by":"auto","created_at":"2024-11-20 06:05:41","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":536113,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption capacity of OFM800 towards metals and metalloids in the one- and two-adsorbate systems: As adsorption with or without Se (a), Se adsorption with or without As (b), As/Se adsorption with or without herbicides (c,d), Cu adsorption with and without Cd (e), Cd adsorption with and without Cu (f), Cu/Cd adsorption with and without herbicides (g,h)\u003c/p\u003e","description":"","filename":"Manuscript6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/2726f5819c9b5d6d8cbfe3d0.jpg"},{"id":73694097,"identity":"69e45528-f027-4e1f-aed6-5a475877b4d0","added_by":"auto","created_at":"2025-01-13 16:10:59","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5280585,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/15f28e74-0e3d-440d-80a7-552677e229e6.pdf"},{"id":69410758,"identity":"6119e9e8-aa11-4095-a69e-e1eed2efb850","added_by":"auto","created_at":"2024-11-20 06:05:42","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2622525,"visible":true,"origin":"","legend":"","description":"","filename":"SUPLEMENTARYINFORMATIONfinal.docx","url":"https://assets-eu.researchsquare.com/files/rs-5037429/v1/a6ffe8f91be2d2893e055d26.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Designing of fruit waste-derived activated carbon through CO2-consuming and microwave- assisted preparation to enhance and understand its adsorption performance towards metal, metalloid and polymer species","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eA significant amount of peel waste comes from fruit and vegetable processing in both industrial settings and household kitchens, which has a serious nutritional, economic, and environmental consequences. The waste stream from processing of fruits and vegetables alone accounts for approximately 25\u0026ndash;30% of total production (Kumar et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). This waste typically includes pomace, peels, rinds, and seeds. Orange processing is one of the sectors that generate the most waste. Global orange production is estimated at roughly 60\u0026nbsp;million tonnes per year, with an annual yield of orange peel totaling 32\u0026nbsp;million tonnes (Michael-Igolima et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). These waste can be successfully used in various industrial areas, e.g. in cosmetics, pharmacy, and agriculture. In this last case, bio-waste is used not only as compost, but is also transformed into biochars (BCs) or activated carbons (ACs) and applied as soil conditioners. BCs and ACs can be practically produced from any material rich in organic carbon (Paraskeva et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2008\u003c/span\u003e). However, few researchers use fruit waste to produce carbonaceous materials and to develop new adsorbents of polymers, metals or metaloids suitable for environmental samples. So far, only Selvarajoo et al. (\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2022\u003c/span\u003e) produced BC from citrus peels at 500 ℃, which was characterized by higher heating value than sub-bituminous coal.\u003c/p\u003e \u003cp\u003eApplication of BCs and ACs is one of the ways to minimize the amount of toxic metals (including heavy metals (HMs)) and metalloids in the soil-water environment as well as to reduce their bioavailability. Metalloids, arsenic/As(V) and selenium/Se(IV), as well as metals, cadmium/Cd(II) and copper/Cu(II), pose a threat to natural ecosystems. Cd, similar to As, devoid of any physiological role, is frequently recognized as a toxic substance (Genchi et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Rahaman et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Cu and Se are micronutrient essential for organisms. However, their high concentrations are dangerous for plants, animals, and humans (Handy et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Handrup and Ravn-Haren, 2020). The mobility of hazardous ions in the environment can additionally be limited by the use of polymeric compounds (Szewczuk-Karpisz et al. \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe main aim of the study was to develop new fruit waste-derived activated carbon via pyrolysis and CO\u003csub\u003e2\u003c/sub\u003e-consuming, microwave-assisted activation. The authors described changes in textural, surface chemistry and sorption characteristics of fruit waste (chokeberry seeds, black currant seeds, orange peels) as well as BCs and ACs prepared using it. The precursors and products used were characterized using various analytical methods, i.e., low-temperature nitrogen (N\u003csub\u003e2\u003c/sub\u003e) adsorption/desorption, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), potentiometric titration, elemental analysis (CHNS), scanning electron microscopy etc. Their adsorption ability was determined towards Cu, Cd, As and Se ions as well as polymers (ionic polyacrylamide, bacterial polysaccharide), and, based on the obtained results, the most promising adsorbent was selected for further experiments. The adsorption mechanisms were investigated in detail in various systems, taking into account various pH values as well as the additional substance presence in the examined system (e.g., additional metal/metalloid or polymer). Experimental adsorption data were fitted to various theoretical models. To estimate strength of toxic metal or metalloid binding, desorption studies were also performed, also in the presence of macromolecular compounds. The study carried out is consistent with the trends of the circular economy, striving to reuse waste, utilize natural resources efficiently as well as reduce pollutant emissions. The authors describe a new strategy for fruit waste management towards the production of effective adsorbents of toxic metal/metalloid ions or polymer macromolecules as well as soil additives that retain their properties in various environments.\u003c/p\u003e"},{"header":"2. Materials and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003e \u003cb\u003eBiomass\u003c/b\u003e Three types of biomass (B): chokeberry (\u003cem\u003eAronia melanocarpa\u003c/em\u003e) seeds (AB), orange (\u003cem\u003eCitrus sinensis\u003c/em\u003e) peels (OB) and black currant (\u003cem\u003eRibes nigrum\u003c/em\u003e) seeds (RB) were used in the study. They were transformed into BCs and ACs by simple thermochemical treatment. Before the experiments, Bs were dried at 110\u0026deg;C (AB and RB were dried without prior grinding, OB was cut into 3\u0026ndash;5 mm pieces). Chokeberry and black currant seeds were delivered by GAMA Zbigniew Olejnicki, P.P.H.U, whereas orange peels by the Skworcu company.\u003c/p\u003e \u003cp\u003e \u003cb\u003eIons/herbicides\u003c/b\u003e Cadmium(II) chloride (CdCl\u003csub\u003e2\u003c/sub\u003e, CAS 10108-64-2, Acros Organics) and sodium arsenate dibasic heptahydrate (Na\u003csub\u003e2\u003c/sub\u003eHAsO\u003csub\u003e4\u003c/sub\u003e\u0026middot;7H\u003csub\u003e2\u003c/sub\u003eO, CAS 10048-95-0, Sigma Aldrich), copper(II) chloride (CuCl\u003csub\u003e2\u003c/sub\u003e, CAS 7447-39-4, Chempur), and sodium selenite (Na\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003eSe, CAS 10102-18-8, Glentham Life Sciences) were used as a source of metal/metalloid ions. In turn, diuron (DCMU, C\u003csub\u003e9\u003c/sub\u003eH\u003csub\u003e10\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO, CAS 330-54-1, Aldrich Chemistry) and glyphosate (GLY, C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003eNO\u003csub\u003e5\u003c/sub\u003eP, CAS 1071-83-6, Sigma Aldrich) were used as examples of herbicides. The concentration of stock solutions of Cd, Cu, As, and Se ions was 1000 mg/L, whereas that of diuron and glyphosate, 100 mg/L. In the case of diuron, a methanol (CH\u003csub\u003e3\u003c/sub\u003eOH, CAS 67-56-1, Chemsolute) solution was made due to its limited solubility in water.\u003c/p\u003e \u003cp\u003e \u003cb\u003ePolymers\u003c/b\u003e In the experiments, natural and synthetic polymers were used. There were: (1) exopolysaccharide (EPS) synthesized by soil bacteria \u003cem\u003eRhizobium leguminosarum\u003c/em\u003e bv. \u003cem\u003etrifolii\u003c/em\u003e, (2) cationic polyacrylamide (CtPAM), anionic polyacrylamide (AnPAM). EPS was isolated courtesy of scientists from the Institute of Biological Sciences, Maria Curie-Skłodowska University in Lublin according to the procedure described elsewhere (Szewczuk-Karpisz et al., \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Anionic (AnPAM, \u003cem\u003eAN945\u003c/em\u003e) and cationic (CtPAM, \u003cem\u003eFO4350SH\u003c/em\u003e) polyacrylamide were synthesized and delivered by SNF Floerger. The average molecular weight of AnPAM and CtPAM was 6.8 and 13 kDa, respectively. CtPAM contained 25% of the quaternary amine groups, while AnPAM contained 40% of carboxyl ones (Szewczuk-Karpisz et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). The polymer stock solutions had a concentration of 500 mg/L. The structures of applied organic compounds are presented in Table A.1.\u003c/p\u003e \u003cp\u003e \u003cb\u003eOthers\u003c/b\u003e The pH value of the examined systems was adjusted with hydrochloric acid (HCl, CAS 7647-01-0, Chempur) and sodium hydroxide (NaOH, CAS 1310-73-2, Chempur). To determine AnPAM concentration, hyamine 1622 (0.004 mol/dm\u003csup\u003e3\u003c/sup\u003e, CAS 121-54-0, POCH) was used. Calcium chloride (CaCl\u003csub\u003e2\u003c/sub\u003e, CAS 10043-52-4, Chempur) with the concentration of 0.001 mol/dm\u003csup\u003e3\u003c/sup\u003e was applied as a supporting electrolyte. The glyphosate derivatization was performed with use of: borate buffer (Na\u003csub\u003e2\u003c/sub\u003eB\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e7\u003c/sub\u003e\u0026middot;10H\u003csub\u003e2\u003c/sub\u003eO, CAS 1303\u0026thinsp;\u0026minus;\u0026thinsp;964, Chempur),\u003c/p\u003e \u003cp\u003e9-fluorenylmethylchloromethane (FMOC-Cl, CAS 28920-43-6, Glentham Life Sciences), acetonitrile (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e3\u003c/sub\u003eN, CAS 75-05-8, Chemsolute) and dichloromethane (CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, CAS 75-09-2, POCH).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Methods\u003c/h2\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003e2.2.1. Biochar (BC) and activated carbon (AC) synthesis\u003c/h2\u003e \u003cp\u003eIn order to obtain BCs, pyrolysis of dried Bs was performed at 400\u0026deg;C in a conventional laboratory single-zone resistance furnace (PRW75/LM, Czylok), equipped with a 75 mm diameter quartz tubular reactor or in a muffle microwave furnace (Phoenix, CEM Corporation). The pyrolysis was carried out in an atmosphere of inert gas \u0026ndash; technical nitrogen (Linde Gaz Polska), with a flow of 200 mL/min. About 15 g of precursors were placed in nickel boats or quartz crucibles (in case of conventional or microwave furnace, respectively), and then subjected to two-stage thermal treatment: 1) heating with a temperature gradient of 5\u0026deg;C/min until reaching the final pyrolysis temperature, 2) annealing the sample at 400\u0026deg;C for a period of 45 min. Then, the pyrolysis products were cooling to the room temperature under the flow of inert gas. ACs were produced in two ways: 1) by activating the BCs or 2) by direct activation of Bs, in the appropriate type of furnace. About 10 g of BCs or precursors were placed in nickel boats (conventional heating) or quartz crucibles (microwave heating), and then put in the appropriate furnace preheated to a temperature of 700 or 800 \u0026deg;C for 45 min in the carbon dioxide (Linde Gaz Polska) atmosphere, with a flow of 250 mL/min. Then, the samples were cooled in nitrogen flow. After reaching room temperature, each material was ground in a planetary ball mill (Pulverisette 6 Classic Line, Fritsch). The obtained materials were marked as: (1) BCC \u0026ndash; BC obtained in conventional furnace at 400\u0026deg;C, (2) BCM \u0026ndash; BC obtained in microwave furnace at 400\u0026deg;C, (3) ACC \u0026ndash; AC obtained in a conventional furnace at 800\u0026deg;C from BCC, (4) ACM \u0026ndash; AC obtained in a microwave furnace at 800\u0026deg;C from BCM, (5) FC700 and (6) FC800 \u0026ndash; AC obtained in a conventional furnace at 700 or 800\u0026deg;C directly from B, (7) FM700 and (8) FM800 \u0026ndash; AC obtained in a microwave furnace at 700 or 800\u0026deg;C directly from B. If the material was prepared using chokeberry seeds, the \u0026lsquo;A\u0026rsquo; prefix was assigned to it, if from orange peels, \u0026lsquo;O\u0026rsquo; was added, and if from black currant seeds, \u0026lsquo;R\u0026rsquo; was used.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.2.2. Bs, BCs and ACs characteristics\u003c/h2\u003e \u003cp\u003eLow-temperature nitrogen (N\u003csub\u003e2\u003c/sub\u003e) adsorption/desorption method was applied to determine textural parameters of Bs, BCs, and ACs (Quadrasorb SI, Quantachrome Instruments). Specific surface area (S\u003csub\u003eBET\u003c/sub\u003e) was calculated using Brunauer-Emmet-Teller (BET) equation, whereas pore size distribution, by the Barett, Joyner and Halenda (BJH) method. Porosity parameters were estimated using the adsorption branch of the isotherm. Micropore volume (V\u003csub\u003emic\u003c/sub\u003e) was calculated using the t-plot method, and total pore volume (V\u003csub\u003et\u003c/sub\u003e), under relative pressure conditions p/p\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.99. Before the measurements, the samples were outgassed at 200\u0026deg;C for 20 h. Morphology of the tested solids was observed using scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) (Phenom ProX, PiK Instruments). The apparatus was also used to plot maps of the element distribution on the solid surface, before and after adsorption of metals and metalloids. Determination of surface functional groups was performed using Fourier transform infrared spectroscopy (Tensor27, Bruker Germany), from 128 scans in 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e intervals, in the range of 4000\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Each spectrum was corrected with a linear baseline using OMNIC (v.8.2, Thermo Scientific).\u003c/p\u003e \u003cp\u003eTo determine the point of zero charge (pH\u003csub\u003epzc\u003c/sub\u003e) and surface charge density (σ\u003csub\u003e0\u003c/sub\u003e) of the investigated solids, the potentiometric titration with automatic burette (Titrino 702 SM, Methrom) and 0.1 M NaOH as the titrant was applied. The titration was performed at pH values of 3\u0026ndash;10. Surface charge density was calculated using Janusz (\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e1999\u003c/span\u003e) method.\u003c/p\u003e \u003cp\u003eThe form of metals and metalloids adsorbed on the solids was determined using X-ray photoelectron spectroscopy (XPS) (UHV surface analysis system (SPECS)). The elemental composition of the solids was also determined using a 2400 Series II CHNS/O Elemental Analyzer (Perkin Elemer) The ash content in the materials was established according to the DNS 1171:2002 standard. The amount of acidic and basic groups on the solid surface was determined by the Boehm back titration method (Boehm, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e1994\u003c/span\u003e) using 0.1 M NaOH and HCl volumetric standards as the titrants and methyl orange as the indicator. The pH of water suspensions of each material was determined by adding a portion of 0.5 g of the solid to 25 mL of distilled water and stirring for 24 h to reach equilibrium. After the time passes, the pH of the suspensions was measured using CP-401 pH-meter (Elmetron) equipped with EPS-1 glass electrode.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e2.2.3. Adsorption study\u003c/h2\u003e \u003cp\u003eAdsorption study was performed for metals, metalloids, herbicides, and polymers in both single and mixed systems. Their adsorbed amount (Γ, mg/g) was determined based on the difference in their concentration in the solution before and after the adsorption process, using the following formula:\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:\\varGamma\\:=\\frac{{C}_{ads}\\bullet\\:V}{m}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere: C\u003csub\u003eads\u003c/sub\u003e \u0026ndash; the adsorbed amount of metal/metalloid ions, herbicide or polymers molecules (C\u003csub\u003eads\u003c/sub\u003e = C\u003csub\u003e0\u003c/sub\u003e-C\u003csub\u003eeq\u003c/sub\u003e) [mg/L], C\u003csub\u003e0\u003c/sub\u003e \u0026ndash; the initial adsorbate concentration [mg/L], C\u003csub\u003eeq\u003c/sub\u003e \u0026ndash; the equilibrium adsorbate concentration in the solution [mg/L], V \u0026ndash; the system volume [L], m \u0026ndash; the solid weight [g].\u003c/p\u003e \u003cp\u003eThe adsorption efficiency was calculated as follows:\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$\\:E=\\:\\frac{{C}_{ads}}{{C}_{0}}\\bullet\\:100\\%$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eFor Cu, Cd, polymers and herbicides, the solid weight of 0.02 g was used. In turn, for As and Se, 0.04 g of solid was applied. The solid samples were added to 10 mL of the solution containing selected adsorbate and supporting electrolyte (0.001 mol/L CaCl\u003csub\u003e2\u003c/sub\u003e). The concentration of metals/metalloids, used to estimate adsorption isotherms, ranged from 10 to 250 mg/L. The adsorption kinetics were assessed for their concentration of 100 mg/L. The adsorbed amount of polymers and herbicides was determined for their initial concentration of 100 mg/L and 10 mg/L, respectively. In the mixed systems, the concentration of metals and metalloids was 10, 100 or 250 mg/L, whereas that of polymers was 100 mg/L and herbicides was 10 or 20 mg/L. Mixed adsorption tests were conducted in following combinations: metal\u0026thinsp;+\u0026thinsp;metal, metalloid\u0026thinsp;+\u0026thinsp;metalloid, metal\u0026thinsp;+\u0026thinsp;herbicide, metalloid\u0026thinsp;+\u0026thinsp;herbicide. After preparing the suspension, the pH value was adjusted to 6, and the adsorption was conducted for 24 h under continuous shaking conditions. The pH value was monitored throughout the adsorption process, and any fluctuations were corrected to maintain a value of 6. After the process completion, the concentration of metals and metalloids was determined using atomic absorption spectrometer (ContrAA 800, Analytik Jena) working in the graphite cuvette technique. The concentration of AnPAM after adsorption was determined using hyamine 1622 (Kang et al. \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). CtPAM and EPS concentration was measured with total organic carbon (TOC) analyzer (Multi N/C 2000, HT 1300, Analytik Jena). The concentration of diuron was determined using high performance liquid chromatography (HPLC, Dionex Ultimate 3000, Thermo Scientific), whereas the one of glyphosate, using the method developed by Waiman et al. (\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2012\u003c/span\u003e) and Specord 200 PLUS spectrophotometer (Analytik Jena).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.2.4. Adsorption data modeling\u003c/h2\u003e \u003cp\u003eFor the adsorption of metal and metalloid ions, the equilibrium data were fitted to Langmuir, Freundlich, Langmuir-Freundlich, Temkin, Redlich-Peterson, and Dubinin-Radushkevitch models. The kinetics data were fitted to the pseudo I-order (PFO), pseudo II-order (PSO), intra-particle diffusion (IPD) and Elovich models. The Microsoft Excel Solver was used for data modelling. All equations used are shown in Table A.2. The adsorption of macromolecules is completely different than that of ions. Specific conformations including \u0026lsquo;loops\u0026rsquo; and \u0026lsquo;tails\u0026rsquo; are formed on the solid surface. One polymer chain can interact with several active sites (Szewczuk-Karpisz et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), and therefore the isotherms for polymers were not modeled. Their adsorbed amounts were presented only in the form of histograms.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.2.5. Statistical analysis\u003c/h2\u003e \u003cp\u003eAll measurements were made in triplicate. The standard deviation was calculated from the obtained data.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Characterization of Bs, BCs and ACs\u003c/h2\u003e \u003cp\u003eAccording to IUPAC classification, the N\u003csub\u003e2\u003c/sub\u003e adsorption/desorption isotherms of the tested materials were close to type IV with hysteresis loops of H3 or H4 type (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, A.1). The H3 hysteresis, visible mainly for Bs and BCs, is usually attributed to wedge-shaped pores formed by the loose stacking of flaky particles. The H4 type, observed for all ACs, corresponds with slit-shaped pores resulting from internal parallel pore structure (Xu et al., \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Among all precursors, S\u003csub\u003eBET\u003c/sub\u003e of black currant seeds was the largest (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Pyrolysis in a conventional furnace did not promote the development of the specific surface area, and therefore, the prepared BCs had even lower S\u003csub\u003eBET\u003c/sub\u003e than precursors. Microwave-assisted pyrolysis had an opposite effect and resulted in a higher S\u003csub\u003eBET\u003c/sub\u003e value for BC. In most cases, the obtained BCs did not contain micropores. The CO\u003csub\u003e2\u003c/sub\u003e activation improved specific surface area and made content of micropores higher (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). The Boudouard reaction: C\u003csub\u003eb\u003c/sub\u003e + CO\u003csub\u003e2\u003c/sub\u003e ↔ 2CO (where: C\u003csub\u003eb\u003c/sub\u003e – the carbon in BC structure) was involved in the BC activation. CO\u003csub\u003e2\u003c/sub\u003e underwent dissociative chemisorption on the surface and formed the following oxides on it: C(O) and CO. Then, C(O) was desorbed, resulting in the formation the pore structure. CO, as a gaseous product, could also be adsorbed on active sites and retarded gasification (Sajjadi et al., 2018). The effect was even stronger when microwave heating was applied. During conventional heating only the surface layers of the material were exposed to high temperature and activating agent. Thanks to microwave heating, the both factors also affected deeper layers, which contributed to a significant improvement in textural parameters (Sajjadi et al., 2018). ACs obtained from AB and OB through direct activation at 800°C were characterized by the largest S\u003csub\u003eBET\u003c/sub\u003e and the highest V\u003csub\u003em\u003c/sub\u003e/V\u003csub\u003et\u003c/sub\u003e ratio among all tested solids. They also had the highest V\u003csub\u003et\u003c/sub\u003e values and the smallest D parameters as well.\u003c/p\u003e \u003cp\u003eTab. 1. Physicochemical characterization of Bs, BCs, and ACs\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd\u003e\u003cbr\u003e\u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eS\u003csub\u003eBET\u003c/sub\u003e [m\u003csup\u003e2\u003c/sup\u003e/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eV\u003csub\u003et\u003c/sub\u003e [cm\u003csup\u003e3\u003c/sup\u003e/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eD [nm]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eS\u003csub\u003emicro\u003c/sub\u003e [m\u003csup\u003e2\u003c/sup\u003e/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eV\u003csub\u003emicro\u003c/sub\u003e [cm\u003csup\u003e3\u003c/sup\u003e/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eS\u003csub\u003em\u003c/sub\u003e/S\u003csub\u003eBET\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003epH\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003epHpzc\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eash [% wt.]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eH:C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eO:C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003e(O+N):C\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eacidic groups [mmol/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003ebasic groups [mmol/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003etotal \u0026nbsp;groups content [mmol/g]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eAB\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.0015\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6.3432\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e4.512\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e3.12\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.13\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.66\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.71\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.004\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.224\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.228\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eABCC\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.0015\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6.365\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6.805\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6.4\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e10.05\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.07\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.19\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.26\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.201\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.250\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.451\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eABCM\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.0099\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e6.1754\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n 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\u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.02\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.30\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.37\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.025\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.396\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.421\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eRFM700\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e196\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.133\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e2.718\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e126\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.065\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.64\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e7.695\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e8.6\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e16.99\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.02\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.46\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.54\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.496\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.343\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.839\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eRFC800\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e88\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.063\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e2.836\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e50\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.025\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.56\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e8.570\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e8.4\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e16.58\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.01\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.39\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.099\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.671\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.770\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd\u003e\n \u003cp\u003e\u003cstrong\u003eRFM800\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e219\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.144\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e2.614\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e143\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.075\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.65\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e7.963\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e9.6\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e18.05\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.02\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.46\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.54\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e0.495\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.372\u003c/p\u003e\n \u003c/td\u003e\u003ctd\u003e\n \u003cp\u003e1.866\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003cp\u003eSEM was used to observe morphology of Bs, BCs, and ACs (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec, Fig A.2). BCs and ACs had a heterogeneous structure rich in cracks, crevices and channels. Such structures are typical for materials obtained by pyrolysis/activation of biomass at high temperatures (Tomczyk and Szewczuk-Karpisz, \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Comparing Bs, BCs, and ACs, the morphology became more and more complex due to the aggregation of mineral compounds (Suman et al., \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe acidic/basic groups content in the materials changed after pyrolysis and activation. In most cases, the solids obtained from OB had the largest number of functional groups (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Activation with carbon dioxide increased content of basic groups. In the case of ACs obtained directly from OB in both furnace types or indirectly in microwave furnace, the complete disappearance of acidic groups in favor of basic ones was visible. BCs produced at high temperatures (600–700°C) exhibited highly hydrophobic nature and were characterized by lower contents of H- and O-containing functional groups. This phenomenon was associated with dehydration and deoxygenation of biomass. During heating, chemical bonds in the precursor structure are being broken and rearranged, which resulted in formation of new functional moieties (Tomczyk et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). For example, carbonyl groups crack to CO around 400°C, whereas carboxyl groups start to decompose into CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO at 200°C due to lower thermal stability (Cui et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). In most cases, the water extracts of the products of OB pyrolysis/activation had the highest pH values among all tested materials.\u003c/p\u003e \u003cp\u003eThe results of potentiometric titration indicated that surface charge density and the pH\u003csub\u003epzc\u003c/sub\u003e parameters of Bs, BCs, and ACs differed significantly (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Fig. A.3a-c). The pH\u003csub\u003epzc\u003c/sub\u003e value of orange peels was 4.5, which meant that at pH 6, at which the adsorption study was performed, their surface was negatively charged. BCs and ACs were positively charged during sorption experiments since their pH\u003csub\u003epzc\u003c/sub\u003e values were higher than 8.\u003c/p\u003e \u003cp\u003eThe study on elemental composition indicated that the H:C, O:C, and (N + O):C ratios decreased after heat treatment (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Biomass pyrolysis and activation increased aromaticity and hydrophobicity of materials as it was indicated by lower values of the H:C and (O + N):C ratios, respectively. The decrease in the O:C ratio was equivalent to lower content of polar functional groups (Qiu et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). The H:C parameter was also employed to assess the level of BCs carbonization, which is closely associated with the BCs long-term stability within the environment. According European BC Certificate, the O:C ratio should be less than 0.4, and H:C, less than 0.7, when BCs are appropriate for environmental applications (Tomczyk et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). This criterions were fulfilled for almost all investigated carbon-rich materials. The only exceptions were two ACs prepared from black currant seeds (RFM700 and RFM800) that had the O:C ratio equal to 0.46. Spokas (\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2010\u003c/span\u003e) suggested that lower O:C molar ratios were reflected in a longer BC half-life (t\u003csub\u003e1/2\u003c/sub\u003e) (in laboratory conditions). The researcher identified 3 approximate ranges for the BC t\u003csub\u003e1/2\u003c/sub\u003e parameter, categorized by the O:C ratio, i.e., t\u003csub\u003e1/2\u003c/sub\u003e \u0026gt; 1000 years for O:C \u0026lt; 0.2, 100 years \u0026lt; t\u003csub\u003e1/2\u003c/sub\u003e \u0026lt; 1000 years for O:C 0.2–0.6, and t\u003csub\u003e1/2\u003c/sub\u003e \u0026lt; 100 years for O:C \u0026gt; 0.6. According to it, the produced BCs and ACs can be classified as those of high stability.\u003c/p\u003e \u003cp\u003eBased on the FTIR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) it was stated that physical activation of OB, regardless of the heating method, resulted in relatively minor changes in its surface chemistry. The FTIR spectra of Bs, BCs, and ACs were similar, and only intensity of specific bands was the difference between them. The FTIR spectrum of OB was composed of the following bands at: 3900 − 3500 cm\u003csup\u003e− 1\u003c/sup\u003e (corresponding with the vibrations of free -OH bonds in alcohols, phenols, or other compounds containing hydroxyl groups that are not dissociated (Dai et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2023\u003c/span\u003e)), 2278 cm\u003csup\u003e− 1\u003c/sup\u003e (attributed to C ≡ N stretching vibration), 1700 − 1500 cm\u003csup\u003e− 1\u003c/sup\u003e (stretching vibration of C = O bond in non-ionic carboxyl groups (–COOH, –COOCH\u003csub\u003e3\u003c/sub\u003e), carboxylic acids, or their esters), 1600 − 1455 cm\u003csup\u003e− 1\u003c/sup\u003e (asymmetric and symmetric stretching vibrations of ionic carboxylic groups (–COO\u003csup\u003e−\u003c/sup\u003e)), 1042 cm\u003csup\u003e− 1\u003c/sup\u003e (the C–O stretching vibrations associated with sugars or esters (Feng et al., \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2011\u003c/span\u003e)). These bands were also visible for AB and RB. The FTIR spectrum of AB (Fig. A.3a) and RB (Fig. A.3b) contained bands at: 3277 cm\u003csup\u003e− 1\u003c/sup\u003e (corresponding with –OH stretching vibrations), 2922 − 2853 cm\u003csup\u003e− 1\u003c/sup\u003e (the C–H stretching vibrations), 1634 − 1611 cm\u003csup\u003e− 1\u003c/sup\u003e (the C = O stretching vibration). In the case of BCs/ACs, the band at 1042 cm\u003csup\u003e− 1\u003c/sup\u003e could be attributed to the C–O and C–O–C stretching vibrations associated with phenol, ester, and alcohol groups from cellulose degradation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe XPS results (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) confirmed the presence of C = C, C-H, C-O, C-N, COO\u003csup\u003e−\u003c/sup\u003e groups in OB and OB-derived BCs and ACs. It was also shown that the materials obtained in microwave furnace contained higher amount of N compared to those obtained in conventional one. Such BCs and ACs were characterized by higher content of O, which formed mainly C = O, C-O-C, C = N-O groups. The materials obtained using conventional heating were rich in C-OH moieties.\u003c/p\u003e\u003cp\u003eTab. 2. Content of individual forms of C, N, O, Ca, and K in OB and BCs/ACs prepared from them\u003c/p\u003e\n \u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003eOB\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003eOBCC\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003eOBCM\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003eOFCC800\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003eOFCM800\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eC\u003csub\u003etotal\u003c/sub\u003e [at. %]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e77.96\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e86.41\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e81.70\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e84.41\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e76.96\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC=C / C-H\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e43.30\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e68.24\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e57.83\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e67.10\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e52.73\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC-O / C-N\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e20.27\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e11.49\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e17.34\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e22.43\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e15.69\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC=O\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e11.37\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e4.05\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e3.61\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e5.83\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e4.72\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eCOO\u003csup\u003e-\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e3.02\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e2.63\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e2.91\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e4.64\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e3.82\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eN\u003csub\u003etotal\u003c/sub\u003e [at. %]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e1.41\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e0.50\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e2.39\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e1.44\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e2.13\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eN-5 (pyrrolic / pyridonic)\u0026nbsp;\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e1.41\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e0.50\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e2.39\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e1.44\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e2.13\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eO\u003csub\u003etotal\u003c/sub\u003e [at. %]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e20.63\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e13.09\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e15.90\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e12.72\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e17.9\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC=O\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e5.98\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e4.14\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e11.75\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e1.79\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e12.26\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC-OH\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e8.95\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e10.93\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eC-O-C / C=N-O\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e14.65\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e4.15\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e5.64\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eCOO\u003csup\u003e-\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCa\u003csub\u003etotal\u003c/sub\u003e [at. %]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e1.43\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e1.86\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eCa 2p 3/2\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.95\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e1.24\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eCa 2p 1/2\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.47\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.62\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003e\u003cstrong\u003eK\u003csub\u003etotal\u003c/sub\u003e [at. %]\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e-\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e0.01\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e\u003cstrong\u003e1.14\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eK 2p 3/2\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.01\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.76\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd valign=\"top\" style=\"width: 29.4776%;\"\u003e\n \u003cp\u003eK 2p 1/2\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 12.3134%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 14.1791%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e-\u003c/p\u003e\n \u003c/td\u003e\u003ctd valign=\"top\" style=\"width: 15.8582%;\"\u003e\n \u003cp\u003e0.38\u003c/p\u003e\n \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\n\u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Selection of optimal precursor for production of carbon-rich materials\u003c/h2\u003e \u003cp\u003eThe best material for further research was selected based on the results of adsorption tests (Fig. A.5). The highest adsorption capacities towards selected metal/metalloid ions were noted for OB- and RB-derived materials. In the case of GLY, RS-derived materials had better sorption properties than OB-derived ones, but BCs from this biomass proved unsuitable for environmental applications (their O:C ratio was too high). As a result, for further experiments aiming at the determination of the kinetics, isotherms, and mechanism of metal/metalloid adsorption, only the solids obtained from OB, i.e., OBCC, OBCM, OFC800, OFM800, and OB were selected. More detailed studies, such as those performed in the polymer presence, were carried out only on the most promising adsorbent – OFM800. For initial metal/metalloid concentration equal to 100 mg/L, its adsorption capacity was 3.7, 2.6, 28.7, and 23.4 mg/g for As, Se, Cu, and Cd, respectively. For initial herbicide concentration equal to 10 mg/L, its adsorption capacity towards DCMU was 36.57, while towards GLY, 1.26 mg/g. The production of exactly this material is the most economically justified. Orange peels are the biggest problem among all the biomasses studied due to the huge amounts of them generated every year.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Metal/metalloid adsorption mechanisms on the OB-derived materials\u003c/h2\u003e \u003cp\u003eMetal/metalloid adsorption kinetics and isotherms were determined at pH 6. Then, As(V) ions occurred as H\u003csub\u003e2\u003c/sub\u003eAsO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e (85%) and HAsO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2−\u003c/sup\u003e (15%) (Lupa et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), Se(IV) ions, as HSeO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e (100%) (Lichtfouse et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), Cd(II) ions, as Cd\u003csup\u003e2+\u003c/sup\u003e (100%) (Oyetade et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2018\u003c/span\u003e), and Cu(II) ions, as Cu\u003csup\u003e2+\u003c/sup\u003e (almost 100%) (Quiroz, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e \u003cdiv id=\"Sec14\" class=\"Section3\"\u003e \u003ch2\u003e3.3.1. Contact time effect\u003c/h2\u003e \u003cp\u003eThe experimental data of Cd, Cu, As and Se adsorption kinetics with fitting to the Elovich model are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, whereas the calculated parameters of PFO, PSO, IPD and Elovich models are presented in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Metal/metalloid adsorption was a two-stage process, especially for ACs. This suggested strong interactions between active sites of BCs/ACs and the examined metal ions. During the first stage, there was a rapid increase in the adsorbed amount of all ions until thermodynamic equilibrium was achieved (i.e., plateau, the second stage). This state was reached after 60–120 min in the case of Cu and As adsorption on all carbonaceous materials as well as for the Se adsorption on ACs. For the Cd adsorption on BCs, the equilibrium was reached later, after 120–240 min. The adsorbed amount of all ions remained practically unchanged after 24 h, which is why exactly this time was selected for equilibrium tests.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAmong all theoretical kinetics models, Elovich equation best described experimental data. The correlation coefficients were high (R\u003csup\u003e2\u003c/sup\u003e ≥ 0.994) for the Cd, Cu, As, and Se adsorption on all studied materials (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The calculated theoretical qe values derived from the Elovich model were close to the observed experimental adsorption capacity. Experimental qe for the As adsorption on OFM800 was 4.01 mg/g, whereas theoretical one was 4.06 mg/g. For Se, these values were 2.59 and 2.84 mg/g, for Cd, 28.69 and 31.50 mg/g, while for Cu, 23.46 and 25.92 mg/g, respectively. The Elovich model is suitable for heterogenous adsorbents and allows to predict the mass and surface diffusion as well as activation and deactivation energy of the system (Wu et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Ouyang et al., 2020). The high fitting obtained for the tested suspensions indicated that chemisorption occurs in them, wherein valence forces come into play via the sharing or exchange of electrons between the adsorbent and metal ions as well as covalent forces and ion exchange (Kończyk et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eDesorption degree of metals/metalloids with and without polymers as well as complexation degree of metals/metalloids by polymers\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDesorption degree [%]\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eAs\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eSe\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"3\" nameend=\"c10\" namest=\"c8\"\u003e \u003cp\u003eCu\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"3\" nameend=\"c13\" namest=\"c11\"\u003e \u003cp\u003eCd\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ecycle number\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eI\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eIII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eI\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eIII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003eI\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003eII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003eIII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003eI\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003eII\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003eIII\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.36\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4.61\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.28\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e23.20\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e21.64\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e21.12\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e9.94\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e2.97\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e3.08\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L EPS\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e7.97\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.86\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.43\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4.15\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.22\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e8.45\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e7.48\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e6.44\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e5.47\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e1.33\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e2.22\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L EPS\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e11.12\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.76\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.56\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e12.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e5.19\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e4.34\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e1.74\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L Ct PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e9.28\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e5.11\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.26\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e13.92\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e17.14\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e17.51\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e7.74\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e5.93\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e5.22\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L Ct PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e11.47\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.75\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.40\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.67\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.27\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e44.61\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e62.20\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e86.17\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e7.95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e6.64\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e6.34\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L An PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e11.10\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.23\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.19\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.27\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.96\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e4.43\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.16\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e6.37\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e1.46\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e0.16\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L An PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e10.15\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.72\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.33\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e12.71\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.41\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e4.23\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e1.25\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e0.34\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eComplexation degree [%]\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003eAs\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"3\" nameend=\"c7\" namest=\"c5\"\u003e \u003cp\u003eSe\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"3\" nameend=\"c10\" namest=\"c8\"\u003e \u003cp\u003eCu\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"3\" nameend=\"c13\" namest=\"c11\"\u003e \u003cp\u003eCd\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003einitial concentration of metal/metalloid\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e250\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L EPS\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.83\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e4.84\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.71\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e8.29\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e13.14\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e24.60\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e25.30\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e24.40\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L EPS\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.30\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.32\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2.29\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.29\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e9.37\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e26.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e26.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e24.40\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L Ct PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3.42\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e7.28\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.78\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.43\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e11.71\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e22.80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e22.80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e22.40\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L Ct PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e10.96\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e9.31\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e7.58\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.60\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e20.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e24.40\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e23.60\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e10 mg/L An PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.59\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.78\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.88\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.48\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e12.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e12.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e12.23\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e30.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e26.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e24.80\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e100 mg/L An PAM\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.36\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e4.02\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.22\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e32.29\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e15.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e14.23\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e40.80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e \u003cp\u003e37.40\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e \u003cp\u003e29.20\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003cp\u003eAnother model with very high correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e ≥ 0.997) was the IPD model. This model had a bit worse compliance of the experimental and theoretical values of sorption capacity than the Elovich one. The C parameter in IPD model gives the information about thickness of the boundary layer. The higher it is, the greater the thickness of the boundary layer is observed. In addition, if the C parameter is greater than 0, it indicates that intraparticle diffusion (ion diffusion in the material pores, seen as a plateau) is not the only process controlling the adsorption rate. There are also external diffusion (ion diffusion towards the external surface, seen as sudden increase at the beginning of the process) (Kończyk et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Among all tested systems, the C parameter had the greatest impact on the Cu adsorption on each material, i.e., the C value was in range of 4.157–11.733. In case of Cd and As adsorption on OB, OBCC, and OBCM, the C parameter was in range of 0-0.166. In turn, for Se, it was in range of 0.565–1.094.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section3\"\u003e \u003ch2\u003e3.3.2. Effect of initial metal/metalloid concentration\u003c/h2\u003e \u003cp\u003eFor isotherm modelling, three-parameter models (Langmuir-Freundlich (L-F), Redlich-Peterson (R-P), Dubinin-Radushkevich (D-R)), and two-parameter ones (Langmuir, Freundlich, Temkin) were applied. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e shows experimental isotherms and their fitting to L-F model, whereas Table A.3 presents all calculated isotherm parameters.\u003c/p\u003e \u003cp\u003eThe Langmuir model is valid for monolayer and uniform adsorption, when there are no interactions between the neighboring molecules/ions. On the other hand, the Freundlich model assumes that adsorption is multilayer and active sites are heterogeneous (Belhachemi and Addoun, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). The D-R model describes adsorption in porous structures, which is based on both physical and chemical forces (Kończyk et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). In the case of performed metal/metalloid adsorption, none of these models fit the experimental data well.\u003c/p\u003e \u003cp\u003eL-F and R-P are a combination of the Langmuir and Freundlich models. L-F gives information about energy of adsorption (the K\u003csub\u003eLF\u003c/sub\u003e constant; it increases when adsorbate affinity to the solid is higher), the number of active sides on the adsorbent (the A\u003csub\u003em\u003c/sub\u003e parameter) and the solid heterogenity (the m parameter) (Belhachemi and Addoun, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Tomczyk et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). For the L-F model, the R\u003csup\u003e2\u003c/sup\u003e coefficient was higher than 0.997 for all tested systems, and thus it can be used to describe experimental data. The highest affinity to the adsorbent was noted for Cu adsorption on OFM800 (K\u003csub\u003eLF\u003c/sub\u003e = 0.318 L mg\u003csup\u003e− 1\u003c/sup\u003e). Lesser affinity was noted for Cu binding on OBCM and OFC800 (0.183 and 0.199 L mg\u003csup\u003e− 1\u003c/sup\u003e, respectively). For other systems, this parameter was lower than 0.035 L mg\u003csup\u003e− 1\u003c/sup\u003e, which was equivalent to very low ion affinity to the adsorbent surface. For Se, there was almost none affinity for the studied solids. However, it must be emphasized that the affinity of all ions increased, when the microwave muffle furnace was used in the material production. For As, the K\u003csub\u003eLF\u003c/sub\u003e parameter was 0.009 L mg\u003csup\u003e− 1\u003c/sup\u003e for OFC800, while for OFM800, 0.025 L mg\u003csup\u003e− 1\u003c/sup\u003e. In most cases, this was associated with a greater number of adsorbent active sites.\u003c/p\u003e \u003cp\u003eR-P is used to the systems, where adsorption process is more complicated and involves homogeneous and heterogeneous adsorption types. The β parameter adopts values in the range from 0 to 1. When β equals 1, the aforementioned equation simplifies to the Langmuir isotherm. In turn, when it is close to 0, the Freundlich model describes the adsorption process (Belhachemi and Addoun, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Tomczyk et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). For all examined systems, the R-P model also fitted the experimental data very well (R\u003csup\u003e2\u003c/sup\u003e ≥ 0.991). For As adsorption on OFC800 and OFM800, Se adsorption on all tested materials, Cd adsorption on OB, OFC800, and OFM800, and Cu adsorption on OBCC and OBCM, the β parameter was close to 1 and ranged of 0.619-1.000. This allowed to state that the monolayer adsorption occurred in these systems. In the remaining cases, both mono- and multilayer adsorption took place.\u003c/p\u003e \u003cp\u003eThe Temkin model assumes that the adsorption heat (the b\u003csub\u003eT\u003c/sub\u003e parameter) decreases linearly as the coverage of the adsorbent surface increases. Additionally, the adsorption distribution is characterized by uniform dispersion of binding energy (the K\u003csub\u003eT\u003c/sub\u003e parameter) (Piccin et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). When b\u003csub\u003eT\u003c/sub\u003e constant is less than 1.0 kcal/mol, the adsorption is physical. When b\u003csub\u003eT\u003c/sub\u003e is in the range of 1–20 kcal/mol, there is ion exchange, whereas when it exceeds 20 kcal/mol, the process is classified as chemisorption (Kończyk et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The Temkin model described experimental isotherms with the R\u003csup\u003e2\u003c/sup\u003e coefficient equal or higher than 0.993. For As adsorption on B and BCC as well as Se adsorption on OFC800 and OFM800 samples, the b\u003csub\u003eT\u003c/sub\u003e constants of 1.247, 1.240, 1.602, and 1.042 kcal/mol, were obtained, respectively, which confirmed the ion exchange mechanism. In the remaining cases, physical adsorption occurred.\u003c/p\u003e \u003cp\u003eThe adsorbed amounts of Cd and Cu ions differed significantly, which was dictated by their various radii and electronegativity. Van der Waals atomic radius of Cu is 140 pm, while that of Cd 158 pm (National Center for Biotechnology Information). Due to the smaller size of Cu ions (compared to Cd ones), they can penetrate pores easier and in larger quantities. It seems that negatively charged As and Se ions should be adsorbed in larger quantities than Cd and Cu, due to the positive charge of the adsorbents surface at the selected pH value. However, the metalloid adsorption was significantly lower. This was probably associated with the sizes of As and Se ions, which are much larger than those of Cd and Cu ions. As and Se occur in the solution as oxyanions, and the van der Waals atomic radius of these metalloids are also larger (185 and 190 pm, respectively).\u003c/p\u003e \u003cp\u003eIn general, the amounts adsorbed were higher for the materials obtained in a microwave furnace compared to analogous samples prepared in a conventional one. There was also a clear difference between adsorption on BCs and ACs, which was caused by more developed specific surface area, better porosity and higher content of functional groups of ACs compared to BCs. The only exception was Se adsorption, during which the best adsorption properties were observed for OBCC.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section3\"\u003e \u003ch2\u003e3.3.3. Effect of solution pH value\u003c/h2\u003e \u003cp\u003eThe solution pH value affects adsorbent surface charge, as well as alters adsorbate ionization and species. During the study, for As concentration 100 mg/L, the highest removal efficiency was observed at pH 5 (Γ = 3.94 mg/g) (Fig. A.6). For pH 6 and 7, a slight decrease in adsorption capacity was observed (it was equal to 3.69 and 3.01 mg/g, respectively). Similar effect was visible for Se, that is, its adsorbed amount was slightly reduced at higher pH values (2.78, 2.59, and 2.43 mg/g for pH 5, 6, and 7, respectively). Surface charge density of OFM800 was less positive at higher pH values and thus electrostatic attraction between oxyanions and the solid particles were weakened. On the contrary, for Cd and Cu, the adsorption capacity of OFM800 adsorbent increased at higher pH values. When the pH value increased, the solid surface became protonated and had a less positive charge. As a result, the electrostatic repulsion between cations and positively charged solid was reduced, which made their contact easier. The amounts of Cu adsorbed on the selected adsorbents were 19.94, 23.40, and 29.22 mg/g, whereas those of Cd were 22.22, 28.66, and 33.76 mg/g for pH 5, 6, and 7, respectively.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section3\"\u003e \u003ch2\u003e3.3.4. XPS, EDS and FTIR after adsorption studies with metals and metaloids\u003c/h2\u003e \u003cp\u003eThe EDS analyses (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, A.7) confirmed that Cu, Cd, As, and Se were adsorbed on the OFM800 surface. Additional peaks corresponding to metal/metalloid ions were visible in the spectra. The changes in the FTIR spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb) after ion adsorption were not significant. The XPS results (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) indicated that As was adsorbed as arsenic oxide compounds (45 eV) (Tian et al., \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), whereas Se, as NaSeO\u003csub\u003e3\u003c/sub\u003e (59 eV) and HSeO\u003csub\u003e3\u003c/sub\u003e (60–61 eV) (Naveau et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2007\u003c/span\u003e). The peaks registered for Cd corresponded to its + 2 oxidation state (413–416 eV, 406–409 eV), namely Cd(OH)\u003csup\u003e+\u003c/sup\u003e or Cd(OH)\u003csub\u003e2\u003c/sub\u003e (Wang et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). In turn, Cu ions formed Cu\u003csub\u003e2\u003c/sub\u003eO (932 eV) and CuCl\u003csub\u003e2\u003c/sub\u003e (935 eV) on the solid surface (Biesinger, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Polymer adsorption mechanisms on the OB-derived materials\u003c/h2\u003e \u003cp\u003eThe measured amounts of polymers adsorbed on OBCC, OBCM, OFC800 and OFM800 at different pH values are presented in Fig.\u0026nbsp;5ab. The EPS and AnPAM adsorption decreased slightly with increasing pH value. For the initial EPS concentration of 100 mg/L, its adsorbed amount was 20.75 mg/g at pH 5, 16.14 mg/g at pH 6 and 4.15 mg/g at pH 7. Carboxylic groups present in the EPS chains underwent gradual dissociation as the pH of the solution increased. According to Szewczuk-Karpisz et al. (\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), the pK\u003csub\u003ea\u003c/sub\u003e parameter of EPS was 5.1 (50% of carboxylic groups were dissociated then). At pH 7, 98.7% of the groups were dissociated, which was equivalent to more expanded conformation of the macromolecules. Such polymer chains occupied a much larger area of the solid during adsorption, and consequently, the amount of adsorbed EPS was reduced at higher pH value. The EPS and AnPAM adsorption was favoured by electrostatic attraction occurring between the negatively charged macromolecules and the positively charged surface of solid. For CtPAM, the tendency was completely different, i.e., its adsorption increased with increasing pH. This was connected with different conformation of polymer chains. AnPAM formed adsorption layer of lower thickness with ‘loops’ and ‘tails’ of short length. In turn, due to the electrostatic repulsion between positively charged CtPAM macromolecules and adsorbent particles, this polymer formed long ‘loops’ and ‘tails’, which limited its contact with the surface. As a result, more chains could fit on a unit area of the solid and the amount of adsorbed polymer was greater.\u003c/p\u003e \u003cdiv id=\"Sec19\" class=\"Section3\"\u003e \u003ch2\u003e3.4.1. Polymer impact on solid surface charge\u003c/h2\u003e \u003cp\u003eThe modification of OFM800 clearly influenced its surface charge density as well as the pH\u003csub\u003epzc\u003c/sub\u003e value (Fig. A.3d). This effect was strongly dependent on the type of polymer and the content of ionizable groups in the macromolecules. Typically, dissociated carboxylic groups (-COO\u003csup\u003e−\u003c/sup\u003e) of the polymer fragments located near the surface contribute to the reduction in absolute values of negative σ\u003csub\u003e0\u003c/sub\u003e parameter. Conversely, the -COO\u003csup\u003e−\u003c/sup\u003e moieties found in 'loops' and 'tails' of the adsorbed polymer chains lead to increase in the absolute values of negative σ\u003csub\u003e0\u003c/sub\u003e parameter (Szewczuk-Karpisz et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). In the analyzed systems, the latter phenomenon prevailed. In the presence of AnPAM a significant increase in the absolute values of negative surface charge was observed, and pH\u003csub\u003epzc\u003c/sub\u003e decreased from 10.1 to 8.3. The positive groups still prevailed on the OFM800 surface – the σ\u003csub\u003e0\u003c/sub\u003e parameter equaled 20 µC/cm\u003csup\u003e2\u003c/sup\u003e at pH 5, 16.3 µC/cm\u003csup\u003e2\u003c/sup\u003e, pH 6, and 6.3 µC/cm\u003csup\u003e2\u003c/sup\u003e at pH 7. The EPS adsorption contributed to a slight reduction in the pH\u003csub\u003epzc\u003c/sub\u003e value to 9.8 as well as in the absolute values of negative surface charge. This was also induced by the dissociated -COO\u003csup\u003e−\u003c/sup\u003e groups present in the ‘loops’ and ‘tails’ of the adsorbed polymer chains.\u003c/p\u003e \u003cp\u003eThe quaternary amine groups of CtPAM also influenced the OFM800 surface charge. Generally, when positive moieties are situated in segments of the adsorbed polymer (very close to the solid surface), they contribute to an increase in the absolute values of negative surface charge. Conversely, their placement in polymer fragments located in the by-surface layer, resulted in a reduction in the absolute values of negative surface charge (Szewczuk-Karpisz et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). In the case of the examined systems, the influence of CtPAM was not clear. Probably, the the number of positively charged groups in the adsorbed segments and those located within the 'loops' and 'tails' was very similar. CtPAM caused only a slight reduction in pH\u003csub\u003epzc\u003c/sub\u003e to 9.8.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Adsorption in the mixed systems\u003c/h2\u003e \u003cdiv id=\"Sec21\" class=\"Section3\"\u003e \u003ch2\u003e3.5.1. Mixed systems of metal/metalloid ions and herbicide\u003c/h2\u003e \u003cp\u003eIn the mixed systems containing two metal/metalloid ions or one metal/metalloid ion and one herbicide simultaneously, adsorption was different than in the single ones (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003e). As, Se, Cd, and Cu ions were adsorbed in larger amounts after addition of DCMU and GLY. Similarly, when As and Se were present together in the system, their adsorption was enhanced. In both cases, the formation of complexes between metal and metalloid ions or two metalloid ions based on hydrogen bonds took place (Fijałkowska et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). The simultaneous presence of metal ions, Cd and Cu, reduced their adsorption on the solid surface, which was dictated by the competition between both cations for active sites.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec22\" class=\"Section3\"\u003e \u003ch2\u003e3.5.2. Mixed systems of metal/metalloid ions and macromolecular compounds\u003c/h2\u003e \u003cp\u003eModification of solids with polymers also influenced the metal/metalloid adsorption (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e5\u003c/span\u003ec-f), which was mainly associated with the complexation of macromolecular compounds and ions (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). CtPAM made Se and As adsorption higher by 2.2- and 2.6-times, respectively, when initial metalloid concentration was 100 mg/L. This polymer contributed to higher absolute values of positive surface charge at pH 6, which facilitated contact between oxyanions and solid particles. In the case of Cu, CtPAM significantly reduced its adsorption (by almost 80%), which was the result of strong electrostatic repulsion between positively charged quaternary amine groups and Cu cations. Surprisingly, this phenomenon did not occur for Cd. Probably, both metals, due to differences in electronegativity (Cu = 1.90 and Cd = 1.70 in Pauling’s scale), formed different types of complexes with CtPAM, i.e., intramolecular or intermolecular one (Szewczuk-Karpisz et al., \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). CtPAM is composed of fragments with quaternary amine moieties (-N(CH\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e) being a source of positive charge as well as neutral amide groups. The latter have free electron pairs located on the N atom, that may participate in the formation of a covalent bond between CtPAM and cations (Zhou et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Anionic polymers, EPS and AnPAM, increased adsorption of most metals and metalloids. Se adsorption in the presence of AnPAM was only one exception. In the case of metals, the adsorption was greater even by 1.6 times in the EPS presence. This was mainly associated with the introduction of additional negative groups (-COO\u003csup\u003e−\u003c/sup\u003e) together with anionic macromolecules, with which cations could interact electrostatically. On the other hand, As oxyanions were involved in hydrogen bond formation with the polymer functional groups. The formed ion-polymer complexes were adsorbed on the solid surface and, as a result, Cd/Cu/As adsorbed amount increased.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section2\"\u003e \u003ch2\u003e3.6. Desorption of metal/metalloids from B and produced materials\u003c/h2\u003e \u003cp\u003eDesorption study allowed to determine the binding strength of selected metal/metalloids with and without polymers (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Desorption was performed in three cycles, and, as expected, it was the highest in the first cycle. Due to the weakness of the interaction between Cd/Cu cations and positively charged OFM800, their desorption was the greatest among all ions. In the first cycle, it was in the range 5.96–44.61% for Cu and 4.23–9.44% for Cd. For As/Se, that were electrostatically attracted to the surface, the desorption degree was much lower, 0.72–4.36%. The immobilization of metals/metalloids was enhanced by polymers. A clear reduction in desorption was observed for Se with AnPAM as well as Cu/Cd with EPS/AnPAM. Then, ion-polymer complexation as well as polymer adsorption on the solid surface limited the leaching of metals and metalloids and thus reduced their bioavailability.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eThe authors developed fruit waste-derived activated carbons produced using CO\u003csub\u003e2\u003c/sub\u003e-consuming microwave-assisted method of satisfied adsorption capacity towards various substances. For initial metal concentration of 100 mg/L, it adsorbed 57.32% of Cu and 46.8% Cd. Surprisingly, these values increased in the mixed systems with diuron (10 mg/L) to the values of 64.42% and 61.5%, respectively, which meant that the investigated adsorbed remained high ability to bind toxic compounds in the solutions with both organic and inorganic compounds. The selected orange peels AC had enhanced adsorption capacity also in the systems with metals/metalloids and polymers. The CtPAM presence increased Se/As adsorption, whereas the one with EPS or AnPAM, enhanced Cd/Cu/As binding. The Cu removal rate was equal to even 96.52% in the EPS presence (100 mg/L). Anionic polymers made metal/metalloid immobilization stronger limiting their bioavailability. Thus, the produced material is of high environmental importance.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eAuthor ContributionsSylwia Kukowska: Conceptualization, Investigation, Writing \u0026ndash; Original draft preparation, Data Curation, Visualization, Methodology, Piotr Nowicki: Investigation, Resources, Writing \u0026ndash; Reviewing and editing, Katarzyna Szewczuk-Karpisz: Writing \u0026ndash; Reviewing and editing, Supervision, Project administration.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThe study was financed by National Science Centre, Poland (OPUS21, 2021/41/B/NZ9/03059).\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eData will be made available on request to the corresponding author.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eBelhachemi, M., Addoun, F., 2011. 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Molybdenite Flotation in the Presence of a Polyacrylamide of Low Anionicity Subjected to Different Conditions of Mechanical Shearing. Minerals 10, 895.\u003c/li\u003e\n\u003cli\u003eFeng, N., Guo, X., Liang, S., Zhu, Y., Liu, J., 2011. Biosorption of heavy metals from aqueous solutions by chemically modified orange peel. J. Hazard. Mater. 185(1), 49\u0026ndash;54.\u003c/li\u003e\n\u003cli\u003eFijałkowska, G., Szewczuk-Karpisz, K., Wiśniewska, M., 2019. Chromium(VI) and lead(II) accumulation at the montmorillonite/aqueous solution interface in the presence of polyacrylamide containing quaternary amine groups. J. Mol. Liq. 293, 111514.\u003c/li\u003e\n\u003cli\u003eGenchi, G., Sinicropi, M.S., Lauria, G., Carocci, A., Catalano, A., 2020. The Effects of Cadmium Toxicity. Int. J. Environ. Res. Public Health 17, 3782.\u003c/li\u003e\n\u003cli\u003eGiacomazzi, S., Cochet, N., 2004. Environmental impact of diuron transformation: a review. 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Competitive adsorption of Hg\u003csup\u003e2+\u003c/sup\u003e, Pb\u003csup\u003e2+\u003c/sup\u003e and Co\u003csup\u003e2+\u003c/sup\u003e ions on polyacrylamide/attapulgite. Desalination 270, 269\u0026ndash;274.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"direct/indirect physical activation, conventional/microwave heating, adsorption, polymers, pollutants, waste management","lastPublishedDoi":"10.21203/rs.3.rs-5037429/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5037429/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe main aim of the study was to develop fruit waste-derived activated carbon of high adsorption performance towards metals, metalloids, and polymers by the use of CO\u003csub\u003e2\u003c/sub\u003e-consuming, microwave-assisted method. The authors investigate textural, surface chemistry, and elemental parameters of precursors (chokeberry seeds, black currant seeds, orange peels), biochars (BCs) and activated carbons (ACs) obtained from them. Furthermore, the adsorption mechanisms of metalloids (arsenic, selenium), metals (copper, cadmium) and macromolecular compounds (bacterial exopolysaccharide, ionic polyacrylamides) were studied in one- and two-component systems. ACs prepared via direct and indirect activation as well as through conventional and microwave heating were compared. Microwave heating favoured surface development and, consequently, enhance ability to bind ions or macromolecules. Direct biomass activation led to higher microporosity compared to indirect, two-stage one, whilst CO\u003csub\u003e2\u003c/sub\u003e-consuming activation increased aromaticity and hydrophobicity of the solids. In the selected systems, polymers favoured metal/metalloid adsorption limiting their bioavailability.\u003c/p\u003e","manuscriptTitle":"Designing of fruit waste-derived activated carbon through CO2-consuming and microwave- assisted preparation to enhance and understand its adsorption performance towards metal, metalloid and polymer species","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-11-20 05:56:47","doi":"10.21203/rs.3.rs-5037429/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-10-18T11:26:01+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-10-06T02:17:59+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"332676868492516846723949930170887442172","date":"2024-10-04T07:50:13+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"183002243127205830212874399519644219323","date":"2024-10-04T06:31:34+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-10-03T15:42:01+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"39159079151916485710161552077133351194","date":"2024-10-03T14:15:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"70623705707745348026391787316473354712","date":"2024-10-03T14:10:32+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-10-03T14:08:25+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-10-03T13:55:52+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2024-09-17T02:37:05+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-09-13T15:32:18+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2024-09-05T10:25:56+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"4b8deafa-b4db-4b71-be6f-c36f0bfcebb6","owner":[],"postedDate":"November 20th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":39122887,"name":"Earth and environmental sciences/Environmental sciences"},{"id":39122888,"name":"Earth and environmental sciences/Natural hazards"},{"id":39122889,"name":"Physical sciences/Chemistry"},{"id":39122890,"name":"Physical sciences/Engineering"}],"tags":[],"updatedAt":"2025-01-13T16:05:03+00:00","versionOfRecord":{"articleIdentity":"rs-5037429","link":"https://doi.org/10.1038/s41598-025-85409-0","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-01-07 15:58:03","publishedOnDateReadable":"January 7th, 2025"},"versionCreatedAt":"2024-11-20 05:56:47","video":"","vorDoi":"10.1038/s41598-025-85409-0","vorDoiUrl":"https://doi.org/10.1038/s41598-025-85409-0","workflowStages":[]},"version":"v1","identity":"rs-5037429","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5037429","identity":"rs-5037429","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}