Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Smart guanyl thiosemicarbazide functionalized dialdehyde cellulose for removal of heavy metal ions from aquatic solutions: adsorption characteristics and mechanism study

Smart guanyl thiosemicarbazide functionalized dialdehyde cellulose for removal of heavy metal... In recent years, facing the problem of improving environmental quality, cellulose and cellulose-based (nano) composites have received great attention as adsorbents. In this work, we report the modification and functionalization of cellulose by nitrogen- and sulfur-containing moieties through a three-steps process; native cellulose is first oxidized by potassium periodate (KIO ) to form dialdehyde cellulose (DAC), which then condenses with aminoguanidine and react with phenyl isothiocyanate to form 4-phenyl guanyl thiosemicarbazide dialdehyde cellulose (DAC@GuTSC). The prepared DAC@GuTSC is characterized by a number of techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental analysis (EA), Brunauer–Emmett–Teller (BET) and thermogravimetric analysis (TGA). The prepared DAC@ 2+ 2+ 2+ GuTSC adsorbent was used to remove Cu Hg and Pb from aqueous solution and environmental water samples. The influence of various factors on the adsorption efficiency including pH, initial metal concentration, contact time, adsorbent dosage, temperature, and ions interfering with adsorption was investigated. Under optimal adsorption conditions, the adsorp- 2+ 2+ 2+ −1 tion capacity of Cu, Hg and Pb was 50, 94 and 55 mg  g , respectively. The adsorption process is well described by the Langmuir model, and it was found to follow the pseudo-second-order kinetics model. The spontaneous and endothermic 2+ 2+ 2+ adsorption of Cu, Hg and Pb was confirmed by the calculated thermodynamic functions. The prepared DAC@GuTSC 2+ 2+ 2+ composite has been successfully applied to remove Cu, Hg and Pb from real water samples with recovery greater than 2+ 2+ 2+ 90% and relative standard deviation (RSD) less than 3%. The reasonable Cu , Hg and Pb adsorption mechanism on the prepared DAC@GuTSC composite has been elucidated. Keywords Adsorption · Cellulose · Aminoguanidine · Phenyl isothiocyanate · Heavy metals · Water treatment Introduction and persist for long periods (Nouri et al. 2007). These heavy metals can cause a number of diseases and disorders, even Clean and safe water is an eternal need of every individual. at very small concentrations (Gotoh et al. 2004a, 2004b). In recent decades, freshwater resources have been directly For example, lead has a number of health effects, includ- threatened by increasing industrialization worldwide (Jamil ing anemia, hypertension and digestive disorders (Gherasim et al. 2009).Discharged industrial waste significantly con - and Mikulášek 2014; Martin and Griswold 2009) while high taminates water sources by releasing a number of pollutants, copper levels can cause abdominal strain and kidney failure including organics and heavy metals (Liu and Huang 2011). (Bilal et al. 2013; Chaturvedi 2013) mercury is believed to Unlike organic pollutants, heavy metals such as Hg, Pb, Cu, have toxic effects on the nervous system, leading to serious Cd and Zn are not biodegradable and tend to accumulate disorders such as brain damage, memory loss, behavioral abnormalities and autism (Chang 1977; Clarkson 1993; Clarkson and Magos 2006; Friberg and Mottet 1989; Guzzi * Magda A. Akl and La Porta 2008; Magos and Clarkson 2006). magdaakl@yahoo.com To avoid serious impacts on the environment and public 1 health, several techniques have been developed to remove Department of Chemistry, Faculty of Science, Mansoura heavy metals from water, including ion exchange, chemical University, Mansoura 35516, Egypt Vol.:(0123456789) 1 3 144 Page 2 of 18 Applied Water Science (2023) 13:144 precipitation, membrane filtration and adsorption. (Akl et al. 2013, 2005, 2004; Atta et al. 2013; Ibrahim et al. 2019; Kur- niawan et al. 2006; Lee et al. 2007; Meena et al. 2005; Mon- ier et al. 2014b, 2014a; Nayl et al. 2020; O’Connell et al. 2008; Shoueir et al. 2016, 2017; Wang and Li 2013; Zewail and Yousef 2015). However, adsorption is widely preferred Scheme 1 Schematic representation of determination of the aldehyde over other conventional techniques due to its affordability, content (Dacrory 2021) simplicity, high efficiency and eco-friendly nature (Aydın et  al. 2008; Hua et al. 2012; Khan et al. 2004; Pan et al. 2009; Zhao et al. 2010). iv. Investigating the ideal parameters required for optimal Cellulose is one of the most commonly used biosorbents, adsorption of the studied metal ions, e.g., pH, temper- showing great heavy metal adsorption potential, especially ature, the initial concentration of the three investigated when chemically modified by binding to novel groups via metal ions, the mass of DAC@GuTSC composite and complexation or chelation significantly improves its adsorp- the oscillation time, as well as the interfering ions. tion capacity (Acemioglu and Alma 2001; Aydın et al. 2008; v. Studying the various adsorption isotherm, kinetics and Dridi-Dhaouadi et  al. 2011; Gupta 2009; Navarro et  al. thermodynamic parameters. 1996; Suhas et al. 2016; Wu et al. 2012). It has been shown vi. Comparative evaluation of metal removal efficiency that introducing aminoguanidine to cellulose after oxidizing and reusability of DAC@GuTSC composite with it with KIO improves its adsorption capacity and leads to other previously reported adsorbents. satisfactory removal results for Cu ions, Hg, Pb, Cd and Zn vii. Elucidation of the mechanisms involved in the process +2 +2 +2 of aqueous solutions (Kenawy et al. 2018). of adsorption of Cu , Hg and Pb onto DAC@ In this study, an attempt was made to modify cellulose GuTSC composite. by adding an additional procedure to the above method, that is, adding phenyl isothiocyanate to aminoguanidine modi- fied cellulose and investigating its effectiveness in adsorbing Experimental and methods three heavy metals (i.e., Cu, Hg and Pb) from aqueous solu- tion and real sample. This modification leads to the forma- Materials tion of a new adsorbent 4-pheny guanyl thiosemicarbazide functionalized dialdehyde cellulose (DAC@GuTSC) con- Aminoguanidine monohydrochloride, cellulose powder, taining potentially electron-donating N and S atoms. The phenyl isothiocyanate, potassium metaperiodate (KIO ), presence of N/S atoms provides a stronger chelation regime CuSO, HgCl , Pb(NO ) and triethylamine were purchased 4 2 3 2 with metal ions. from Sigma-Aldrich and directly used. To our knowledge, the modification of cellulose using a nitrogen-containing ligand (aminoguanidine) and a sulfur- Preparations nitrogen phenyl isothiocyanate has not been reported in the literature. Again, no data were found on using DAC@ Preparation of dialdehyde cellulose (DAC) GuTSC modified cellulose as an effective adsorbent for 2+ 2+ 2+ Cu, Hg and Pb from actual polluted water samples. One gram of the native cellulose was oxidized using 100 ml Accordingly, the current study was performed out with these objectives: of 4% potassium periodate. The previous mixture was shaken for 1 h in complete darkness to form dialdehyde cellulose i. Design and synthesis of N and S containing guanyl (DAC), Scheme 1. The obtained DAC was washed several times with dist.H O and was dried in an oven at 50 °C. thiosemicarbazide functionalized dialdehyde cellu- losic composite (DAC@GuTSC) for adsorption of +2 +2 +2 Determination of aldehyde content The aldehyde content Cu, Hg and Pb metal ions in single and multi- component metal ions’ solutions. of DAC is determined by the Schiff base reaction in Fig.  1 according to refs (Dacrory 2021; Dacrory et al. 2019) in ii. Characterization of the as-prepared DAC@GuTSC composite using physical (optical images) elemental which hydroxylamine hydrochloride is used to convert the aldehyde group to the corresponding oxime. 0.3 g of analysis and spectroscopic (FTIR), SEM and TGA instrumental performances. DAC sample was dispersed in 20  ml of distilled water and adjusted to (pH ≈ 5) with NAOH solution. 20 ml of iii. Batch sorption experiments in single and multi-com- 2+ 2+ 2+ ponent metal ions utilizing Cu, Hg and Pb as hydroxylamine hydrochloride solution (0.72 mol/l) of pH 5 was then added. The mixture was stirred at 40  °C for pollutants. 1 3 Applied Water Science (2023) 13:144 Page 3 of 18 144 Fig. 1 a Filtrate of 0.25 M hydroxylamine after stirring for 2.5 h with DAC; b after titration with 0.1 M NaOH 4 h. Released HCl was titrated with 1.0 M NaOH solution. Instrumentation The amount of NaOH consumed when the pH of the solu- tion reached 5.0 was recorded (Ibrahim et al. 2019). The The FTIR spectra of the prepared samples were recorded −1 amount of NaOH solution consumed in the titration was between 4000 and 400  cm . Disks were prepared by first recorded as Va (liters). A pH 5.0 cellulose solution of the mixing 1 mg of dried samples with 500 mg of KBr (Merck, same concentration was used as a blank and the volume for spectroscopy) in an agate mortar and then pressing the −2 of 1.0  M NaOH consumed was recorded as Vc (liters). resulting mixture successively at 8 tons cm . Elemental Aldehyde content (% w/w) calculated using the following analysis was done using a Perkin-Elmer 2400 analyzer. formula (Dacrory 2021) Brunauer–Emmett–Teller (BET) analysis was conducted to evaluate the surface area of the DAC@GuTSC. Ther- −CHO + NH OH − HCl → −CHNOH + HCl + H O 2 2 mogravimetric analysis (TGA) was performed by thermo HCl + NaOH → NaCl + H O analyzer Shimatzu DT40 (Japan) over temperature range of 30–800 °C with N atmosphere and with the heating flow 10 °C/min. In addition, scanning electron microscope (SEM) The aldehyde content for DAC was calculated as shown was used to study the morphology of native cellulose, DAC in Eq. 1: and DAC@GuTSC samples. The samples were sputtered and coated with gold before using scanning electron micro- M V − V NaOH sample control 2+ 2+ 2+ AC(%) = × 100 (1) scope. The concentrations of Cu , Hg and Pb in metal Mwt solutions before and after adsorption were estimated using Agilent's 5100 ICP OES. Where M is the used NaOH concentration (0.1 mol), NaOH The point of zero charge (pH ) was determined using m is the prepared DAC weight, and Mwt is the molecular PZC the solid addition method. In a series of 100 ml jacketed weight of the DAC repeating unit (C H O ) that is equal to 6 8 10 n glasses, 50 ml of KNO solutions of known concentration 160.124 g/mol. V and V are the recorded volumes sample control was transferred. The solutions of different initial pH (pH ) of the NaOH consumption for the DAC sample and control i between 2 and 12 were prepared by adding either 0.1 M HCl one, respectively. The determination of the aldehyde content or 0.1 M NaOH. One gram of DAC@GuTSC composite for DAC is schematically represented in scheme 1 was then added to each solution with stirring for 48 h. The final pH (pH ) was measured and the difference between the initial and final pH values (ΔpH = pH- pH ) was plotted Preparation of the Schiff base guanyl thiosemicarbazide i f against pHi. The pHpzc value is the point where the curve functionalized dialdehyde cellulose (DAC@GuTSC) ΔpH vs pHi crosses the line ΔpH = 0. Guanyl dialdehyde cellulose (DAC@Gu) was prepared by Batch adsorption experiments the same procedure followed in the mentioned study [45] except for increasing the oxidation time for 6 h. Then, 5 ml 2+ 2+ 2+ Batch adsorption of Cu, Hg and Pb was performed in of phenyl isothiocyanate was added to 0.5 g of the guanyl 100 mL reagent bottles containing 50 mL of known initial modified cellulose and immersed in 100 ml of ethanol in concentrations (50, 100, 150, 200) ppm of the metals under the presence of triethylamine. The obtained mixture was investigation and known DAC@GuTSC weights (0.01, 0.03, allowed to reflux for 3 h at 80 °C. Yellow powder of the 0.05) g at a pH of (3–7) adjusted by the addition of 0.1 M guanyl 4-phenyl thiosemicarbazide functionalized dialde- NaOH and/or 0.1 M HCL and a temperature of (25–45)°C hyde cellulose composite (DAC@GuTSC) was obtained (at time intervals of 1–24 h). Bottles containing samples at the end. were shaken on a mechanical shaker for (20–120 min) and 1 3 144 Page 4 of 18 Applied Water Science (2023) 13:144 filtered. Metal ion concentrations in the supernatants were and dried. No reduction in total mass was observed. The determined by ICP OES. DAC@GuTSC adsorbent was insoluble in water. Scheme 2 Then, adsorption capacity and the removal efficiency represents the proposed steps of the synthetic reaction. were evaluated by Eqs. (2) and (3), respectively. Characterization q = C − C V∕W (2) e i e Infrared spectroscopy C − C i e Removal (%) = × 100 (3) The obtained IR spectra for native, DAC, DAC@Gu and DAC@GuTSC samples are presented in Fig. 2(a–d). −1 where q is the adsorption capacity in mg  g , C is the initial e i The FTIR spectrum of unmodified natural cellulose −1 concentration of metal ion under study in (mg  L ), C is Fig. 2a and (Fig.S1a) shows some characteristic peaks in −1 the equilibrium concentration of metal ions in (mg  L ), V −1 the range of 1000–1200  cm corresponding to C-O elon- volume of solution in (liter), and W is adsorbent mass in (g). gation. While the peaks present at 1260–1410 cm − 1 are attributed to the OH bending vibrations, the peaks present −1 between 3600 and 3200  cm correspond to the OH stretch- Results and discussion ing vibrations (Xu et al. 2013). Other peaks occurring at −1 2700–3000  cm are due to C–H elongation. Materials' design The IR spectrum of DAC in Fig. 2.b and (Fig. S1b) shows an extremely sharp peak that is moderately sharp at about Synthesis of dialdehyde cellulose (DAC) −1 1650  cm , which is due to prolonged oscillations of the groups carbonyl (C=O) is formed during oxidation ( Akl KIO , a known selective oxidizing agent, oxidizes two et al. 2021). hydroxyl groups on two neighboring carbon atoms C –C 2 3 Modification of DAC by reaction with aminoguanidine bond of the glucopyranoside ring that will be cleaved and causes some changes in the IR spectrum, notably a sharp converted into two dialdehyde groups. The oxidation degree −1 peak at about 1720  cm , possibly due to C=N formation which represents the percentage of monosaccharide units between the aldehyde groups present in the cellulose being that reacted with KI O is calculated by aldehyde content oxidants and amino groups of the added aminoguanidine determination (Akl et al. 2021). The aldehyde content of the [45] as shown in Fig. 2c and (Fig. S1c). prepared DAC is 35.71% as it is presented in Table1. Figure 2d and (Fig. S1d) show the IR spectrum of DAC@ GuTSC composite after insertion of phenyl isothiocy- Synthesis of the Schiff base DAC@GuTSC composite −1 anate. The presence of new peaks between 1120  cm and −1 960  cm may be related to group C=S [49] present in the Natural cellulose powder was selectively oxidized by KIO inserted phenyl isothiocyanate. Alternatively, the broad peak to give the dialdehyde form (DAC) with aminoguanidine at −1 at about 2900  cm could be due to the introduction of a 80 °C. The product (DAC@Gu) was further reacted with phenyl group. Furthermore, the overlapping peaks occurring phenyl isothiocyanate to form the DAC@GuTSC compos- −1 −1 between 1520  cm and 1650  cm can be attributed to the ite with additional nitrogen and sulfur functionalities. The unsaturated C–N–H, N=CH– and C=C bonds in the aro- water solubility of the DAC@GuTSC adsorbent was tested matic rings of the phenyl group (Balachandran and Murali by suspending a 1.00 g sample of the DAC@GuTSC adsor- 2011). The observed differences in IR spectra support the bent in 50.0 mL of water. After stirring the suspension for denaturation of natural cellulose and the insertion of new about 3.0 h, the resulting solid was collected by filtration N and S functional groups into the newly prepared DAC@ GuTSC composite. Elemental analysis Table 1 Volumetric titration of DAC for determination of average aldehyde content percentage (AC, %) The results of elemental analysis for native cellulose and Vcontrol Vsample CNaOH m (gm) AC % Average modified cellulose are summarized in Table  2. The results (ml) (ml) (M) AC% revealed an addition of nitrogen and sulfur to the elemen- 0.5 2.7 0.1 0.1 35.2 35.71 tal composition of cellulose which indicates the successful 0.5 2.7 0.1 0.1 35.2 0.5 2.8 0.1 0.1 36.8 1 3 Applied Water Science (2023) 13:144 Page 5 of 18 144 Scheme 2 Synthesis of DAC@GuTSC composite Scanning electron microscopy (SEM) (d) The surface morphology of DAC and DAC@GuTSC com- posite was studied by scanning electron microscopy at (c) 5000X, 15000X and 27000X magnifications. Figure  3 shows the SEM images obtained at three magnifications. One can (b) directly notice that the surface of the cellulose becomes rougher after being modified, which indicates the inser - (a) tion of new moieties into the original structure. In addition, 50 the surface of DAC@GuTSC has been shown to have large pores and pores that can help trapping metal ions during adsorption. 4000 3500 3000 2500 2000 1500 1000 500 -1 Wavenumber (cm ) Brunauer–Emmett–Teller analysis (BET) Fig. 2 FTIR of a native cellulose, b DAC, c DAC@Gu and d DAC@ The BET surface analysis was applied to evaluate the spe- GuTSC composite cific surface properties of the samples. The results indicate that natural cellulose and the DAC@GuTSC sorbent are Table 2 Elemental analysis of native cellulose and DAC@GuTSC microporous materials in nature. In addition, BET-specific surface area calculations showed that natural cellulose fib- Sample Carbon (%) Hydrogen Nitrogen (%) Sulfur (%) 2 −1 ers have a higher surface area (21.264 m  g ) than DAC@ (%) 2 −1 GuTSC composite (3.038 m   g ), Table 3. The decrease Native cel- 44.5 7.14 – – in surface area after chemical modification may be due to lulose the covering of cellulose pores by anchoring guanyl thio- DAC@ 46.4 5.81 8.32 3.81 semicarbazide moieties which reduces the adsorption of N GuTSC molecules used in the surface measurement. The relatively low surface area of the functionalized fibers suggests that modification of cellulose by introduction of new nitrogen the adsorption occurs mainly through the coordination of and sulfur functional groups. the N, N- and N, S donors of the guanyl thiosemicarbazide moieties with metal ions. 1 3 Transmittance (%) 144 Page 6 of 18 Applied Water Science (2023) 13:144 Fig. 3 SEM images of oxidized cellulose at a 5000×, b 15000×, c 27,000× and DAC@GuTSC at d 5000×, b 15,000× and f 27000× Table 3 BET analysis results Fig. 4a shows four stages of thermal decomposition, which in turn confirms the appearance of a change in the com- Sample Adsorp- Adsorp- Mean Surface Total pore position of natural cellulose. At 750 °C, the final residual weight tive tion tem- pore area volume 2 −1 3 −1 perature diameter (m  g ) (cm  g ) weight of DAC@GuTSC composite is 0.96%, indicating the (nm) remarkable thermal stability of DAC@GuTSC composite at very high temperatures. After adsorption of metal ions, the 0.0753 N2 77 K 4.7503 3.038 0.003608 final remaining mass of the DAC@GuTSC–metal complex at 750 °C was 41.3%, 40.2% and 56.1% for DAC@, GuTSC- Thermal gravimetric analysis (TGA) Cu, DAC@GuTSC-Hg and DAC@GuTSC-Pb, respectively. The increased residue value after metal adsorption compared A thermal gravimetric analysis (TGA) was performed to with DAC@GuTSC composite indicates their higher ther- mal stability. investigate the thermal decomposition of the DAC@GuTSC adsorbent before and after adsorption of heavy metal ions. Adsorption studies As shown in Fig. 4, in the temperature range (0–200)  °C, there is a very slight weight loss that actually starts after Point of zero charge (pH ) 100 °C mainly due to the evaporation of the water parts. PZC The reduced mass started to increase from about 250 °C The pH of adsorbent is one way to understand the to about 450 °C due to the pyrolysis of the sample. Simi- PZC lar decomposition behavior was observed before and after absorption mechanism. The surface charge of the DAC@ GuTSC adsorbent was assessed by measuring the pH . adsorption. The heatmap of natural cellulose shows two PZC stages of thermal degradation that typically yield levoglu- In general, adsorbents will show better affinity for anions at pH < pH and vice versa. The pH value obtained cosan and anhydrocellulose (Mohan et al. 2006). While the PZC PZC thermogram obtained from DAC@GuTSC composite in for the DAC@GuTSC composite is about 5.75, Figure 1 3 Applied Water Science (2023) 13:144 Page 7 of 18 144 Fig. 4 TGA curves of a DAC@GuTSC, b DAC@GuTSC-Cu, c DAC@GuTSC-Hg, d DAC@GuTSC-Pb S2. It is expected that the adsorption of metal ions can Eec ff t of pH be increased at the experimental pH (pH = 6) by electro- static interaction between Hg(II), Cu(II) and Pb(II), and The influence of pH value in the range 1.0–7.0 on metal the nitrogen-containing functional groups on the surface removal by DAC@GuTSC is shown in Fig. 5. The adsorp- of DAC@GuTSC. tion capacity (qe) exhibits an increasing trend with increase 2+ 2+ 2+ in pH value until peaking at pH 6 for Cu, Hg and Pb . The observed decrease trend in the removal % at low pH values can be explained by protonation taking place in an Fig. 5 Effect of pH on the 100 adsorption of Cu, Hg and Pb Cu onto DAC@GuTSC composite Hg Pb 123456 7 pH 1 3 q (mg/g) e 144 Page 8 of 18 Applied Water Science (2023) 13:144 acidic environment where protons are attached to negatively ions per unit volume increases. The chance of metal ions charged groups on the fiber of the adsorbent, thereby com- contacting DAC@GuTSC composite increases, resulting peting with the intended metal ions to be adsorbed. in a rapid increase in the amount of metal ions adsorbed. However, with a further increase in the initial concentration, Eec ff t of adsorbent dose the adsorption efficiency of DAC@GuTSC for metal ions reaches saturation, and the growth rate of the adsorption The adsorbent dosage was varied from 0.01 g to 0.1 g and curve becomes flat. the adsorption capacity was estimated for each dose. Fig- To better represent the effect of initial concentration on ure 6 describes the relationship between adsorbent dosage adsorption, Langmuir and Freundlich’s adsorption isotherm and adsorption capacity of DAC@GuTSC adsorbent. From models were used using linearization Eqs. (4) and (5) the figure, it can be concluded that the adsorption capacity ln q = ln K + 1∕n ln C (4) e F e increases as the adsorbent dose increases in a direct relation- ship, which may simply be due to the increased number of C ∕q = 1∕K q + C ∕q active sites. Then, when heavy metal saturation is reached, (5) e e L m e m the adsorption capacity becomes constant as the adsorbent 2+ 2+ where q is the equilibrium adsorption capacity, K is the e F dosage increases. Cu and Pb show saturation values at Freundlich constant, n is the heterogeneity coefficient 0.05 g of DAC@GuTSC adsorbent, while the maximum reflecting the energy distribution in the bonds, C is the equi- adsorption capacity for H g is only 0.03 g. The obtained librium metal concentration, K is the Langmuir constant, results have proven that the DAC@GuTSC adsorbent is a L and q is the maximum adsorption capacity of a layer. very effective heavy metal adsorbent with very low dosage. The adsorbent convenience was then investigated by cal- culating (R ) as the constant of the separation coefficient Eec ff t of the initial metal ion's concentration using Eq. (6). and adsorption isotherms R = 1∕ 1 + C K (6) L o L The effect of the initial concentration (C ) of different metal ions on the adsorption performance of DAC@GuTSC com- where K is the Langmuir adsorption constant and C is the L o posite is shown in Fig. 7. All the metal ion adsorption curves initial concentration of metal ions. of DAC@GuTSC composite have similar trends. As the ini- R values greater than 1.0 indicate adsorbent mismatch, tial concentration of metal ions in the solution increases, while R values between 0 and 1 indicate adsorbent concord- the adsorption capacities of DAC@GuTSC composite for ance. The derived parameters are listed in Table 4. From various metal ions show an overall upward trend. After the estimated values of the parameters for DAC@GuTSC, reaching a certain concentration, the upward trend of the it is found that the correlation coefficients in Langmuir’s adsorption curve slows down. An increase in the concentra- model are very high, which means the real data correspond tion of metal ions means that the absolute content of metal Fig. 6 Effect of adsorbent dose on the adsorption of Cu, Hg and Pb 1 3 Applied Water Science (2023) 13:144 Page 9 of 18 144 Fig. 7 Effect of initial metal ion concentration on the adsorption of Cu, Hg and Pb onto DAC@ GuTSC Table 4 Langmuir and Freundlich constants for metal adsorption by Eec ff t oscillation time and adsorption kinetics DAC@GuTSC Figure 8 shows the effects of oscillation time on the adsorp- Langmuir isotherm model 2+ 2+ 2+ tion of Cu, Hg and Pb onto DAC@GuTSC. It can be Adsorbates K (L/g) q (mg/g) R R L m 2 L seen that removal efficiency and adsorption capacity all 2+ Cu 0.384 80.65 0.9992 0.0103– increased rapidly and then remained stable with the increase 0.0495 in oscillation time. In adsorption initial stage, there were 2+ Hg 12.625 99.01 1 0.0003– many usable adsorption sites in the surface DAC@GuTSC, 0.0017 2+ 2+ 2+ accelerating the adsorption speed of Cu , Hg and Pb . 2+ Pb 0.366 84.03 0.9993 0.0108– As time went on, a large number of empty adsorption sites 0.0518 2+ 2+ 2+ had been occupied by Cu , Hg and Pb . This leads to the Freundlich isotherm model reduction of effective adsorption sites and adsorption speed. Adsorbates K n R F 2 Thus, in the later stage, their removal efficiency and adsorp- 2+ tion capacity unchanged insignificantly and finally reached Cu 62.23 24.04 0.7721 2+ equilibrium. The selection of proper adsorption equilibrium Hg 82.02 21.23 0.8716 2+ time can effectively shorten adsorption period. Thus, the Pb 64.70 24.04 0.8479 2+ 2+ 2+ oscillation time for the adsorption of Cu , Hg and Pb was 240 min. significantly to the model Langmuir. Meanwhile, the R Figure 8 represents the relationship between time of con- 2+ coefficients obtained from the Freundlich isotherm plot are tact and adsorption capacity for DAC@GuTSC-Hg by much lower. In addition, the maximum adsorption capacity DAC@GuTSC composite was the most rapid followed by 2+ 2+ for one layer (q ) obtained from the Langmuir plot is con- Pb and C u . Maximum adsorption capacity of DAC@ sistent with the experimental records, which clearly confirms GuTSC composite was reached approximately in the first that the adsorption process will be better described by Lang- 6 h and then equilibrium was reached. muir’s isothermal model. All calculated values of R ranged The obtained experimental data have been adapted to two from 0.0 to 1.0, confirming the suitability of DAC@GuTSC kinetic adsorption models; pseudo-first and pseudo-second- as adsorbent for the metal ions studied. order models to predict the adsorption mechanism. The kin- ematic parameters are calculated using Eqs. (7) and (8). 1 3 144 Page 10 of 18 Applied Water Science (2023) 13:144 Fig. 8 Effect of oscillation time on the adsorption of Cu, Hg and Pb onto DAC@GuTSC Pseudo-first-order (PFO) linear equation: Table 5 Kinetic parameters derived from pseudo-first-order model 2+ 2+ and pseudo-second-order model for adsorption of (Cu, Hg and 2+ 1∕q = k ∕q t + 1∕q Pb ) by DAC@GuTSC t(ads) 1 e(ads) e(ads) (7) 2+ 2+ 2+ Cu Hg Pb Pseudo-second-order (PSO) linear equation: Pseudo-first order t∕q = 1∕k q + 1∕q t (8) t(ads) 2 e(ads) e(ads)  q (mg/g) 62.11 108.7 64.9 e(ads) −1  K (min ) 116.77 135.97 97.51 where q is the equilibrium adsorption capacity, q e(ads) t(ads) 2  R 0.9712 0.9031 0.9709 is the adsorption capacity at time t, K is the adsorption Pseudo-second order rate constant of the pseudo-first-order model, and K is the  q (mg/g) 53 105.26 58 e(ads) adsorption rate constant. -4 −5 −4  k (g/(mg min)3.9 ×  108.65 ×  103.47 ×  10 The estimated kinetic parameters from the two models  R 0.9943 0.9842 0.9959 are summarized in Table  5, while the plotted curves are shown in Fig.  9. From the parameters obtained from the pseudo-first-order curves, it can be seen that the correlation coefficients (R ) are high, but the theoretical equilibrium chemisorption is the main dominant process and it is also adsorption capacity q for each metal does not match believed to be the limiting factor. e(ads) the experimental profile. On the other hand, the parame- ters calculated by pseudo-second-order model are consist- ent with the experimental results because the R value is Eec ff t of temperature thermodynamic parameters also high when approaching 1 and the adsorption capacity is consistent with the experimental results. Regarding the To investigate the effect of temperature on the adsorption of rate constants (K and K ) calculated in each model, it can the studied metal ions, several thermodynamic properties 1 2 be directly observed that the rate constants calculated from were investigated, including the Gibbs free energy change the first-order model are high, that is, the adsorption rate is (ΔG°), the thermal equilibrium constant (K ), standard slow, and therefore, it is inconsistent with the experimen- entropy change (ΔS°) and standard enthalpy change (ΔH°). tal results. Meanwhile, the rate constants obtained from the The values of the mentioned thermodynamic parameters are pseudo-second-order model are much smaller, which is more calculated after plotting 1/T vs LnK using Eqs. 9–11. significant and correlated with experimental results. Thus, it K = C ∕C 2+ 2+ 2+ (9) C ad e can be deduced that the adsorption of Cu , Hg and Pb by the DAC@GuTSC composite exhibits a pseudo-second- o o ln K =ΔS ∕R −ΔH ∕RT order kinetic model perfectly. It can also be concluded that C (10) ads ads 1 3 Applied Water Science (2023) 13:144 Page 11 of 18 144 Fig. 9 Adsorption kinetics models: a PFO, b PSO models Fig. 10 Relation between Lnk and 1/T for adsorption of Cu , +2 +2 Hg and Pb onto DAC@ GuTSC +2 +2 R is gas constant (8.314 J/mol K). Table 6 Thermodynamic parameters of adsorption of Cu, Hg and Pb by DAC@GuTSC ΔG =−RT ln K C (11) ads o o o ΔG (KJ /mol) ΔH (KJ/mol) ΔS (J/mol K) ads ads ads Figure 10 shows that the curves are plotted and the values 298 K 308 K 318 K − 421.39 − 1335.15 obtained are all listed in Table  6. The temperature range 2+ Cu − 26.82 − 2.42 − 0.59 studied is 298–318 K. The thermodynamic parameters of 2+ Hg − 28.39 − 2.55 − 0.85 − 442.58 − 1401.82 +2 +2 +2 the adsorption of C u, Hg and P b by DAC@GuTSC 2+ Pb − 27.06 − 4.54 − 0.74 − 422.31 − 1335.48 adsorbent are described in Table 6. Gibbs (ΔG ) free energy values for the whole adsorp- ads tion process show the spontaneity of the adsorption pro- metal ions of the studied adsorbent. Therefore, it is best to cess in the studied temperature range. The enthalpy change conduct adsorption experiments at moderately low temper- values (ΔH°) are also negative for all adsorption processes atures such as 298 K which is normal room temperature. indicating their exothermic behavior. The standard entropy change (ΔS°) is a measure of the randomness or distribu- Eec ff t of some selected interfering ions: tion of energy in a system. The negative ΔS° values also indicate that the low randomness reflects the high affinity The effect of the presence of foreign ions on heavy metal between the two modified cellulose (DAC@GuTSC) and adsorption was investigated under optimal adsorption condi- the adsorbed metal ions, which is a very good indication tions. The percentage removal for each metal is estimated at of the adsorption efficiency. Thus, it can be concluded that 50 ppm for certain interfering ions. The concentration of the high temperature is not favorable for the adsorption of 1 3 144 Page 12 of 18 Applied Water Science (2023) 13:144 Table 7 Removal of heavy metals on DAC@GuTSC in the presence Table 8 Repeated adsorption Cycle Recovery (%) 2+ 2+ of interfering ions of metal ions Cu, Hg and number 2+ −1 2+ 2+ 2+ Pb (50 ml of 50 mg L L ) Cu Hg Pb Interfering ions Added concentrations of % Removal by DAC@GuTSC sorbent interfering ions (ppm) 1 99.4 99.6 99.1 2+ 2+ 2+ (0.050 g), pH 6, time of shaking Cu Hg Pb 120 min, 25 oC, desorption by 2 98.5 98.6 98.1 2+ 5 mL of 0.5 mol/L HNO3 Mg 50 99.3 100 99.6 3 97.7 97.2 97.3 2+ Fe 50 98.7 98.4 98.1 4 96.4 96.3 96.8 2+ Ca 50 99.1 100 99.7 5 95.6 95.2 95.6 3+ Al 50 95.3 96.1 97.6 3− PO 50 84.6 99.4 98.5 Acetate 50 98.2 98.7 97.6 multi-metal solutions. As shown in Table  9, the percent- Oxalate 50 98.3 98.6 99.1 age removal shows the same trend of single-metal solutions Edetate 50 98.2 98.1 97.2 without obvious difference. The results also correlate with the conclusion obtained in the ionic hindrance that DAC@ GuTSC will perform efficiently in complex multi-component interfering ions is exactly equal to the metal concentration. All samples. The ICP OES is used to simultaneously determine results are summarized in Table 7. From the results obtained, the concentrations of multiple metal ions in the solutions it can be concluded that the presence of 50 ppm cations such studied. 2+ 2+ 2+ 3+ 3− as Mg, Fe, Ca and Al and anions such as PO , ace- tate, oxalate and edetate has no significant effect on heavy Accuracy and application of the method metal removal by DAC@GuTSC. The results give a promis- ing indication of the selectivity of DAC@GuTSC, suggesting To study the accuracy of the proposed procedure, known its potential for efficient operation in more complex media. amounts of analyte ions are added to tap water, Nile water and seawater samples, and then the proposed method is Eec ff t of sample volume applied. The results are presented in Table  10. There is good agreement between the amount of metal added and In order to deal with real samples, especially water samples, the amount measured. The calculated recovery values are containing very low concentrations of the metal ions, the always greater than 95%, thus confirming the accuracy of maximum applicable sample volume must be determined. the proposed procedure and its independence from matrix For this purpose, 25–1000 mL volumes of the model solu- effects. These results confirm the validity of the proposed tions containing 2–20 μg of the trace elements were passed separation/pre-enrichment method. through the column under the optimum conditions. The recovery values as a function of sample volume were quan- Plausible mechanism of adsorption titative and constant up to 1000 mL of the sample solution. The preconcentration factor was calculated as the ratio of To investigate the possible mechanism of metal ion adsorp- the highest sample volume (1000 mL) to the eluent volume tion onto DAC@GuTSC, the morphology, surface charge, (10 mL) and found to be 100 for all the metal ions. optical images and FTIR of the adsorbent were evaluated. Desorption and reusability of DAC@GuTSC composite Optical images Optical images of natural  cellulose, oxi- dized cellulose (DAC), DAC@GuTSC and metal-loaded To test the reusability of DAC@GuTSC, five cycles of modified cellulose: DAC@GuTSC-Cu, DAC@GuTSC-Hg adsorption–desorption have been carried out under the opti- and DAC@GuTSC-Pb are  shown in Fig.  11(a–f), respec- mum conditions, using 5 ml of 0.5 M HN O , the obtained tively. The images show the obvious color change of the results are shown in Table 8. From the results, it was clear modified cellulose before metal absorption (light yellow) that the adsorption efficiency of DAC@GuTSC was only compared with the modified cellulose after metal absorp- slightly decreased after cycle five, the adsorbent maintained tion. These results indicate the tendency of DAC@GuTSC about 95% of its initial efficiency. modified cellulose to adsorb investigated metal ions. Adsorption from multi‑metal solutions FTIR spectra of  DAC@GuTSC before  and  after  adsorption of metal ions The adsorption mechanism of the Cu, Hg and A mixture of metals under study was prepared to investigate Pb metal ions was designed in light of the effective groups the adsorption efficiency of the prepared DAC@GuTSC in available on DAC@GuTSC surface as shown in Fig. 12a and 1 3 Applied Water Science (2023) 13:144 Page 13 of 18 144 2+ 2+ Table 9 Simultaneous removal of multi-metal solution of (Cu , Hg and Pb2 +) (50 ml of 50 mg L-1) by DAC@GuTSC sorbent (0.050 g), pH 6, time of shaking 120 min, 25 °C from natural water samples Sample Metal ion Added (ppm) Found (ppm) % Removal 2+ 2+ 2+ Multi-metal solution of (Cu, Hg Cu 50.0 5.25 89.5 2+ and Pb ) 2+ Hg 50.0 8.4 91.6 2+ Pb 50.0 4.59 90.82 The concentration found in the aqueous solution after adsorption and ICP-AES determination 2+ 2+ 2+ Table 10 Removal of single-metal solution of (Cu , Hg and Pb ) with the coordinating N,N donors and N,S donors present −1 (50 ml of 50 mg L ) by DAC@GuTSC sorbent (0.050 g), pH 6, time onto the DAC@GuTSC chelating fibers. The main charac- of shaking 120  min, 25  °C from natural water samples (sample vol- teristic peaks of azomethine presented obvious, shifted upon ume: 250 mL, final volume: 10 mL, n = 3) 2+ complexation with the Cu ions. Thus, the value of stretch- −1 Sample Metal Ion Added (μg) Found (μg) Recovery % ing vibrations of C=N at 1610  cm was moved to lower −1 2+ value at 1580  cm , and this revealed that the complexation Tap water Cu – – takes place between the two nitrogen atoms of the two C=N 15.0 14.3 95.33 groups and copper ions. Moreover, coordination of thiolate 30.0 29.2 97.33 2+ S atom through –C–S–metal mode after enolization followed Hg – – by deprotonation on sulfur to the metal ion is suggested by 15.0 14.5 96.67 the shift of the ν(C=S) band at lower wave number in all of 30.0 29.4 98,00 2+ the studied complexes. The presence of a new band due to ν Pb – −1 (M–S) at 420–425  cm is another indication of the involve- 15.0 14.6 97.33 ment of the S atom in coordination. 30.0 29.5 98.33 2+ In conclusion, the DAC@GuTSC composite can bind Nile water Cu – to metal ions through N, N donors forming four- and five- 15.0 14.4 96.00 membered chelate rings and through N, S donors forming 30.0 29.6 98.67 2+ six-membered chelate rings, Scheme 3 Hg – 15.0 14.30 95.33 Performance of DAC@GuTSC 30.0 29.4 98.00 2+ Pb – To increase the value of the sorbent, we conducted a com- 15.0 14.4 96.00 parative study of the maximum sorption capacity achieved 30.0 29.6 98.66 2+ for the same contaminants with other sorbents and activated Sea water Cu – carbon described in the literature. Table 11 summarizes dif- 15.0 14.30 95.33 ferent values of q for different sorbents. The adsorption of max 30.0 29.2 97.33 2+ Cu, Hg and Pb observed in this study correlates with other Hg – studies with maximum adsorption capacities q for Cu, max 15.0 14.5 96.67 −1 Hg and Pb at 298 K of 50, 94, and 55 mg  g . Comparing 30.0 29.4 98,00 2+ the adsorption capacities obtained from most of the studies Pb – mentioned, we found that the adsorption capacity of DAC@ 15.0 14.4 96.00 GuTSC is higher. Using Cu as an example, DAC@GuTSC 30.0 29.2 97.33 −1 has an adsorption capacity of 50 mg  g , while all the meth- ods described gave adsorption capacities ranging from 1.75 −1 to 36 mg  g . Differences in Cu, Hg and Pb uptake are due (Fig. S3a). In fact, DAC@GuTSC composite is very abun- dant with active groups that can adsorb the three pollutants. to the morphological properties of each sorbent, including structure, functional groups and surface area. Desorption is These active groups come from the fact that the adsorbent is composed of dialdehyde cellulose and guanyl thiosemicar- an unavoidable process and an intermediate step for adsor- bent regeneration. The latter is a key point for evaluating the bazide which in their origin are rich in active groups. FTIR spectrum of DAC@GuTSC–Cu(II), Fig. 12b and reuse of sorbents for industrial applications due to environ- mental concerns and the need for sustainable development. (Fig. S3b) was also used for evaluation of the mechanism by 2+ which the Cu , as a representative example, can coordinate In the future, experiments can be performed at column scale 1 3 144 Page 14 of 18 Applied Water Science (2023) 13:144 Fig. 11 Optical images of a Native cellulose powder, b DAC oxidized cellulose, c DAC@ GuTSC, d DAC@GuTSC-Cu, e DAC@GuTSC-Hg and f DAC@GuTSC-Pb Conclusions (b) In order to find low-cost adsorbents, having pollutant- binding capacities is highly significant for efficient water treatment. The results of the present study reveal that: (a) i. DAC@GuTSC composite may be highly applicable adsorbent for the removal of heavy metals from aque- ous solutions. ii. Modification of DAC by aminoguanidine and phenyl 4000 3500 3000 2500 2000 1500 1000 500 -1 isothiocyanate significantly increased the nitrogen and Wavenumber (cm ) sulfur-containing groups on the surface of DAC@ GuTSC composite with remarkable change in textural Fig. 12 FTIR of a DAC@GuTSC and b DAC@GuTSC-Cu(II) properties and surface morphology. 2+ 2+ 2+ iii. The adsorption of Cu, Hg and Pb was dependent and in pilot plants. These experiments can be implemented on initial concentration, reaction temperature and pH. to be applied to sewage treatment plants to remove cationic iv. The equilibrium of adsorption process could is well and anionic metal ions and textile dyes from wastewater. described by Langmuir adsorption isotherms, i.e., monolayer adsorption on a homogenous surface. The 2+ Cu Scheme 3 Plausible mechanism NH 2+ S Cu NH NH S of Cu(II) onto DAC@GuTSC N H N N NH 2+ N 0.2M HNO 3 H N H Cu H N NH NH H composite H 2+ Desorption adsorption Cu DAC@GuTSC DAC@GuTSC-Cu(II) DAC@GuTSC 1 3 Transmittance (%) Cellulose Cellulose Cellulose Applied Water Science (2023) 13:144 Page 15 of 18 144 +2 +2 +2 Table 11 Comparison of the adsorption capacities of Cu, Hg and Pb by DAC@GuTSC with other adsorbents Metal ion Adsorbent Adsorption capac- Reference −1 ity (mg  g ) Cu DAC@GuTSC 50 Present work Microfibrillated cellulose modified with aminopropyltriethoxysilane 3.150 Hokkanen et al. (2014) Cellulose modified with acrylic acid 17.2 Güçlü et al. (2003) Cortex banana waste 36.0 Kelly-Vargas et al. (2012) Citric acid modified cellulose 24 Low et al. (2004) Pristine nanocellulose 20 Liu et al. (2015) Peanut shells 25.39 Witek-Krowiak et al. (2011) Orange peels modified with HNO (0.1 M) 15.27 Lasheen et al. (2012) Cationic wheat straw 33.5 Zhong et al. (2014) Tobacco dust as a lignocellulosic source 36.0 Qi and Aldrich (2008) Pomegranate peel 30.12 Ben-Ali et al. (2017) Oil palm shell 1.75 Chong et al. (2013) Rice husk 30.0 Sobhanardakani et al. (2013) Hg DAC@GuTSC 94 Present work Bamboo leaf powder as a cellulose source 27.11 Mondal et al. (2013) Guanyl modified cellulose 48 Khan et al. (2004) Eucalyptus bark 34.60 Ghodbane and Hamdaoui (2008) Bacillus subtilis biomass 68.5 Wang et al. (2010) Silica gel modified with 2-(2-oxoethyl)hydrazine carbothioamide 37.5 3 Chai et al. (2010) Allium sativum L 0.6497 Eom et al. (2011) Magnetic nanoparticles doped with 1,5-diphenylcarbazide 44 Zhai et al. (2010) Pb DAC@GuTSC 55 Present work Cellulose powder modified with acrylic acid 55.9 Güçlü et al. (2003) Guanyl modified cellulose 52 Khan et al. (2004) Nano-TiO 7.41 Poursani et al. (2016) Citric acid modified cellulose 83 Mohan et al. (2006) Cotton as cellulosic biomass 10.78 Wu et al. (2012) Pine cone powder modified with NaOH(0.01 M) 24.75 Ofomaja and Naidoo (2010) Cauliflower waste 47.63 Hossain et al. (2014) Sorghum bicolor L. modified with thiourea 17.82 Ofomaja and Naidoo (2010) Oil palm shell 3.39 Chong et al. (2013) Tobacco dust as a lignocellulosic source 39.6 Qi and Aldrich (2008) S. bengalense extract modified with urea 12.65 Din et al. (2014) kinetic studies follow a pseudo-second-order kinetic viii. Submersion of the DAC@GuTSC-loaded metals sam- model. ples in 5 ml of 0.5 M HNO resulted in the desorption o o v. The negative values of (ΔG ) and (∆H ) thermody- of more than 90% of the adsorbed metal ions. 2+ 2+ 2+ namic parameters clarify the spontaneous and exo- ix. The uptake of Cu , Hg and Pb using such DAC@ thermic nature of the adsorption technique. GuTSC composite is highly comparable to the previ- 2+ vi. In this study, the prepared DAC@GuTSC adsorbent ous commercial adsorbents used for removal of Cu , 2+ 2+ 2+ 2+ 2+ has high removal efficiency of Cu, Hg and Pb Hg and Pb . at optimum batch sorption condition with maximum x. The mechanism of adsorption was complex where −1 2+ sorption capacity of 50, 94 and 55 mg  g for Cu , DAC@GuTSC composite, possessing the synergistic 2+ 2+ Hg and Pb , respectively, that was achieved within effects of DAC and guanyl thiosemicarbazide, showed 240 min. surface complexation between the N, N- and N, S 2+ 2+ 2+ vii. The removal of Cu, Hg and Pb from natural donors of the guanyl thiosemicarbazide moiety with water samples was successfully applied using DAC@ metal ions. GuTSC. 1 3 144 Page 16 of 18 Applied Water Science (2023) 13:144 to determination by flame atomic absorption spectrometry. Anal xi. In conclusion, the present work well demonstrated the Sci 21(8):923–931 potential of this technique for wider applications. Akl MA, Sarhan AA, Shoueir KR, Atta AM (2013) Application of crosslinked ionic poly (vinyl alcohol) nanogel as adsorbents for water treatment. J Dispersion Sci Technol 34(10):1399–1408 Supplementary Information The online version contains supplemen- Akl MA, El-Zeny AS, Hashem MA, El-Gharkawy ESRH (2021) tary material available at https://doi. or g/10. 1007/ s13201- 023- 01948-9 . Synthesis, characterization and analytical applications of chemi- cally modified cellulose for remediation of environmental pol- Author contributions Magda A Akl was involved in conceptualization, lutants. Egypt J Chem 64(7):3889–3901. h t t ps : / / d o i . o r g / 1 0 . supervision, investigation, methodology, visualization, writing—origi- 21608/ ejchem. 2021. 65793. 3412 nal draft, writing—review & editing. Abdelrahman S El-Zeny helped in Atta A, Akl MA, Youssef AM, Ibraheim MA (2013) Superparamag- writing—original draft, writing—review & editing. Mohamed Ismail netic core-shell polymeric nanocomposites for efficient removal contributed to supervision. Mohamed Abdalla was involved in super- of methylene blue from aqueous solutions. Adsorpt Sci Technol vision. Dina Abdelgelil helped in investigation, methodology, valida- 31(5):397–419 tion, visualization, writing—original draft, writing & editing. Aya G Aydın H, Bulut Y, Yerlikaya Ç (2008) Removal of copper (II) from Mostafa contributed to investigation, methodology, writing—review aqueous solution by adsorption onto low-cost adsorbents. J & editing. Environ Manage 87(1):37–45 Balachandran V, Murali MK (2011) FT-IR and FT-Raman spectral Funding Open access funding provided by The Science, Technology & analysis of 3-(trifluromethyl) phenyl isothiocyanate. Elixir Vib Innovation Funding Authority (STDF) in cooperation with The Egyp- Spec 40:5105–5107 tian Knowledge Bank (EKB). This study received no support from Ben-Ali S, Jaouali I, Souissi-Najar S, Ouederni A (2017) Charac- public, private or nonprofit funding agencies. terization and adsorption capacity of raw pomegranate peel biosorbent for copper removal. J Clean Prod 142:3809–3821 Availability of data and materials Data supporting the results reported Bilal M, Shah JA, Ashfaq T, Gardazi SMH, Tahir AA, Pervez A, in the article can be requested from authors. Haroon H, Mahmood Q (2013) Waste biomass adsorbents for copper removal from industrial wastewater—a review. J Hazard Declarations Mater 263:322–333 Chai X, Chang X, Hu Z, He Q, Tu Z, Li Z (2010) Solid phase extrac- Ethical approval The authors acknowledge that the current research tion of trace Hg (II) on silica gel modified with 2-(2-oxoethyl) has been conducted ethically. They declared that this manuscript does hydrazine carbothioamide and determination by ICP-AES. Tal- not involve researching about humans or animals. anta 82(5):1791–1796 Chang LW (1977) Neurotoxic effects of mercury—a review. Environ Consent to participate The authors consent to participate in this Res 14(3):329–373 research study. Chaturvedi SI (2013) Electrocoagulation: a novel waste water treat- ment method. Int J Modern Eng Res 3(1):93–100 Chong HLH, Chia PS, Ahmad MN (2013) The adsorption of heavy Conflict of interest Authors declare no known competing interests. metal by Bornean oil palm shell and its potential application as constructed wetland media. Biores Technol 130:181–186 Open Access This article is licensed under a Creative Commons Attri- Clarkson TW (1993) Mercury: major issues in environmental health. bution 4.0 International License, which permits use, sharing, adapta- Environ Health Perspect 100:31–38 tion, distribution and reproduction in any medium or format, as long Clarkson TW, Magos L (2006) The toxicology of mercury and its as you give appropriate credit to the original author(s) and the source, chemical compounds. Crit Rev Toxicol 36(8):609–662 provide a link to the Creative Commons licence, and indicate if changes Dacrory S (2021) Antimicrobial activity, DFT calculations, and were made. The images or other third party material in this article are molecular docking of dialdehyde cellulose/graphene oxide film included in the article's Creative Commons licence, unless indicated against Covid-19. J Polym Environ 29(7):2248–2260. https:// otherwise in a credit line to the material. If material is not included in doi. org/ 10. 1007/ s10924- 020- 02039-5 the article's Creative Commons licence and your intended use is not Dacrory S, Abou-Yousef H, Kamel S, Abou-Zeid RE, Abdel-Aziz permitted by statutory regulation or exceeds the permitted use, you will MS, Elbadry M (2019) Functionalization and cross-linking of need to obtain permission directly from the copyright holder. To view a carboxymethyl cellulose in aqueous media. Cell Chem Technol copy of this licence, visit http://cr eativ ecommons. or g/licen ses/ b y/4.0/ . 53(1–2):23–33 Din MI, Hussain Z, Mirza ML, Shah AT, Athar MM (2014) Adsorp- tion optimization of lead (II) using Saccharum bengalense as a non-conventional low cost biosorbent: isotherm and thermody- References namics modeling. Int J Phytorem 16(9):889–908 Dridi-Dhaouadi S, Douissa-Lazreg NB, M’Henni MF (2011) Acemioglu B, Alma MH (2001) Equilibrium studies on adsorption of Removal of lead and Yellow 44 acid dye in single and binary Cu (II) from aqueous solution onto cellulose. J Colloid Interface component systems by raw Posidonia oceanica and the cellulose Sci 243(1):81–84 extracted from the raw biomass. Environ Technol 32(3):325–340 Akl MAA, Kenawy IMM, Lasheen RR (2004) Organically modified Eom Y, Won JH, Ryu J-Y, Lee TG (2011) Biosorption of mercury silica gel and flame atomic absorption spectrometry: employment (II) ions from aqueous solution by garlic (Allium sativum L.) for separation and preconcentration of nine trace heavy metals powder. Korean J Chem Eng 28:1439–1443 for their determination in natural aqueous systems. Microchem Friberg L, Mottet NK (1989) Accumulation of methylmercury J 78(2):143–156 and inorganic mercury in the brain. Biol Trace Elem Res Akl MAA-E, Kenawy IM, Lasheen RR (2005) Silica gel modified with 21:201–206 N-(3-propyl)-o-phenylenediamine: Functionalization, metal sorp- tion equilibrium studies and application to metal enrichment prior 1 3 Applied Water Science (2023) 13:144 Page 17 of 18 144 Gherasim C-V, Mikulášek P (2014) Influence of operating variables Magos L, Clarkson TW (2006) Overview of the clinical toxicity of on the removal of heavy metal ions from aqueous solutions by mercury. Ann Clin Biochem 43(4):257–268 nanofiltration. Desalination 343:67–74 Martin S, Griswold W (2009) Human health effects of heavy metals. Ghodbane I, Hamdaoui O (2008) Removal of mercury (II) from Environ Sci Technol Briefs Citizens 15:1–6 aqueous media using eucalyptus bark: kinetic and equilibrium Meena AK, Mishra GK, Rai PK, Rajagopal C, Nagar PN (2005) studies. J Hazard Mater 160(2–3):301–309 Removal of heavy metal ions from aqueous solutions using car- Gotoh T, Matsushima K, Kikuchi K-I (2004a) Adsorption of Cu and bon aerogel as an adsorbent. J Hazard Mater 122(1–2):161–170. Mn on covalently cross-linked alginate gel beads. Chemosphere https:// doi. org/ 10. 1016/j. jhazm at. 2005. 03. 024 55(1):57–64 Mohan D, Pittman CU Jr, Steele PH (2006) Pyrolysis of wood/biomass Gotoh T, Matsushima K, Kikuchi K-I (2004b) Preparation of algi- for bio-oil: a critical review. Energy Fuels 20(3):848–889 nate–chitosan hybrid gel beads and adsorption of divalent metal Mondal DK, Nandi BK, Purkait MK (2013) Removal of mercury ions. Chemosphere 55(1):135–140 (II) from aqueous solution using bamboo leaf powder: equilib- Güçlü G, Gürdağ G, Özgümüş S (2003) Competitive removal of rium, thermodynamic and kinetic studies. J Environ Chem Eng heavy metal ions by cellulose graft copolymers. J Appl Polym 1(4):891–898 Sci 90(8):2034–2039 Monier M, Akl MA, Ali W (2014a) Preparation and characterization of Gupta VK (2009) Application of low-cost adsorbents for dye selective phenyl thiosemicarbazide modified Au(III) ion-imprinted removal–a review. J Environ Manage 90(8):2313–2342 cellulosic cotton fibers. J Appl Polym Sci 131(18):9277–9287. Guzzi G, La Porta CAM (2008) Molecular mechanisms triggered by https:// doi. org/ 10. 1002/ app. 40769 mercury. Toxicology 244(1):1–12 Monier M, Akl MA, Ali WM (2014b) Modification and characteriza- Hokkanen S, Repo E, Suopajärvi T, Liimatainen H, Niinimaa J, Sil- tion of cellulose cotton fibers for fast extraction of some precious lanpää M (2014) Adsorption of Ni (II), Cu (II) and Cd (II) from metal ions. Int J Biol Macromol 66:125–134 aqueous solutions by amino modified nanostructured microfi- Navarro RR, Sumi K, Fujii N, Matsumura M (1996) Mercury removal brillated cellulose. Cellulose 21:1471–1487 from wastewater using porous cellulose carrier modified with Hossain MA, Ngo HH, Guo WS, Nguyen TV, Vigneswaran S (2014) polyethyleneimine. Water Res 30(10):2488–2494 Performance of cabbage and cauliflower wastes for heavy metals Nayl AA, Abd-Elhamid AI, Abu-Saied MA, El-Shanshory AA, Soli- removal. Desalin Water Treat 52(4–6):844–860 man HMA, Akl MA, Aly HF (2020) A novel method for highly Hua M, Zhang S, Pan B, Zhang W, Lv L, Zhang Q (2012) Heavy effective removal and determination of binary cationic dyes in metal removal from water/wastewater by nanosized metal aqueous media using a cotton–graphene oxide composite. RSC oxides: a review. J Hazard Mater 211:317–331 Adv 10(13):7791–7802 Ibrahim A, El Fawal GF, Akl MA (2019) Methylene blue and crystal Nouri L, Ghodbane I, Hamdaoui O, Chiha M (2007) Batch sorption violet dyes removal (as A binary system) from aqueous solution dynamics and equilibrium for the removal of cadmium ions from using local soil clay: kinetics study and equilibrium isotherms. aqueous phase using wheat bran. J Hazard Mater 149(1):115–125 Egypt J Chem 62(3):541–554 O’Connell DW, Birkinshaw C, O’Dwyer TF (2008) Heavy metal adsor- Jamil N, Munawar MA, Muntaha ST (2009) Biosorption of Hg (II) bents prepared from the modic fi ation of cellulose: a review. Biores and Cd (II) from waste water by using Zea Mays waste. J Chem Technol 99(15):6709–6724 Soc Pakistan 31 Ofomaja AE, Naidoo EB (2010) Biosorption of lead (II) onto pine cone Kelly-Vargas K, Cerro-Lopez M, Reyna-Tellez S, Bandala ER, powder: studies on biosorption performance and process design Sanchez-Salas JL (2012) Biosorption of heavy metals in pol- to minimize biosorbent mass. Carbohyd Polym 82(4):1031–1042 luted water, using different waste fruit cortex. Phys Chem Earth Pan B, Pan B, Zhang W, Lv L, Zhang Q, Zheng S (2009) Development Parts a/b/c 37:26–29 of polymeric and polymer-based hybrid adsorbents for pollutants Kenawy IM, Hafez MAH, Ismail MA, Hashem MA (2018) Adsorp- removal from waters. Chem Eng J 151(1–3):19–29 tion of Cu(II), Cd(II), Hg(II), Pb(II) and Zn(II) from aqueous Poursani AS, Nilchi A, Hassani A, Shariat SM, Nouri J (2016) The single metal solutions by guanyl-modified cellulose. Int J Biol synthesis of nano TiO 2 and its use for removal of lead ions from Macromol 107:1538–1549. https:// doi. org/ 10. 1016/j. ijbio mac. aqueous solution. J Water Resour Prot 8(04):438 2017. 10. 017 Qi BC, Aldrich C (2008) Biosorption of heavy metals from aqueous Khan NA, Ibrahim S, Subramaniam P (2004) Elimination of heavy solutions with tobacco dust. Biores Technol 99(13):5595–5601 metals from wastewater using agricultural wastes as adsorbents. Shoueir KR, Sarhan AA, Atta AM, Akl MA (2016) Macrogel and Malaysian J Sci 23(1):43–51 nanogel networks based on crosslinked poly (vinyl alcohol) for Kurniawan TA, Chan GYS, Lo W-H, Babel S (2006) Physico–chemi- adsorption of methylene blue from aqua system. Environ Nano- cal treatment techniques for wastewater laden with heavy metals. technol Monitor Manage 5:62–73 Chem Eng J 118(1–2):83–98 Shoueir KR, Atta AM, Sarhan AA, Akl MA (2017) Synthesis of Lasheen MR, Ammar NS, Ibrahim HS (2012) Adsorption/desorption of monodisperse core shell PVA@ P (AMPS-co-NIPAm) nanogels Cd (II), Cu (II) and Pb (II) using chemically modified orange peel: structured for pre-concentration of Fe (III) ions. Environ Technol equilibrium and kinetic studies. Solid State Sci 14(2):202–210 38(8):967–978 Lee I-H, Kuan Y-C, Chern J-M (2007) Equilibrium and kinetics of Sobhanardakani S, Parvizimosaed H, Olyaie E (2013) Heavy metals heavy metal ion exchange. J Chin Inst Chem Eng, 38(1):71–84 removal from wastewaters using organic solid waste—rice husk. Liu B, Huang Y (2011) Polyethyleneimine modified eggshell mem- Environ Sci Pollut Res 20:5265–5271 brane as a novel biosorbent for adsorption and detoxification of Suhas, Gupta VK, Carrott PJM, Singh R, Chaudhary M, Kushwaha Cr (VI) from water. J Mater Chem 21(43):17413–17418 S (2016) Cellulose: a review as natural, modified and activated Liu P, Borrell PF, Božič M, Kokol V, Oksman K, Mathew AP (2015) carbon adsorbent. Bioresour Technol 216:1066–1076. https://d oi. Nanocelluloses and their phosphorylated derivatives for selective org/ 10. 1016/j. biort ech. 2016. 05. 106 adsorption of Ag+, Cu2+ and Fe3+ from industrial effluents. J Wang L, Li J (2013) Adsorption of CI Reactive Red 228 dye from Hazard Mater 294:177–185 aqueous solution by modified cellulose from flax shive: Kinetics, Low KS, Lee CK, Mak SM (2004) Sorption of copper and lead by citric equilibrium, and thermodynamics. Ind Crops Prod 42:153–158 acid modified wood. Wood Sci Technol 38:629–640 1 3 144 Page 18 of 18 Applied Water Science (2023) 13:144 Wang XS, Li FY, He W, Miao HH (2010) Hg (II) removal from aque- solution using magnetic nanoparticles doped with 1,5-diphenyl- ous solutions by Bacillus subtilis biomass. Clean: Soil, Air, Water carbazide. Microchim Acta 169(3):353–360. https:// doi. org/ 10. 38(1):44–481007/ s00604- 010- 0363-8 Witek-Krowiak A, Szafran RG, Modelski S (2011) Biosorption of Zhao G, Wu X, Tan X, Wang X (2010) Sorption of heavy metal ions heavy metals from aqueous solutions onto peanut shell as a low- from aqueous solutions: a review. Open Colloid Sci J 4(1) cost biosorbent. Desalination 265(1–3):126–134 Zhong QQ, Yue QY, Li Q, Gao BY, Xu X (2014) Removal of Cu(II) Wu Z, Cheng Z, Ma W (2012) Adsorption of Pb (II) from glucose solu- and Cr(VI) from wastewater by an amphoteric sorbent based on tion on thiol-functionalized cellulosic biomass. Biores Technol cellulose-rich biomass. Carbohyd Polym 111:788–796. https:// 104:807–809doi. org/ 10. 1016/j. carbp ol. 2014. 05. 043 Xu Y, Huang C, Wang X (2013) Characterization and controlled release aloe extract of collagen protein modified cotton fiber. Carbohyd Publisher's Note Springer Nature remains neutral with regard to Polym 92(2):982–988 jurisdictional claims in published maps and institutional affiliations. Zewail TM, Yousef NS (2015) Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed. Alex Eng J 54(1):83–90 Zhai Y, Duan S, He Q, Yang X, Han Q (2010) Solid phase extrac- tion and preconcentration of trace mercury(II) from aqueous 1 3 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Applied Water Science Springer Journals

Smart guanyl thiosemicarbazide functionalized dialdehyde cellulose for removal of heavy metal ions from aquatic solutions: adsorption characteristics and mechanism study

Loading next page...
 
/lp/springer-journals/smart-guanyl-thiosemicarbazide-functionalized-dialdehyde-cellulose-for-2tGdOOhArM

References (75)

Publisher
Springer Journals
Copyright
Copyright © The Author(s) 2023
ISSN
2190-5487
eISSN
2190-5495
DOI
10.1007/s13201-023-01948-9
Publisher site
See Article on Publisher Site

Abstract

In recent years, facing the problem of improving environmental quality, cellulose and cellulose-based (nano) composites have received great attention as adsorbents. In this work, we report the modification and functionalization of cellulose by nitrogen- and sulfur-containing moieties through a three-steps process; native cellulose is first oxidized by potassium periodate (KIO ) to form dialdehyde cellulose (DAC), which then condenses with aminoguanidine and react with phenyl isothiocyanate to form 4-phenyl guanyl thiosemicarbazide dialdehyde cellulose (DAC@GuTSC). The prepared DAC@GuTSC is characterized by a number of techniques, including Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental analysis (EA), Brunauer–Emmett–Teller (BET) and thermogravimetric analysis (TGA). The prepared DAC@ 2+ 2+ 2+ GuTSC adsorbent was used to remove Cu Hg and Pb from aqueous solution and environmental water samples. The influence of various factors on the adsorption efficiency including pH, initial metal concentration, contact time, adsorbent dosage, temperature, and ions interfering with adsorption was investigated. Under optimal adsorption conditions, the adsorp- 2+ 2+ 2+ −1 tion capacity of Cu, Hg and Pb was 50, 94 and 55 mg  g , respectively. The adsorption process is well described by the Langmuir model, and it was found to follow the pseudo-second-order kinetics model. The spontaneous and endothermic 2+ 2+ 2+ adsorption of Cu, Hg and Pb was confirmed by the calculated thermodynamic functions. The prepared DAC@GuTSC 2+ 2+ 2+ composite has been successfully applied to remove Cu, Hg and Pb from real water samples with recovery greater than 2+ 2+ 2+ 90% and relative standard deviation (RSD) less than 3%. The reasonable Cu , Hg and Pb adsorption mechanism on the prepared DAC@GuTSC composite has been elucidated. Keywords Adsorption · Cellulose · Aminoguanidine · Phenyl isothiocyanate · Heavy metals · Water treatment Introduction and persist for long periods (Nouri et al. 2007). These heavy metals can cause a number of diseases and disorders, even Clean and safe water is an eternal need of every individual. at very small concentrations (Gotoh et al. 2004a, 2004b). In recent decades, freshwater resources have been directly For example, lead has a number of health effects, includ- threatened by increasing industrialization worldwide (Jamil ing anemia, hypertension and digestive disorders (Gherasim et al. 2009).Discharged industrial waste significantly con - and Mikulášek 2014; Martin and Griswold 2009) while high taminates water sources by releasing a number of pollutants, copper levels can cause abdominal strain and kidney failure including organics and heavy metals (Liu and Huang 2011). (Bilal et al. 2013; Chaturvedi 2013) mercury is believed to Unlike organic pollutants, heavy metals such as Hg, Pb, Cu, have toxic effects on the nervous system, leading to serious Cd and Zn are not biodegradable and tend to accumulate disorders such as brain damage, memory loss, behavioral abnormalities and autism (Chang 1977; Clarkson 1993; Clarkson and Magos 2006; Friberg and Mottet 1989; Guzzi * Magda A. Akl and La Porta 2008; Magos and Clarkson 2006). magdaakl@yahoo.com To avoid serious impacts on the environment and public 1 health, several techniques have been developed to remove Department of Chemistry, Faculty of Science, Mansoura heavy metals from water, including ion exchange, chemical University, Mansoura 35516, Egypt Vol.:(0123456789) 1 3 144 Page 2 of 18 Applied Water Science (2023) 13:144 precipitation, membrane filtration and adsorption. (Akl et al. 2013, 2005, 2004; Atta et al. 2013; Ibrahim et al. 2019; Kur- niawan et al. 2006; Lee et al. 2007; Meena et al. 2005; Mon- ier et al. 2014b, 2014a; Nayl et al. 2020; O’Connell et al. 2008; Shoueir et al. 2016, 2017; Wang and Li 2013; Zewail and Yousef 2015). However, adsorption is widely preferred Scheme 1 Schematic representation of determination of the aldehyde over other conventional techniques due to its affordability, content (Dacrory 2021) simplicity, high efficiency and eco-friendly nature (Aydın et  al. 2008; Hua et al. 2012; Khan et al. 2004; Pan et al. 2009; Zhao et al. 2010). iv. Investigating the ideal parameters required for optimal Cellulose is one of the most commonly used biosorbents, adsorption of the studied metal ions, e.g., pH, temper- showing great heavy metal adsorption potential, especially ature, the initial concentration of the three investigated when chemically modified by binding to novel groups via metal ions, the mass of DAC@GuTSC composite and complexation or chelation significantly improves its adsorp- the oscillation time, as well as the interfering ions. tion capacity (Acemioglu and Alma 2001; Aydın et al. 2008; v. Studying the various adsorption isotherm, kinetics and Dridi-Dhaouadi et  al. 2011; Gupta 2009; Navarro et  al. thermodynamic parameters. 1996; Suhas et al. 2016; Wu et al. 2012). It has been shown vi. Comparative evaluation of metal removal efficiency that introducing aminoguanidine to cellulose after oxidizing and reusability of DAC@GuTSC composite with it with KIO improves its adsorption capacity and leads to other previously reported adsorbents. satisfactory removal results for Cu ions, Hg, Pb, Cd and Zn vii. Elucidation of the mechanisms involved in the process +2 +2 +2 of aqueous solutions (Kenawy et al. 2018). of adsorption of Cu , Hg and Pb onto DAC@ In this study, an attempt was made to modify cellulose GuTSC composite. by adding an additional procedure to the above method, that is, adding phenyl isothiocyanate to aminoguanidine modi- fied cellulose and investigating its effectiveness in adsorbing Experimental and methods three heavy metals (i.e., Cu, Hg and Pb) from aqueous solu- tion and real sample. This modification leads to the forma- Materials tion of a new adsorbent 4-pheny guanyl thiosemicarbazide functionalized dialdehyde cellulose (DAC@GuTSC) con- Aminoguanidine monohydrochloride, cellulose powder, taining potentially electron-donating N and S atoms. The phenyl isothiocyanate, potassium metaperiodate (KIO ), presence of N/S atoms provides a stronger chelation regime CuSO, HgCl , Pb(NO ) and triethylamine were purchased 4 2 3 2 with metal ions. from Sigma-Aldrich and directly used. To our knowledge, the modification of cellulose using a nitrogen-containing ligand (aminoguanidine) and a sulfur- Preparations nitrogen phenyl isothiocyanate has not been reported in the literature. Again, no data were found on using DAC@ Preparation of dialdehyde cellulose (DAC) GuTSC modified cellulose as an effective adsorbent for 2+ 2+ 2+ Cu, Hg and Pb from actual polluted water samples. One gram of the native cellulose was oxidized using 100 ml Accordingly, the current study was performed out with these objectives: of 4% potassium periodate. The previous mixture was shaken for 1 h in complete darkness to form dialdehyde cellulose i. Design and synthesis of N and S containing guanyl (DAC), Scheme 1. The obtained DAC was washed several times with dist.H O and was dried in an oven at 50 °C. thiosemicarbazide functionalized dialdehyde cellu- losic composite (DAC@GuTSC) for adsorption of +2 +2 +2 Determination of aldehyde content The aldehyde content Cu, Hg and Pb metal ions in single and multi- component metal ions’ solutions. of DAC is determined by the Schiff base reaction in Fig.  1 according to refs (Dacrory 2021; Dacrory et al. 2019) in ii. Characterization of the as-prepared DAC@GuTSC composite using physical (optical images) elemental which hydroxylamine hydrochloride is used to convert the aldehyde group to the corresponding oxime. 0.3 g of analysis and spectroscopic (FTIR), SEM and TGA instrumental performances. DAC sample was dispersed in 20  ml of distilled water and adjusted to (pH ≈ 5) with NAOH solution. 20 ml of iii. Batch sorption experiments in single and multi-com- 2+ 2+ 2+ ponent metal ions utilizing Cu, Hg and Pb as hydroxylamine hydrochloride solution (0.72 mol/l) of pH 5 was then added. The mixture was stirred at 40  °C for pollutants. 1 3 Applied Water Science (2023) 13:144 Page 3 of 18 144 Fig. 1 a Filtrate of 0.25 M hydroxylamine after stirring for 2.5 h with DAC; b after titration with 0.1 M NaOH 4 h. Released HCl was titrated with 1.0 M NaOH solution. Instrumentation The amount of NaOH consumed when the pH of the solu- tion reached 5.0 was recorded (Ibrahim et al. 2019). The The FTIR spectra of the prepared samples were recorded −1 amount of NaOH solution consumed in the titration was between 4000 and 400  cm . Disks were prepared by first recorded as Va (liters). A pH 5.0 cellulose solution of the mixing 1 mg of dried samples with 500 mg of KBr (Merck, same concentration was used as a blank and the volume for spectroscopy) in an agate mortar and then pressing the −2 of 1.0  M NaOH consumed was recorded as Vc (liters). resulting mixture successively at 8 tons cm . Elemental Aldehyde content (% w/w) calculated using the following analysis was done using a Perkin-Elmer 2400 analyzer. formula (Dacrory 2021) Brunauer–Emmett–Teller (BET) analysis was conducted to evaluate the surface area of the DAC@GuTSC. Ther- −CHO + NH OH − HCl → −CHNOH + HCl + H O 2 2 mogravimetric analysis (TGA) was performed by thermo HCl + NaOH → NaCl + H O analyzer Shimatzu DT40 (Japan) over temperature range of 30–800 °C with N atmosphere and with the heating flow 10 °C/min. In addition, scanning electron microscope (SEM) The aldehyde content for DAC was calculated as shown was used to study the morphology of native cellulose, DAC in Eq. 1: and DAC@GuTSC samples. The samples were sputtered and coated with gold before using scanning electron micro- M V − V NaOH sample control 2+ 2+ 2+ AC(%) = × 100 (1) scope. The concentrations of Cu , Hg and Pb in metal Mwt solutions before and after adsorption were estimated using Agilent's 5100 ICP OES. Where M is the used NaOH concentration (0.1 mol), NaOH The point of zero charge (pH ) was determined using m is the prepared DAC weight, and Mwt is the molecular PZC the solid addition method. In a series of 100 ml jacketed weight of the DAC repeating unit (C H O ) that is equal to 6 8 10 n glasses, 50 ml of KNO solutions of known concentration 160.124 g/mol. V and V are the recorded volumes sample control was transferred. The solutions of different initial pH (pH ) of the NaOH consumption for the DAC sample and control i between 2 and 12 were prepared by adding either 0.1 M HCl one, respectively. The determination of the aldehyde content or 0.1 M NaOH. One gram of DAC@GuTSC composite for DAC is schematically represented in scheme 1 was then added to each solution with stirring for 48 h. The final pH (pH ) was measured and the difference between the initial and final pH values (ΔpH = pH- pH ) was plotted Preparation of the Schiff base guanyl thiosemicarbazide i f against pHi. The pHpzc value is the point where the curve functionalized dialdehyde cellulose (DAC@GuTSC) ΔpH vs pHi crosses the line ΔpH = 0. Guanyl dialdehyde cellulose (DAC@Gu) was prepared by Batch adsorption experiments the same procedure followed in the mentioned study [45] except for increasing the oxidation time for 6 h. Then, 5 ml 2+ 2+ 2+ Batch adsorption of Cu, Hg and Pb was performed in of phenyl isothiocyanate was added to 0.5 g of the guanyl 100 mL reagent bottles containing 50 mL of known initial modified cellulose and immersed in 100 ml of ethanol in concentrations (50, 100, 150, 200) ppm of the metals under the presence of triethylamine. The obtained mixture was investigation and known DAC@GuTSC weights (0.01, 0.03, allowed to reflux for 3 h at 80 °C. Yellow powder of the 0.05) g at a pH of (3–7) adjusted by the addition of 0.1 M guanyl 4-phenyl thiosemicarbazide functionalized dialde- NaOH and/or 0.1 M HCL and a temperature of (25–45)°C hyde cellulose composite (DAC@GuTSC) was obtained (at time intervals of 1–24 h). Bottles containing samples at the end. were shaken on a mechanical shaker for (20–120 min) and 1 3 144 Page 4 of 18 Applied Water Science (2023) 13:144 filtered. Metal ion concentrations in the supernatants were and dried. No reduction in total mass was observed. The determined by ICP OES. DAC@GuTSC adsorbent was insoluble in water. Scheme 2 Then, adsorption capacity and the removal efficiency represents the proposed steps of the synthetic reaction. were evaluated by Eqs. (2) and (3), respectively. Characterization q = C − C V∕W (2) e i e Infrared spectroscopy C − C i e Removal (%) = × 100 (3) The obtained IR spectra for native, DAC, DAC@Gu and DAC@GuTSC samples are presented in Fig. 2(a–d). −1 where q is the adsorption capacity in mg  g , C is the initial e i The FTIR spectrum of unmodified natural cellulose −1 concentration of metal ion under study in (mg  L ), C is Fig. 2a and (Fig.S1a) shows some characteristic peaks in −1 the equilibrium concentration of metal ions in (mg  L ), V −1 the range of 1000–1200  cm corresponding to C-O elon- volume of solution in (liter), and W is adsorbent mass in (g). gation. While the peaks present at 1260–1410 cm − 1 are attributed to the OH bending vibrations, the peaks present −1 between 3600 and 3200  cm correspond to the OH stretch- Results and discussion ing vibrations (Xu et al. 2013). Other peaks occurring at −1 2700–3000  cm are due to C–H elongation. Materials' design The IR spectrum of DAC in Fig. 2.b and (Fig. S1b) shows an extremely sharp peak that is moderately sharp at about Synthesis of dialdehyde cellulose (DAC) −1 1650  cm , which is due to prolonged oscillations of the groups carbonyl (C=O) is formed during oxidation ( Akl KIO , a known selective oxidizing agent, oxidizes two et al. 2021). hydroxyl groups on two neighboring carbon atoms C –C 2 3 Modification of DAC by reaction with aminoguanidine bond of the glucopyranoside ring that will be cleaved and causes some changes in the IR spectrum, notably a sharp converted into two dialdehyde groups. The oxidation degree −1 peak at about 1720  cm , possibly due to C=N formation which represents the percentage of monosaccharide units between the aldehyde groups present in the cellulose being that reacted with KI O is calculated by aldehyde content oxidants and amino groups of the added aminoguanidine determination (Akl et al. 2021). The aldehyde content of the [45] as shown in Fig. 2c and (Fig. S1c). prepared DAC is 35.71% as it is presented in Table1. Figure 2d and (Fig. S1d) show the IR spectrum of DAC@ GuTSC composite after insertion of phenyl isothiocy- Synthesis of the Schiff base DAC@GuTSC composite −1 anate. The presence of new peaks between 1120  cm and −1 960  cm may be related to group C=S [49] present in the Natural cellulose powder was selectively oxidized by KIO inserted phenyl isothiocyanate. Alternatively, the broad peak to give the dialdehyde form (DAC) with aminoguanidine at −1 at about 2900  cm could be due to the introduction of a 80 °C. The product (DAC@Gu) was further reacted with phenyl group. Furthermore, the overlapping peaks occurring phenyl isothiocyanate to form the DAC@GuTSC compos- −1 −1 between 1520  cm and 1650  cm can be attributed to the ite with additional nitrogen and sulfur functionalities. The unsaturated C–N–H, N=CH– and C=C bonds in the aro- water solubility of the DAC@GuTSC adsorbent was tested matic rings of the phenyl group (Balachandran and Murali by suspending a 1.00 g sample of the DAC@GuTSC adsor- 2011). The observed differences in IR spectra support the bent in 50.0 mL of water. After stirring the suspension for denaturation of natural cellulose and the insertion of new about 3.0 h, the resulting solid was collected by filtration N and S functional groups into the newly prepared DAC@ GuTSC composite. Elemental analysis Table 1 Volumetric titration of DAC for determination of average aldehyde content percentage (AC, %) The results of elemental analysis for native cellulose and Vcontrol Vsample CNaOH m (gm) AC % Average modified cellulose are summarized in Table  2. The results (ml) (ml) (M) AC% revealed an addition of nitrogen and sulfur to the elemen- 0.5 2.7 0.1 0.1 35.2 35.71 tal composition of cellulose which indicates the successful 0.5 2.7 0.1 0.1 35.2 0.5 2.8 0.1 0.1 36.8 1 3 Applied Water Science (2023) 13:144 Page 5 of 18 144 Scheme 2 Synthesis of DAC@GuTSC composite Scanning electron microscopy (SEM) (d) The surface morphology of DAC and DAC@GuTSC com- posite was studied by scanning electron microscopy at (c) 5000X, 15000X and 27000X magnifications. Figure  3 shows the SEM images obtained at three magnifications. One can (b) directly notice that the surface of the cellulose becomes rougher after being modified, which indicates the inser - (a) tion of new moieties into the original structure. In addition, 50 the surface of DAC@GuTSC has been shown to have large pores and pores that can help trapping metal ions during adsorption. 4000 3500 3000 2500 2000 1500 1000 500 -1 Wavenumber (cm ) Brunauer–Emmett–Teller analysis (BET) Fig. 2 FTIR of a native cellulose, b DAC, c DAC@Gu and d DAC@ The BET surface analysis was applied to evaluate the spe- GuTSC composite cific surface properties of the samples. The results indicate that natural cellulose and the DAC@GuTSC sorbent are Table 2 Elemental analysis of native cellulose and DAC@GuTSC microporous materials in nature. In addition, BET-specific surface area calculations showed that natural cellulose fib- Sample Carbon (%) Hydrogen Nitrogen (%) Sulfur (%) 2 −1 ers have a higher surface area (21.264 m  g ) than DAC@ (%) 2 −1 GuTSC composite (3.038 m   g ), Table 3. The decrease Native cel- 44.5 7.14 – – in surface area after chemical modification may be due to lulose the covering of cellulose pores by anchoring guanyl thio- DAC@ 46.4 5.81 8.32 3.81 semicarbazide moieties which reduces the adsorption of N GuTSC molecules used in the surface measurement. The relatively low surface area of the functionalized fibers suggests that modification of cellulose by introduction of new nitrogen the adsorption occurs mainly through the coordination of and sulfur functional groups. the N, N- and N, S donors of the guanyl thiosemicarbazide moieties with metal ions. 1 3 Transmittance (%) 144 Page 6 of 18 Applied Water Science (2023) 13:144 Fig. 3 SEM images of oxidized cellulose at a 5000×, b 15000×, c 27,000× and DAC@GuTSC at d 5000×, b 15,000× and f 27000× Table 3 BET analysis results Fig. 4a shows four stages of thermal decomposition, which in turn confirms the appearance of a change in the com- Sample Adsorp- Adsorp- Mean Surface Total pore position of natural cellulose. At 750 °C, the final residual weight tive tion tem- pore area volume 2 −1 3 −1 perature diameter (m  g ) (cm  g ) weight of DAC@GuTSC composite is 0.96%, indicating the (nm) remarkable thermal stability of DAC@GuTSC composite at very high temperatures. After adsorption of metal ions, the 0.0753 N2 77 K 4.7503 3.038 0.003608 final remaining mass of the DAC@GuTSC–metal complex at 750 °C was 41.3%, 40.2% and 56.1% for DAC@, GuTSC- Thermal gravimetric analysis (TGA) Cu, DAC@GuTSC-Hg and DAC@GuTSC-Pb, respectively. The increased residue value after metal adsorption compared A thermal gravimetric analysis (TGA) was performed to with DAC@GuTSC composite indicates their higher ther- mal stability. investigate the thermal decomposition of the DAC@GuTSC adsorbent before and after adsorption of heavy metal ions. Adsorption studies As shown in Fig. 4, in the temperature range (0–200)  °C, there is a very slight weight loss that actually starts after Point of zero charge (pH ) 100 °C mainly due to the evaporation of the water parts. PZC The reduced mass started to increase from about 250 °C The pH of adsorbent is one way to understand the to about 450 °C due to the pyrolysis of the sample. Simi- PZC lar decomposition behavior was observed before and after absorption mechanism. The surface charge of the DAC@ GuTSC adsorbent was assessed by measuring the pH . adsorption. The heatmap of natural cellulose shows two PZC stages of thermal degradation that typically yield levoglu- In general, adsorbents will show better affinity for anions at pH < pH and vice versa. The pH value obtained cosan and anhydrocellulose (Mohan et al. 2006). While the PZC PZC thermogram obtained from DAC@GuTSC composite in for the DAC@GuTSC composite is about 5.75, Figure 1 3 Applied Water Science (2023) 13:144 Page 7 of 18 144 Fig. 4 TGA curves of a DAC@GuTSC, b DAC@GuTSC-Cu, c DAC@GuTSC-Hg, d DAC@GuTSC-Pb S2. It is expected that the adsorption of metal ions can Eec ff t of pH be increased at the experimental pH (pH = 6) by electro- static interaction between Hg(II), Cu(II) and Pb(II), and The influence of pH value in the range 1.0–7.0 on metal the nitrogen-containing functional groups on the surface removal by DAC@GuTSC is shown in Fig. 5. The adsorp- of DAC@GuTSC. tion capacity (qe) exhibits an increasing trend with increase 2+ 2+ 2+ in pH value until peaking at pH 6 for Cu, Hg and Pb . The observed decrease trend in the removal % at low pH values can be explained by protonation taking place in an Fig. 5 Effect of pH on the 100 adsorption of Cu, Hg and Pb Cu onto DAC@GuTSC composite Hg Pb 123456 7 pH 1 3 q (mg/g) e 144 Page 8 of 18 Applied Water Science (2023) 13:144 acidic environment where protons are attached to negatively ions per unit volume increases. The chance of metal ions charged groups on the fiber of the adsorbent, thereby com- contacting DAC@GuTSC composite increases, resulting peting with the intended metal ions to be adsorbed. in a rapid increase in the amount of metal ions adsorbed. However, with a further increase in the initial concentration, Eec ff t of adsorbent dose the adsorption efficiency of DAC@GuTSC for metal ions reaches saturation, and the growth rate of the adsorption The adsorbent dosage was varied from 0.01 g to 0.1 g and curve becomes flat. the adsorption capacity was estimated for each dose. Fig- To better represent the effect of initial concentration on ure 6 describes the relationship between adsorbent dosage adsorption, Langmuir and Freundlich’s adsorption isotherm and adsorption capacity of DAC@GuTSC adsorbent. From models were used using linearization Eqs. (4) and (5) the figure, it can be concluded that the adsorption capacity ln q = ln K + 1∕n ln C (4) e F e increases as the adsorbent dose increases in a direct relation- ship, which may simply be due to the increased number of C ∕q = 1∕K q + C ∕q active sites. Then, when heavy metal saturation is reached, (5) e e L m e m the adsorption capacity becomes constant as the adsorbent 2+ 2+ where q is the equilibrium adsorption capacity, K is the e F dosage increases. Cu and Pb show saturation values at Freundlich constant, n is the heterogeneity coefficient 0.05 g of DAC@GuTSC adsorbent, while the maximum reflecting the energy distribution in the bonds, C is the equi- adsorption capacity for H g is only 0.03 g. The obtained librium metal concentration, K is the Langmuir constant, results have proven that the DAC@GuTSC adsorbent is a L and q is the maximum adsorption capacity of a layer. very effective heavy metal adsorbent with very low dosage. The adsorbent convenience was then investigated by cal- culating (R ) as the constant of the separation coefficient Eec ff t of the initial metal ion's concentration using Eq. (6). and adsorption isotherms R = 1∕ 1 + C K (6) L o L The effect of the initial concentration (C ) of different metal ions on the adsorption performance of DAC@GuTSC com- where K is the Langmuir adsorption constant and C is the L o posite is shown in Fig. 7. All the metal ion adsorption curves initial concentration of metal ions. of DAC@GuTSC composite have similar trends. As the ini- R values greater than 1.0 indicate adsorbent mismatch, tial concentration of metal ions in the solution increases, while R values between 0 and 1 indicate adsorbent concord- the adsorption capacities of DAC@GuTSC composite for ance. The derived parameters are listed in Table 4. From various metal ions show an overall upward trend. After the estimated values of the parameters for DAC@GuTSC, reaching a certain concentration, the upward trend of the it is found that the correlation coefficients in Langmuir’s adsorption curve slows down. An increase in the concentra- model are very high, which means the real data correspond tion of metal ions means that the absolute content of metal Fig. 6 Effect of adsorbent dose on the adsorption of Cu, Hg and Pb 1 3 Applied Water Science (2023) 13:144 Page 9 of 18 144 Fig. 7 Effect of initial metal ion concentration on the adsorption of Cu, Hg and Pb onto DAC@ GuTSC Table 4 Langmuir and Freundlich constants for metal adsorption by Eec ff t oscillation time and adsorption kinetics DAC@GuTSC Figure 8 shows the effects of oscillation time on the adsorp- Langmuir isotherm model 2+ 2+ 2+ tion of Cu, Hg and Pb onto DAC@GuTSC. It can be Adsorbates K (L/g) q (mg/g) R R L m 2 L seen that removal efficiency and adsorption capacity all 2+ Cu 0.384 80.65 0.9992 0.0103– increased rapidly and then remained stable with the increase 0.0495 in oscillation time. In adsorption initial stage, there were 2+ Hg 12.625 99.01 1 0.0003– many usable adsorption sites in the surface DAC@GuTSC, 0.0017 2+ 2+ 2+ accelerating the adsorption speed of Cu , Hg and Pb . 2+ Pb 0.366 84.03 0.9993 0.0108– As time went on, a large number of empty adsorption sites 0.0518 2+ 2+ 2+ had been occupied by Cu , Hg and Pb . This leads to the Freundlich isotherm model reduction of effective adsorption sites and adsorption speed. Adsorbates K n R F 2 Thus, in the later stage, their removal efficiency and adsorp- 2+ tion capacity unchanged insignificantly and finally reached Cu 62.23 24.04 0.7721 2+ equilibrium. The selection of proper adsorption equilibrium Hg 82.02 21.23 0.8716 2+ time can effectively shorten adsorption period. Thus, the Pb 64.70 24.04 0.8479 2+ 2+ 2+ oscillation time for the adsorption of Cu , Hg and Pb was 240 min. significantly to the model Langmuir. Meanwhile, the R Figure 8 represents the relationship between time of con- 2+ coefficients obtained from the Freundlich isotherm plot are tact and adsorption capacity for DAC@GuTSC-Hg by much lower. In addition, the maximum adsorption capacity DAC@GuTSC composite was the most rapid followed by 2+ 2+ for one layer (q ) obtained from the Langmuir plot is con- Pb and C u . Maximum adsorption capacity of DAC@ sistent with the experimental records, which clearly confirms GuTSC composite was reached approximately in the first that the adsorption process will be better described by Lang- 6 h and then equilibrium was reached. muir’s isothermal model. All calculated values of R ranged The obtained experimental data have been adapted to two from 0.0 to 1.0, confirming the suitability of DAC@GuTSC kinetic adsorption models; pseudo-first and pseudo-second- as adsorbent for the metal ions studied. order models to predict the adsorption mechanism. The kin- ematic parameters are calculated using Eqs. (7) and (8). 1 3 144 Page 10 of 18 Applied Water Science (2023) 13:144 Fig. 8 Effect of oscillation time on the adsorption of Cu, Hg and Pb onto DAC@GuTSC Pseudo-first-order (PFO) linear equation: Table 5 Kinetic parameters derived from pseudo-first-order model 2+ 2+ and pseudo-second-order model for adsorption of (Cu, Hg and 2+ 1∕q = k ∕q t + 1∕q Pb ) by DAC@GuTSC t(ads) 1 e(ads) e(ads) (7) 2+ 2+ 2+ Cu Hg Pb Pseudo-second-order (PSO) linear equation: Pseudo-first order t∕q = 1∕k q + 1∕q t (8) t(ads) 2 e(ads) e(ads)  q (mg/g) 62.11 108.7 64.9 e(ads) −1  K (min ) 116.77 135.97 97.51 where q is the equilibrium adsorption capacity, q e(ads) t(ads) 2  R 0.9712 0.9031 0.9709 is the adsorption capacity at time t, K is the adsorption Pseudo-second order rate constant of the pseudo-first-order model, and K is the  q (mg/g) 53 105.26 58 e(ads) adsorption rate constant. -4 −5 −4  k (g/(mg min)3.9 ×  108.65 ×  103.47 ×  10 The estimated kinetic parameters from the two models  R 0.9943 0.9842 0.9959 are summarized in Table  5, while the plotted curves are shown in Fig.  9. From the parameters obtained from the pseudo-first-order curves, it can be seen that the correlation coefficients (R ) are high, but the theoretical equilibrium chemisorption is the main dominant process and it is also adsorption capacity q for each metal does not match believed to be the limiting factor. e(ads) the experimental profile. On the other hand, the parame- ters calculated by pseudo-second-order model are consist- ent with the experimental results because the R value is Eec ff t of temperature thermodynamic parameters also high when approaching 1 and the adsorption capacity is consistent with the experimental results. Regarding the To investigate the effect of temperature on the adsorption of rate constants (K and K ) calculated in each model, it can the studied metal ions, several thermodynamic properties 1 2 be directly observed that the rate constants calculated from were investigated, including the Gibbs free energy change the first-order model are high, that is, the adsorption rate is (ΔG°), the thermal equilibrium constant (K ), standard slow, and therefore, it is inconsistent with the experimen- entropy change (ΔS°) and standard enthalpy change (ΔH°). tal results. Meanwhile, the rate constants obtained from the The values of the mentioned thermodynamic parameters are pseudo-second-order model are much smaller, which is more calculated after plotting 1/T vs LnK using Eqs. 9–11. significant and correlated with experimental results. Thus, it K = C ∕C 2+ 2+ 2+ (9) C ad e can be deduced that the adsorption of Cu , Hg and Pb by the DAC@GuTSC composite exhibits a pseudo-second- o o ln K =ΔS ∕R −ΔH ∕RT order kinetic model perfectly. It can also be concluded that C (10) ads ads 1 3 Applied Water Science (2023) 13:144 Page 11 of 18 144 Fig. 9 Adsorption kinetics models: a PFO, b PSO models Fig. 10 Relation between Lnk and 1/T for adsorption of Cu , +2 +2 Hg and Pb onto DAC@ GuTSC +2 +2 R is gas constant (8.314 J/mol K). Table 6 Thermodynamic parameters of adsorption of Cu, Hg and Pb by DAC@GuTSC ΔG =−RT ln K C (11) ads o o o ΔG (KJ /mol) ΔH (KJ/mol) ΔS (J/mol K) ads ads ads Figure 10 shows that the curves are plotted and the values 298 K 308 K 318 K − 421.39 − 1335.15 obtained are all listed in Table  6. The temperature range 2+ Cu − 26.82 − 2.42 − 0.59 studied is 298–318 K. The thermodynamic parameters of 2+ Hg − 28.39 − 2.55 − 0.85 − 442.58 − 1401.82 +2 +2 +2 the adsorption of C u, Hg and P b by DAC@GuTSC 2+ Pb − 27.06 − 4.54 − 0.74 − 422.31 − 1335.48 adsorbent are described in Table 6. Gibbs (ΔG ) free energy values for the whole adsorp- ads tion process show the spontaneity of the adsorption pro- metal ions of the studied adsorbent. Therefore, it is best to cess in the studied temperature range. The enthalpy change conduct adsorption experiments at moderately low temper- values (ΔH°) are also negative for all adsorption processes atures such as 298 K which is normal room temperature. indicating their exothermic behavior. The standard entropy change (ΔS°) is a measure of the randomness or distribu- Eec ff t of some selected interfering ions: tion of energy in a system. The negative ΔS° values also indicate that the low randomness reflects the high affinity The effect of the presence of foreign ions on heavy metal between the two modified cellulose (DAC@GuTSC) and adsorption was investigated under optimal adsorption condi- the adsorbed metal ions, which is a very good indication tions. The percentage removal for each metal is estimated at of the adsorption efficiency. Thus, it can be concluded that 50 ppm for certain interfering ions. The concentration of the high temperature is not favorable for the adsorption of 1 3 144 Page 12 of 18 Applied Water Science (2023) 13:144 Table 7 Removal of heavy metals on DAC@GuTSC in the presence Table 8 Repeated adsorption Cycle Recovery (%) 2+ 2+ of interfering ions of metal ions Cu, Hg and number 2+ −1 2+ 2+ 2+ Pb (50 ml of 50 mg L L ) Cu Hg Pb Interfering ions Added concentrations of % Removal by DAC@GuTSC sorbent interfering ions (ppm) 1 99.4 99.6 99.1 2+ 2+ 2+ (0.050 g), pH 6, time of shaking Cu Hg Pb 120 min, 25 oC, desorption by 2 98.5 98.6 98.1 2+ 5 mL of 0.5 mol/L HNO3 Mg 50 99.3 100 99.6 3 97.7 97.2 97.3 2+ Fe 50 98.7 98.4 98.1 4 96.4 96.3 96.8 2+ Ca 50 99.1 100 99.7 5 95.6 95.2 95.6 3+ Al 50 95.3 96.1 97.6 3− PO 50 84.6 99.4 98.5 Acetate 50 98.2 98.7 97.6 multi-metal solutions. As shown in Table  9, the percent- Oxalate 50 98.3 98.6 99.1 age removal shows the same trend of single-metal solutions Edetate 50 98.2 98.1 97.2 without obvious difference. The results also correlate with the conclusion obtained in the ionic hindrance that DAC@ GuTSC will perform efficiently in complex multi-component interfering ions is exactly equal to the metal concentration. All samples. The ICP OES is used to simultaneously determine results are summarized in Table 7. From the results obtained, the concentrations of multiple metal ions in the solutions it can be concluded that the presence of 50 ppm cations such studied. 2+ 2+ 2+ 3+ 3− as Mg, Fe, Ca and Al and anions such as PO , ace- tate, oxalate and edetate has no significant effect on heavy Accuracy and application of the method metal removal by DAC@GuTSC. The results give a promis- ing indication of the selectivity of DAC@GuTSC, suggesting To study the accuracy of the proposed procedure, known its potential for efficient operation in more complex media. amounts of analyte ions are added to tap water, Nile water and seawater samples, and then the proposed method is Eec ff t of sample volume applied. The results are presented in Table  10. There is good agreement between the amount of metal added and In order to deal with real samples, especially water samples, the amount measured. The calculated recovery values are containing very low concentrations of the metal ions, the always greater than 95%, thus confirming the accuracy of maximum applicable sample volume must be determined. the proposed procedure and its independence from matrix For this purpose, 25–1000 mL volumes of the model solu- effects. These results confirm the validity of the proposed tions containing 2–20 μg of the trace elements were passed separation/pre-enrichment method. through the column under the optimum conditions. The recovery values as a function of sample volume were quan- Plausible mechanism of adsorption titative and constant up to 1000 mL of the sample solution. The preconcentration factor was calculated as the ratio of To investigate the possible mechanism of metal ion adsorp- the highest sample volume (1000 mL) to the eluent volume tion onto DAC@GuTSC, the morphology, surface charge, (10 mL) and found to be 100 for all the metal ions. optical images and FTIR of the adsorbent were evaluated. Desorption and reusability of DAC@GuTSC composite Optical images Optical images of natural  cellulose, oxi- dized cellulose (DAC), DAC@GuTSC and metal-loaded To test the reusability of DAC@GuTSC, five cycles of modified cellulose: DAC@GuTSC-Cu, DAC@GuTSC-Hg adsorption–desorption have been carried out under the opti- and DAC@GuTSC-Pb are  shown in Fig.  11(a–f), respec- mum conditions, using 5 ml of 0.5 M HN O , the obtained tively. The images show the obvious color change of the results are shown in Table 8. From the results, it was clear modified cellulose before metal absorption (light yellow) that the adsorption efficiency of DAC@GuTSC was only compared with the modified cellulose after metal absorp- slightly decreased after cycle five, the adsorbent maintained tion. These results indicate the tendency of DAC@GuTSC about 95% of its initial efficiency. modified cellulose to adsorb investigated metal ions. Adsorption from multi‑metal solutions FTIR spectra of  DAC@GuTSC before  and  after  adsorption of metal ions The adsorption mechanism of the Cu, Hg and A mixture of metals under study was prepared to investigate Pb metal ions was designed in light of the effective groups the adsorption efficiency of the prepared DAC@GuTSC in available on DAC@GuTSC surface as shown in Fig. 12a and 1 3 Applied Water Science (2023) 13:144 Page 13 of 18 144 2+ 2+ Table 9 Simultaneous removal of multi-metal solution of (Cu , Hg and Pb2 +) (50 ml of 50 mg L-1) by DAC@GuTSC sorbent (0.050 g), pH 6, time of shaking 120 min, 25 °C from natural water samples Sample Metal ion Added (ppm) Found (ppm) % Removal 2+ 2+ 2+ Multi-metal solution of (Cu, Hg Cu 50.0 5.25 89.5 2+ and Pb ) 2+ Hg 50.0 8.4 91.6 2+ Pb 50.0 4.59 90.82 The concentration found in the aqueous solution after adsorption and ICP-AES determination 2+ 2+ 2+ Table 10 Removal of single-metal solution of (Cu , Hg and Pb ) with the coordinating N,N donors and N,S donors present −1 (50 ml of 50 mg L ) by DAC@GuTSC sorbent (0.050 g), pH 6, time onto the DAC@GuTSC chelating fibers. The main charac- of shaking 120  min, 25  °C from natural water samples (sample vol- teristic peaks of azomethine presented obvious, shifted upon ume: 250 mL, final volume: 10 mL, n = 3) 2+ complexation with the Cu ions. Thus, the value of stretch- −1 Sample Metal Ion Added (μg) Found (μg) Recovery % ing vibrations of C=N at 1610  cm was moved to lower −1 2+ value at 1580  cm , and this revealed that the complexation Tap water Cu – – takes place between the two nitrogen atoms of the two C=N 15.0 14.3 95.33 groups and copper ions. Moreover, coordination of thiolate 30.0 29.2 97.33 2+ S atom through –C–S–metal mode after enolization followed Hg – – by deprotonation on sulfur to the metal ion is suggested by 15.0 14.5 96.67 the shift of the ν(C=S) band at lower wave number in all of 30.0 29.4 98,00 2+ the studied complexes. The presence of a new band due to ν Pb – −1 (M–S) at 420–425  cm is another indication of the involve- 15.0 14.6 97.33 ment of the S atom in coordination. 30.0 29.5 98.33 2+ In conclusion, the DAC@GuTSC composite can bind Nile water Cu – to metal ions through N, N donors forming four- and five- 15.0 14.4 96.00 membered chelate rings and through N, S donors forming 30.0 29.6 98.67 2+ six-membered chelate rings, Scheme 3 Hg – 15.0 14.30 95.33 Performance of DAC@GuTSC 30.0 29.4 98.00 2+ Pb – To increase the value of the sorbent, we conducted a com- 15.0 14.4 96.00 parative study of the maximum sorption capacity achieved 30.0 29.6 98.66 2+ for the same contaminants with other sorbents and activated Sea water Cu – carbon described in the literature. Table 11 summarizes dif- 15.0 14.30 95.33 ferent values of q for different sorbents. The adsorption of max 30.0 29.2 97.33 2+ Cu, Hg and Pb observed in this study correlates with other Hg – studies with maximum adsorption capacities q for Cu, max 15.0 14.5 96.67 −1 Hg and Pb at 298 K of 50, 94, and 55 mg  g . Comparing 30.0 29.4 98,00 2+ the adsorption capacities obtained from most of the studies Pb – mentioned, we found that the adsorption capacity of DAC@ 15.0 14.4 96.00 GuTSC is higher. Using Cu as an example, DAC@GuTSC 30.0 29.2 97.33 −1 has an adsorption capacity of 50 mg  g , while all the meth- ods described gave adsorption capacities ranging from 1.75 −1 to 36 mg  g . Differences in Cu, Hg and Pb uptake are due (Fig. S3a). In fact, DAC@GuTSC composite is very abun- dant with active groups that can adsorb the three pollutants. to the morphological properties of each sorbent, including structure, functional groups and surface area. Desorption is These active groups come from the fact that the adsorbent is composed of dialdehyde cellulose and guanyl thiosemicar- an unavoidable process and an intermediate step for adsor- bent regeneration. The latter is a key point for evaluating the bazide which in their origin are rich in active groups. FTIR spectrum of DAC@GuTSC–Cu(II), Fig. 12b and reuse of sorbents for industrial applications due to environ- mental concerns and the need for sustainable development. (Fig. S3b) was also used for evaluation of the mechanism by 2+ which the Cu , as a representative example, can coordinate In the future, experiments can be performed at column scale 1 3 144 Page 14 of 18 Applied Water Science (2023) 13:144 Fig. 11 Optical images of a Native cellulose powder, b DAC oxidized cellulose, c DAC@ GuTSC, d DAC@GuTSC-Cu, e DAC@GuTSC-Hg and f DAC@GuTSC-Pb Conclusions (b) In order to find low-cost adsorbents, having pollutant- binding capacities is highly significant for efficient water treatment. The results of the present study reveal that: (a) i. DAC@GuTSC composite may be highly applicable adsorbent for the removal of heavy metals from aque- ous solutions. ii. Modification of DAC by aminoguanidine and phenyl 4000 3500 3000 2500 2000 1500 1000 500 -1 isothiocyanate significantly increased the nitrogen and Wavenumber (cm ) sulfur-containing groups on the surface of DAC@ GuTSC composite with remarkable change in textural Fig. 12 FTIR of a DAC@GuTSC and b DAC@GuTSC-Cu(II) properties and surface morphology. 2+ 2+ 2+ iii. The adsorption of Cu, Hg and Pb was dependent and in pilot plants. These experiments can be implemented on initial concentration, reaction temperature and pH. to be applied to sewage treatment plants to remove cationic iv. The equilibrium of adsorption process could is well and anionic metal ions and textile dyes from wastewater. described by Langmuir adsorption isotherms, i.e., monolayer adsorption on a homogenous surface. The 2+ Cu Scheme 3 Plausible mechanism NH 2+ S Cu NH NH S of Cu(II) onto DAC@GuTSC N H N N NH 2+ N 0.2M HNO 3 H N H Cu H N NH NH H composite H 2+ Desorption adsorption Cu DAC@GuTSC DAC@GuTSC-Cu(II) DAC@GuTSC 1 3 Transmittance (%) Cellulose Cellulose Cellulose Applied Water Science (2023) 13:144 Page 15 of 18 144 +2 +2 +2 Table 11 Comparison of the adsorption capacities of Cu, Hg and Pb by DAC@GuTSC with other adsorbents Metal ion Adsorbent Adsorption capac- Reference −1 ity (mg  g ) Cu DAC@GuTSC 50 Present work Microfibrillated cellulose modified with aminopropyltriethoxysilane 3.150 Hokkanen et al. (2014) Cellulose modified with acrylic acid 17.2 Güçlü et al. (2003) Cortex banana waste 36.0 Kelly-Vargas et al. (2012) Citric acid modified cellulose 24 Low et al. (2004) Pristine nanocellulose 20 Liu et al. (2015) Peanut shells 25.39 Witek-Krowiak et al. (2011) Orange peels modified with HNO (0.1 M) 15.27 Lasheen et al. (2012) Cationic wheat straw 33.5 Zhong et al. (2014) Tobacco dust as a lignocellulosic source 36.0 Qi and Aldrich (2008) Pomegranate peel 30.12 Ben-Ali et al. (2017) Oil palm shell 1.75 Chong et al. (2013) Rice husk 30.0 Sobhanardakani et al. (2013) Hg DAC@GuTSC 94 Present work Bamboo leaf powder as a cellulose source 27.11 Mondal et al. (2013) Guanyl modified cellulose 48 Khan et al. (2004) Eucalyptus bark 34.60 Ghodbane and Hamdaoui (2008) Bacillus subtilis biomass 68.5 Wang et al. (2010) Silica gel modified with 2-(2-oxoethyl)hydrazine carbothioamide 37.5 3 Chai et al. (2010) Allium sativum L 0.6497 Eom et al. (2011) Magnetic nanoparticles doped with 1,5-diphenylcarbazide 44 Zhai et al. (2010) Pb DAC@GuTSC 55 Present work Cellulose powder modified with acrylic acid 55.9 Güçlü et al. (2003) Guanyl modified cellulose 52 Khan et al. (2004) Nano-TiO 7.41 Poursani et al. (2016) Citric acid modified cellulose 83 Mohan et al. (2006) Cotton as cellulosic biomass 10.78 Wu et al. (2012) Pine cone powder modified with NaOH(0.01 M) 24.75 Ofomaja and Naidoo (2010) Cauliflower waste 47.63 Hossain et al. (2014) Sorghum bicolor L. modified with thiourea 17.82 Ofomaja and Naidoo (2010) Oil palm shell 3.39 Chong et al. (2013) Tobacco dust as a lignocellulosic source 39.6 Qi and Aldrich (2008) S. bengalense extract modified with urea 12.65 Din et al. (2014) kinetic studies follow a pseudo-second-order kinetic viii. Submersion of the DAC@GuTSC-loaded metals sam- model. ples in 5 ml of 0.5 M HNO resulted in the desorption o o v. The negative values of (ΔG ) and (∆H ) thermody- of more than 90% of the adsorbed metal ions. 2+ 2+ 2+ namic parameters clarify the spontaneous and exo- ix. The uptake of Cu , Hg and Pb using such DAC@ thermic nature of the adsorption technique. GuTSC composite is highly comparable to the previ- 2+ vi. In this study, the prepared DAC@GuTSC adsorbent ous commercial adsorbents used for removal of Cu , 2+ 2+ 2+ 2+ 2+ has high removal efficiency of Cu, Hg and Pb Hg and Pb . at optimum batch sorption condition with maximum x. The mechanism of adsorption was complex where −1 2+ sorption capacity of 50, 94 and 55 mg  g for Cu , DAC@GuTSC composite, possessing the synergistic 2+ 2+ Hg and Pb , respectively, that was achieved within effects of DAC and guanyl thiosemicarbazide, showed 240 min. surface complexation between the N, N- and N, S 2+ 2+ 2+ vii. The removal of Cu, Hg and Pb from natural donors of the guanyl thiosemicarbazide moiety with water samples was successfully applied using DAC@ metal ions. GuTSC. 1 3 144 Page 16 of 18 Applied Water Science (2023) 13:144 to determination by flame atomic absorption spectrometry. Anal xi. In conclusion, the present work well demonstrated the Sci 21(8):923–931 potential of this technique for wider applications. Akl MA, Sarhan AA, Shoueir KR, Atta AM (2013) Application of crosslinked ionic poly (vinyl alcohol) nanogel as adsorbents for water treatment. J Dispersion Sci Technol 34(10):1399–1408 Supplementary Information The online version contains supplemen- Akl MA, El-Zeny AS, Hashem MA, El-Gharkawy ESRH (2021) tary material available at https://doi. or g/10. 1007/ s13201- 023- 01948-9 . Synthesis, characterization and analytical applications of chemi- cally modified cellulose for remediation of environmental pol- Author contributions Magda A Akl was involved in conceptualization, lutants. Egypt J Chem 64(7):3889–3901. h t t ps : / / d o i . o r g / 1 0 . supervision, investigation, methodology, visualization, writing—origi- 21608/ ejchem. 2021. 65793. 3412 nal draft, writing—review & editing. Abdelrahman S El-Zeny helped in Atta A, Akl MA, Youssef AM, Ibraheim MA (2013) Superparamag- writing—original draft, writing—review & editing. Mohamed Ismail netic core-shell polymeric nanocomposites for efficient removal contributed to supervision. Mohamed Abdalla was involved in super- of methylene blue from aqueous solutions. Adsorpt Sci Technol vision. Dina Abdelgelil helped in investigation, methodology, valida- 31(5):397–419 tion, visualization, writing—original draft, writing & editing. Aya G Aydın H, Bulut Y, Yerlikaya Ç (2008) Removal of copper (II) from Mostafa contributed to investigation, methodology, writing—review aqueous solution by adsorption onto low-cost adsorbents. J & editing. Environ Manage 87(1):37–45 Balachandran V, Murali MK (2011) FT-IR and FT-Raman spectral Funding Open access funding provided by The Science, Technology & analysis of 3-(trifluromethyl) phenyl isothiocyanate. Elixir Vib Innovation Funding Authority (STDF) in cooperation with The Egyp- Spec 40:5105–5107 tian Knowledge Bank (EKB). This study received no support from Ben-Ali S, Jaouali I, Souissi-Najar S, Ouederni A (2017) Charac- public, private or nonprofit funding agencies. terization and adsorption capacity of raw pomegranate peel biosorbent for copper removal. J Clean Prod 142:3809–3821 Availability of data and materials Data supporting the results reported Bilal M, Shah JA, Ashfaq T, Gardazi SMH, Tahir AA, Pervez A, in the article can be requested from authors. Haroon H, Mahmood Q (2013) Waste biomass adsorbents for copper removal from industrial wastewater—a review. J Hazard Declarations Mater 263:322–333 Chai X, Chang X, Hu Z, He Q, Tu Z, Li Z (2010) Solid phase extrac- Ethical approval The authors acknowledge that the current research tion of trace Hg (II) on silica gel modified with 2-(2-oxoethyl) has been conducted ethically. They declared that this manuscript does hydrazine carbothioamide and determination by ICP-AES. Tal- not involve researching about humans or animals. anta 82(5):1791–1796 Chang LW (1977) Neurotoxic effects of mercury—a review. Environ Consent to participate The authors consent to participate in this Res 14(3):329–373 research study. Chaturvedi SI (2013) Electrocoagulation: a novel waste water treat- ment method. Int J Modern Eng Res 3(1):93–100 Chong HLH, Chia PS, Ahmad MN (2013) The adsorption of heavy Conflict of interest Authors declare no known competing interests. metal by Bornean oil palm shell and its potential application as constructed wetland media. Biores Technol 130:181–186 Open Access This article is licensed under a Creative Commons Attri- Clarkson TW (1993) Mercury: major issues in environmental health. bution 4.0 International License, which permits use, sharing, adapta- Environ Health Perspect 100:31–38 tion, distribution and reproduction in any medium or format, as long Clarkson TW, Magos L (2006) The toxicology of mercury and its as you give appropriate credit to the original author(s) and the source, chemical compounds. Crit Rev Toxicol 36(8):609–662 provide a link to the Creative Commons licence, and indicate if changes Dacrory S (2021) Antimicrobial activity, DFT calculations, and were made. The images or other third party material in this article are molecular docking of dialdehyde cellulose/graphene oxide film included in the article's Creative Commons licence, unless indicated against Covid-19. J Polym Environ 29(7):2248–2260. https:// otherwise in a credit line to the material. If material is not included in doi. org/ 10. 1007/ s10924- 020- 02039-5 the article's Creative Commons licence and your intended use is not Dacrory S, Abou-Yousef H, Kamel S, Abou-Zeid RE, Abdel-Aziz permitted by statutory regulation or exceeds the permitted use, you will MS, Elbadry M (2019) Functionalization and cross-linking of need to obtain permission directly from the copyright holder. To view a carboxymethyl cellulose in aqueous media. Cell Chem Technol copy of this licence, visit http://cr eativ ecommons. or g/licen ses/ b y/4.0/ . 53(1–2):23–33 Din MI, Hussain Z, Mirza ML, Shah AT, Athar MM (2014) Adsorp- tion optimization of lead (II) using Saccharum bengalense as a non-conventional low cost biosorbent: isotherm and thermody- References namics modeling. Int J Phytorem 16(9):889–908 Dridi-Dhaouadi S, Douissa-Lazreg NB, M’Henni MF (2011) Acemioglu B, Alma MH (2001) Equilibrium studies on adsorption of Removal of lead and Yellow 44 acid dye in single and binary Cu (II) from aqueous solution onto cellulose. J Colloid Interface component systems by raw Posidonia oceanica and the cellulose Sci 243(1):81–84 extracted from the raw biomass. Environ Technol 32(3):325–340 Akl MAA, Kenawy IMM, Lasheen RR (2004) Organically modified Eom Y, Won JH, Ryu J-Y, Lee TG (2011) Biosorption of mercury silica gel and flame atomic absorption spectrometry: employment (II) ions from aqueous solution by garlic (Allium sativum L.) for separation and preconcentration of nine trace heavy metals powder. Korean J Chem Eng 28:1439–1443 for their determination in natural aqueous systems. Microchem Friberg L, Mottet NK (1989) Accumulation of methylmercury J 78(2):143–156 and inorganic mercury in the brain. Biol Trace Elem Res Akl MAA-E, Kenawy IM, Lasheen RR (2005) Silica gel modified with 21:201–206 N-(3-propyl)-o-phenylenediamine: Functionalization, metal sorp- tion equilibrium studies and application to metal enrichment prior 1 3 Applied Water Science (2023) 13:144 Page 17 of 18 144 Gherasim C-V, Mikulášek P (2014) Influence of operating variables Magos L, Clarkson TW (2006) Overview of the clinical toxicity of on the removal of heavy metal ions from aqueous solutions by mercury. Ann Clin Biochem 43(4):257–268 nanofiltration. Desalination 343:67–74 Martin S, Griswold W (2009) Human health effects of heavy metals. Ghodbane I, Hamdaoui O (2008) Removal of mercury (II) from Environ Sci Technol Briefs Citizens 15:1–6 aqueous media using eucalyptus bark: kinetic and equilibrium Meena AK, Mishra GK, Rai PK, Rajagopal C, Nagar PN (2005) studies. J Hazard Mater 160(2–3):301–309 Removal of heavy metal ions from aqueous solutions using car- Gotoh T, Matsushima K, Kikuchi K-I (2004a) Adsorption of Cu and bon aerogel as an adsorbent. J Hazard Mater 122(1–2):161–170. Mn on covalently cross-linked alginate gel beads. Chemosphere https:// doi. org/ 10. 1016/j. jhazm at. 2005. 03. 024 55(1):57–64 Mohan D, Pittman CU Jr, Steele PH (2006) Pyrolysis of wood/biomass Gotoh T, Matsushima K, Kikuchi K-I (2004b) Preparation of algi- for bio-oil: a critical review. Energy Fuels 20(3):848–889 nate–chitosan hybrid gel beads and adsorption of divalent metal Mondal DK, Nandi BK, Purkait MK (2013) Removal of mercury ions. Chemosphere 55(1):135–140 (II) from aqueous solution using bamboo leaf powder: equilib- Güçlü G, Gürdağ G, Özgümüş S (2003) Competitive removal of rium, thermodynamic and kinetic studies. J Environ Chem Eng heavy metal ions by cellulose graft copolymers. J Appl Polym 1(4):891–898 Sci 90(8):2034–2039 Monier M, Akl MA, Ali W (2014a) Preparation and characterization of Gupta VK (2009) Application of low-cost adsorbents for dye selective phenyl thiosemicarbazide modified Au(III) ion-imprinted removal–a review. J Environ Manage 90(8):2313–2342 cellulosic cotton fibers. J Appl Polym Sci 131(18):9277–9287. Guzzi G, La Porta CAM (2008) Molecular mechanisms triggered by https:// doi. org/ 10. 1002/ app. 40769 mercury. Toxicology 244(1):1–12 Monier M, Akl MA, Ali WM (2014b) Modification and characteriza- Hokkanen S, Repo E, Suopajärvi T, Liimatainen H, Niinimaa J, Sil- tion of cellulose cotton fibers for fast extraction of some precious lanpää M (2014) Adsorption of Ni (II), Cu (II) and Cd (II) from metal ions. Int J Biol Macromol 66:125–134 aqueous solutions by amino modified nanostructured microfi- Navarro RR, Sumi K, Fujii N, Matsumura M (1996) Mercury removal brillated cellulose. Cellulose 21:1471–1487 from wastewater using porous cellulose carrier modified with Hossain MA, Ngo HH, Guo WS, Nguyen TV, Vigneswaran S (2014) polyethyleneimine. Water Res 30(10):2488–2494 Performance of cabbage and cauliflower wastes for heavy metals Nayl AA, Abd-Elhamid AI, Abu-Saied MA, El-Shanshory AA, Soli- removal. Desalin Water Treat 52(4–6):844–860 man HMA, Akl MA, Aly HF (2020) A novel method for highly Hua M, Zhang S, Pan B, Zhang W, Lv L, Zhang Q (2012) Heavy effective removal and determination of binary cationic dyes in metal removal from water/wastewater by nanosized metal aqueous media using a cotton–graphene oxide composite. RSC oxides: a review. J Hazard Mater 211:317–331 Adv 10(13):7791–7802 Ibrahim A, El Fawal GF, Akl MA (2019) Methylene blue and crystal Nouri L, Ghodbane I, Hamdaoui O, Chiha M (2007) Batch sorption violet dyes removal (as A binary system) from aqueous solution dynamics and equilibrium for the removal of cadmium ions from using local soil clay: kinetics study and equilibrium isotherms. aqueous phase using wheat bran. J Hazard Mater 149(1):115–125 Egypt J Chem 62(3):541–554 O’Connell DW, Birkinshaw C, O’Dwyer TF (2008) Heavy metal adsor- Jamil N, Munawar MA, Muntaha ST (2009) Biosorption of Hg (II) bents prepared from the modic fi ation of cellulose: a review. Biores and Cd (II) from waste water by using Zea Mays waste. J Chem Technol 99(15):6709–6724 Soc Pakistan 31 Ofomaja AE, Naidoo EB (2010) Biosorption of lead (II) onto pine cone Kelly-Vargas K, Cerro-Lopez M, Reyna-Tellez S, Bandala ER, powder: studies on biosorption performance and process design Sanchez-Salas JL (2012) Biosorption of heavy metals in pol- to minimize biosorbent mass. Carbohyd Polym 82(4):1031–1042 luted water, using different waste fruit cortex. Phys Chem Earth Pan B, Pan B, Zhang W, Lv L, Zhang Q, Zheng S (2009) Development Parts a/b/c 37:26–29 of polymeric and polymer-based hybrid adsorbents for pollutants Kenawy IM, Hafez MAH, Ismail MA, Hashem MA (2018) Adsorp- removal from waters. Chem Eng J 151(1–3):19–29 tion of Cu(II), Cd(II), Hg(II), Pb(II) and Zn(II) from aqueous Poursani AS, Nilchi A, Hassani A, Shariat SM, Nouri J (2016) The single metal solutions by guanyl-modified cellulose. Int J Biol synthesis of nano TiO 2 and its use for removal of lead ions from Macromol 107:1538–1549. https:// doi. org/ 10. 1016/j. ijbio mac. aqueous solution. J Water Resour Prot 8(04):438 2017. 10. 017 Qi BC, Aldrich C (2008) Biosorption of heavy metals from aqueous Khan NA, Ibrahim S, Subramaniam P (2004) Elimination of heavy solutions with tobacco dust. Biores Technol 99(13):5595–5601 metals from wastewater using agricultural wastes as adsorbents. Shoueir KR, Sarhan AA, Atta AM, Akl MA (2016) Macrogel and Malaysian J Sci 23(1):43–51 nanogel networks based on crosslinked poly (vinyl alcohol) for Kurniawan TA, Chan GYS, Lo W-H, Babel S (2006) Physico–chemi- adsorption of methylene blue from aqua system. Environ Nano- cal treatment techniques for wastewater laden with heavy metals. technol Monitor Manage 5:62–73 Chem Eng J 118(1–2):83–98 Shoueir KR, Atta AM, Sarhan AA, Akl MA (2017) Synthesis of Lasheen MR, Ammar NS, Ibrahim HS (2012) Adsorption/desorption of monodisperse core shell PVA@ P (AMPS-co-NIPAm) nanogels Cd (II), Cu (II) and Pb (II) using chemically modified orange peel: structured for pre-concentration of Fe (III) ions. Environ Technol equilibrium and kinetic studies. Solid State Sci 14(2):202–210 38(8):967–978 Lee I-H, Kuan Y-C, Chern J-M (2007) Equilibrium and kinetics of Sobhanardakani S, Parvizimosaed H, Olyaie E (2013) Heavy metals heavy metal ion exchange. J Chin Inst Chem Eng, 38(1):71–84 removal from wastewaters using organic solid waste—rice husk. Liu B, Huang Y (2011) Polyethyleneimine modified eggshell mem- Environ Sci Pollut Res 20:5265–5271 brane as a novel biosorbent for adsorption and detoxification of Suhas, Gupta VK, Carrott PJM, Singh R, Chaudhary M, Kushwaha Cr (VI) from water. J Mater Chem 21(43):17413–17418 S (2016) Cellulose: a review as natural, modified and activated Liu P, Borrell PF, Božič M, Kokol V, Oksman K, Mathew AP (2015) carbon adsorbent. Bioresour Technol 216:1066–1076. https://d oi. Nanocelluloses and their phosphorylated derivatives for selective org/ 10. 1016/j. biort ech. 2016. 05. 106 adsorption of Ag+, Cu2+ and Fe3+ from industrial effluents. J Wang L, Li J (2013) Adsorption of CI Reactive Red 228 dye from Hazard Mater 294:177–185 aqueous solution by modified cellulose from flax shive: Kinetics, Low KS, Lee CK, Mak SM (2004) Sorption of copper and lead by citric equilibrium, and thermodynamics. Ind Crops Prod 42:153–158 acid modified wood. Wood Sci Technol 38:629–640 1 3 144 Page 18 of 18 Applied Water Science (2023) 13:144 Wang XS, Li FY, He W, Miao HH (2010) Hg (II) removal from aque- solution using magnetic nanoparticles doped with 1,5-diphenyl- ous solutions by Bacillus subtilis biomass. Clean: Soil, Air, Water carbazide. Microchim Acta 169(3):353–360. https:// doi. org/ 10. 38(1):44–481007/ s00604- 010- 0363-8 Witek-Krowiak A, Szafran RG, Modelski S (2011) Biosorption of Zhao G, Wu X, Tan X, Wang X (2010) Sorption of heavy metal ions heavy metals from aqueous solutions onto peanut shell as a low- from aqueous solutions: a review. Open Colloid Sci J 4(1) cost biosorbent. Desalination 265(1–3):126–134 Zhong QQ, Yue QY, Li Q, Gao BY, Xu X (2014) Removal of Cu(II) Wu Z, Cheng Z, Ma W (2012) Adsorption of Pb (II) from glucose solu- and Cr(VI) from wastewater by an amphoteric sorbent based on tion on thiol-functionalized cellulosic biomass. Biores Technol cellulose-rich biomass. Carbohyd Polym 111:788–796. https:// 104:807–809doi. org/ 10. 1016/j. carbp ol. 2014. 05. 043 Xu Y, Huang C, Wang X (2013) Characterization and controlled release aloe extract of collagen protein modified cotton fiber. Carbohyd Publisher's Note Springer Nature remains neutral with regard to Polym 92(2):982–988 jurisdictional claims in published maps and institutional affiliations. Zewail TM, Yousef NS (2015) Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed. Alex Eng J 54(1):83–90 Zhai Y, Duan S, He Q, Yang X, Han Q (2010) Solid phase extrac- tion and preconcentration of trace mercury(II) from aqueous 1 3

Journal

Applied Water ScienceSpringer Journals

Published: Jun 1, 2023

Keywords: Adsorption; Cellulose; Aminoguanidine; Phenyl isothiocyanate; Heavy metals; Water treatment

There are no references for this article.