Abstract
The current study is focused on using tannery waste called buffing dust to remove hexavalent chromium from an aqueous solution. The buffing dust was characterised by using different technique like FTIR, SEM, and BET analysis. The adsorption experiment was conducted in batch mode. The different operating factors including contact time, dose and initial Cr (VI) concentration were investigated. The optimum adsorption capacity was observed at contact time of 240 min and dose of 1g/100 mL. The adsorption isotherm such as Langmuir, Freundlich and Temkin were investigated at different initial concentration. It was observed that Langmuir isotherm model was best fitted for present study with maximum adsorption efficiency of 11.33 mg/g. The kinetic study was performed for pseudo first order and pseudo second order and it was found that pseudo second order model was provided the best match with regression coefficient (R2) of 0.9991.
Keywords: Adsorption, Buffing dust, Hexavalent chromium, Tannery
Graphical abstract
1. Introduction
Chromium is a one of the most easily available elements in the earth's crust. It is a transition element and ranges from Cr (II) to Cr (VI) in numerous oxidation states, but trivalent and hexavalent chromium are most accepted and stable valence states [1]. Cr (III) is an essential nutrient in low doses [2]. It plays an important role to potentiate insulin and regulate glucose metabolism. Chromium (VI) has very hazardous effect on the environment and human health. Hexavalent chromium is very well known to be carcinogenic [3]. In general it is assumed that toxicity level of hexavalent chromium is 100 fold more than trivalent chromium [4].
Ingestion, Inhalation and dermal contact are the main exposure pathway for chromium in human body [5]. People who work directly in the chrome business have reported diseases like kidney failure, mouth ulcers, indigestion, acute tubular necrosis, vomiting, and other health issues as a result of contact with Cr (VI). They may be more susceptible to irritative dermatitis and chronic skin ulcers. Dermatitis is caused by chromates and Cr (III), which are released from alloys and Cr-plated objects. Inhalation exposure to chromium is majorly due to industrial emission of chromium industries like welding, chromate production, pigment production and chrome plating which consist mixed exposure of tri and hexavalent chromium. During the conversion of Cr (VI) to Cr (III) lung tissue absorbs trivalent chromium [6]. Cr (VI) causes Rhinitis bronchospasm and pneumonia to chrome workers [7]. It also leads to lung cancer [8].
The leather manufacturing sectors are one of the main causes of water contamination. The groundwater could get contaminated with chrome from the tanneries wastewater, putting the local population at risk if they drink it. Even a low quantity of hexavalent chromium is harmful to humans [9]. EPA suggested Cr (VI) tolerance levels of 0.1 and 0.05 mg/L for inland surface water and potable water respectively [2,10]. Based on the plenty of evidences for the carcinogenicity of hexavalent chrome compounds as found in chromate production, chrome plating industries, refractory material, tannery, textile industry, mining of chrome ore, dye and pigment industries, International Agency for Research on Cancer reveals that hexavalent chromium is carcinogenic in nature.
Metallurgical, Chemical and Refractory are the well-known Industries where chromium is used in substantial quantity. The leather sector is well known for hazardous environmental issues worldwide due to high amount of heavy metals pollution. In tannery the basic chrome sulphate Cr (OH)SO4 which is formed through reduction of Na2Cr2O7 is the most common tanning agent because of its exceptional tanning properties. Formation of cross links between collagen fibre and chromium takes place which stabilize the leather [11]. More than 80% of the tanneries in India adopted the chrome tanning process due to its tanning speed, low operational cost and durability of the processed leather. In the Chrome tanning process raw hide takes only 60 to 70% of the added basic chrome sulphate and the remaining salt is discharged as chrome effluent into waste water [12,13]. Despite the use of Cr (III) sulphate during operation of leather processing, substantial amount of Cr (VI) is generated due to oxidation of Cr (III). Oxidation of Cr (III) may take place due to the use of unsaturated lipids and vegetable oils in fatliquoring operation [14]. High temperature, a dry environment and exposure to UV radiation are also the reason for oxidation of Cr (III) into Cr (VI) [15]. Cr (VI) in the chrome drain may also be increased by the unreduced dichromate present in the cationic chrome liquor.
Various techniques such as adsorption, chemical precipitation [16], coagulation [17], flocculation [18], reverse osmosis membrane [19], filtration, electrochemical treatment [20,21], electrocoagulation [22,23], electro-oxidation, ion–exchange [24], phytoremediation [25] and surfactant-assisted bioremediation [26] etc., are being used for the removal of chromium from waste water [12,27].
Attempts were made to remove chromium ions from water/waste water by many scholars using different sorbent material such as tires waste-derived magnetic-activated carbon [28], coffee husk [29], activated carbon primed from sugarcane bagasse [30], chrome saving (Cs) and Cs tannins [31], expholiated graphene oxide [32], sawdust [33,34], maize bran [35], waste tea [36], sunflower stem [37], sawdust [38], waste newspaper [39], reticulated chitosan micro/nanoparticles from seafood processing waste [40], magnetic natural zeolite-polymer composite [41], apple residue [42], zero-valent iron nanoparticles [43], acid-washed zero-valent aluminium [44], sugar waste [45], badam shell bio-char [46], wheat straw & press mud biochar [47], douglas fir [48], sugarcane bagasse biochar [49], almond hull [50], magnetic titanium nanotubes coated phosphorene [51], silica [52], hyacinth roots [53], canadian peat and coconut fiber [54], vesicular basalt [55], eucalyptus saw dust [56] activated biochar from rice husk [57]. The hexavalent chromium is removed from the aqueous phase utilising an adsorption strategy in the current investigations due to its simplicity and cost-effectiveness. In the current work, an effort has been made to remove the hexavalent chromium ion from aqueous phase utilising buffing dust as an adsorbent. Adsorption isotherm and kinetic model is also elaborated in the present study.
Buffing dust is a by-product of leather industry (Tannery). It is micro fine proteinous solid compound which contains chromium, fat, tanning agent and dye molecule [58]. Buffing operation is an essential mechanical process for the development of velvety nap and writing effect on the flesh side of suede leather and on the grain side of nubuck leather. This process produces buffing dust, which is one among the tanned collagenous solid wastes generated from tannery. Size of buffing dust depends upon the grit of emery paper used in buffing operation. Emery paper of high grit (600, 800 and 1000) as in case of production of nubuck leather produces fine buffing dust. Emery paper of high grit produces short and very fine nap on the leather. Contrary to this, emery paper of low grit (100, 200) which is generally used to make suede leather where velvety naps developed on the flesh side produces coarse buffing dust. Approx 2–6 kg of buffing dust is generated per ton of processed leather [59]. Buffing dust itself carries 2.7% Cr on dry weight basis [60].
2. Material and methods
2.1. Preparation and characterization of adsorbent
Emery paper of 600 and 800 grit was used to develop the fine velvety nap on the grain side of nubuck leather. Because the sands of the aforementioned grit are very minute so it produces a fine powder form buffing dust. For the experiment purpose, the buffing dust was collected from Super tannery, Kanpur, without any pre-treatment, sun dried for 2 h and kept in desiccator for further studies. Functional groups of the buffing dust are identified by Fourier Transform Infrared Spectroscopy (PerkinElmer, Spectrum −2). FTIR spectrum of buffing dust is recorded between 400 and 4000 cm−1, using KBr. Surface morphology of buffing dust before and after adsorption was recorded by Carl Zeiss Supra 55 SEM analyser, at 100 & 200 nm resolution. Total chromium content before adsorption and after adsorption in the buffing dust were recorded by ICP-OES (Plasma Quant 9000-Analytikjena) to cross check the leaching of the same during the adsorption. The pore volume, pore size, and BET surface area were recorded by NOVA touch LX4, Quantachrome Instruments of buffing dust before adsorption, after degassing of the same for 6 h at 140 °C.
2.2. Preparation of adsorbate solution
K2Cr2O7 (2.829 gm) was dissolved in 1000 mL of deionized water to prepare stock solution of 1000 mg/L concentration. Deionized water was used to further dilute the aforementioned stock solutions to prepare the necessary concentration (50–400 mg/L) for the experiment.
2.3. Adsorption experiment
The removal of Cr (VI) was done by adsorption method in batch mode, using an indigenous orbital shaker. The solutions of different concentrations were made in a 250 mL conical flask. A certain amount of buffing dust was mixed into the 100 mL solution of Cr (VI) having initial concentrations varied between 50 and 400 mg/L and shaked at a speed of 180 rpm for specified duration 30–240 min at 30 °C temperature. After the completion of the adsorption experiments, the solution was centrifuged to get the supernatant, which was used to find out the residual Cr (VI) concentrations. A single beam UV–Vis spectrophotometer (Elico, SL-159) was used to measure the remaining concentration of Cr (VI) at 540 nm (λmax), in the aqueous solution by colorimetric method using 1, 5-diphenylcarbazide as complexing agent. All experiments were done in triplet and their mean value was considered.
The values of (Adsorption capacity) and % adsorption of Cr (VI) was calculated using Eqs. (1), (2):
| (1) |
| (2) |
Where, & represents the initial & equilibrium concentration of Cr (VI) in mg/L; V denotes volume of the solutions (L) and ‘m’ represents mass of adsorbent (buffing dust) in gram.
2.4. Adsorption isotherms
The adsorption isotherm is an important tool to identify the equilibrium data of the adsorption process. The different isotherms explain how the adsorbate molecules adsorbed on the surface of solid adsorbent, and to reveal the variation of concentration of adsorbate affecting the relationship between these two, at particular temperature. In the present work the Langmuir, Temkin and Freundlich isotherms models were used for investigating the adsorbate-adsorbent relationship.
2.4.1. Langmuir isotherm
This model is applicable for homogeneous surface when no interaction occurs between adsorbed species [61]. The liner equation which explains the Langmuir isotherm is presented as:
| (3) |
Where, the terms Ce, qe, qm, and b are the equilibrium concentration of Cr (VI) in mg/L, adsorption capacity of adsorbent in mg/g, maximum adsorption capacity of adsorbent in mg/g, and Langmuir constant respectivelyy (Eq. (3)). The dimensionless value RL is calculated by Langmuir isotherm model which explains whether the adsorption is favourable or not. The value of the same should be less than unity for a favourable adsorption isotherm. The following expression (Eq. (4)) is used to compute the component (RL) from the Langmuir isotherm [62]:
| (4) |
2.4.2. Freundlich model
This isotherm model assumes that the surface behaves like heterogeneous in nature and adsorption on one site affects the adsorption for other sites [63]. Following equation presents the Freundlich isotherm model in its linear version (Eq. (5)).
| (5) |
Where, represents the Freundlich constant, and n denotes the intensity of heterogeneity factor.
2.4.3. Temkin model
This isotherm assumes that the heat of adsorption reduces linearly with the increase of surface coverage [39]. The linear equation for Temkin isotherm is expressed as:
| (6) |
| (7) |
Where, (in L/g) is equilibrium binding constant denoting the maximum binding energy, constant B explains the heat of sorption (in J/mol), R the universal gas constant (8.314 J/mol/K) and b is Temkin isotherm constant corresponding to the potential of the adsorbent for the adsorption (Eqs. (6), (7))).
2.5. Kinetics study
2.5.1. Pseudo first-order model
The kinetic model is based on mass transfer of adsorbate molecule from aqueous phase to the sorption sites. The model is presented as follows [64,65]:
| (8) |
Where, is the rate constant (), and represents the adsorbate quantity adsorbed (mg/g) at equilibrium and time t (min) respectively (Eq. (8)).
2.5.2. Pseudo second-order model
The pseudo-second order model is used to explain the adsorption kinetics, and the equation is provided below [66]:
| (9) |
Where qt (mg/g) and qe (mg/g) are the uptake amount of the adsorbate by the adsorbent at time t and equilibrium respectively. k2 [g/(mg min)] represents rate constant for pseudo second order (Eq. (9)).
3. Result and discussion
3.1. Characterization of buffing dust
3.1.1. FTIR analysis
Fig. 1 showed the FTIR spectrum of buffing dust before (Fig. 1a) and after adsorption (Fig. 1b). The band 3300 cm−1 and 1330 cm−1 correspond to O–H stretching and bending respectively. Band 2923 cm−1 corresponds to N–H stretching [67]. Band 2853 cm−1 and 1452 cm−1 corresponds to C–H stretching and C–H bending respectively [68]. Band 1638 cm−1,1547 cm−1,1234 cm−1, and 1032 cm−1 represents C C stretching, N–O stretching, C–O stretching and S O stretching respectively [69]. The FTIR of buffing dust before and after adsorption reveals that the adsorption was physical in nature since there was no evidence of any significant chemical modification of the functional groups. The interaction of metal ion with buffing dust involves the electronic interaction of electronegative atoms of proteinous components present in the buffing dust with positive chromium ion.
Fig. 1.
FTIR spectrum of buffing dust (a) before adsorption and (b) after adsorption.
3.1.2. SEM analysis
SEM images shown in Fig. 2, exhibits the helical fibrous structure of adsorbent, the thickness size of the samples was found to be lie in between 67 and 144 nm, with an average of 102 ± 22 nm as determine by Image-J software. It was observed that the alignment of the fibrous thread like structures was of highly ordered manner in the post absorption (Fig. 2 b & d) as compared with pre adsorption (Fig. 2 a & c) of Cr (VI) by the buffing dust.
Fig. 2.
SEM images of buffing dust with different magnification before (a, c) & after adsorption (b, d).
3.1.3. BET surface area
The BET surface area, pore volume and average pore size of the buffing dust before adsorption observed to be 9.591 m2/g, 0.01927 cc/g and 3.384 nm respectively. There are several reports towards utilisation of the adsorbent having low surface area, used for removal of the Cr from effluents, e. g. egg cell (0.38 m2/g) [70], polyaniline biochar (8.2 m2/g) [71], stem of sun flower (2 m2/g) [37]. Due to the lower surface area, and presence of the Cr in the sample, the further studies of the BET surface area after adsorption was not recorded as this data was not able to provide any further impact on the adsorption result (which should decrease after adsorption) along with to financial constrain.
3.1.4. Chromium content of buffing dust
Total chromium content of buffing dust before adsorption was observed to be 26.918 mg/g and was in accordance with the results reported by Sekaran et al. (1998) [60], by ICP-OES analysis. Chromium content in buffing dust after adsorption was determined to be 27.385 mg/g for the batch experiment of C0 (100 mg/L), buffing dust dose (2g/100 mL), running time (120 min) and rotation speed (180 rpm). The above result was inferred to conclude that the adsorption process was occurred without any leaching. The result of this analysis confirmed that the buffing dust have capacity to adsorb chromium, the adsorption process was effective and can be studied in detail, as discussed in subsequent sections based on UV–Vis data.
3.2. Effect of contact time
The contact time play a vital role in adsorption process. The percentage removal and metal uptake were investigated at different time ranging from 30 min to 240 min. From analysis of Fig. 3, it is clear that the adsorption intensity of the buffing dust was more at the initial stage due to availability of more sorption site, and the same was getting slow with the exhausted of sites [72]. The trend of the contact time over the removal of the Cr (VI) by the buffing dust, was observed to be effective from 120 to 240 min. This suggested that the optimised time for equilibrium stage the study can be screened in between 120 and 240 min, since most of the sorption sites were saturated, and the same was selected as 240 min [73].
Fig. 3.
Effect of contact time on concentration in solution & percentage removal of Cr (VI) by buffing dust.
3.3. Effect of adsorbent dose
To investigate the effect of adsorption, dose the experiment was conducted for different dose (0.25, 0.50, 1, 1.5, 2, 2.5, 3, 3.5 and 4 g/100 mL). By increasing the initial dose of buffing dust from 0.25 g to 4g/100 mL more surface areas was available and more sorption sites for adsorption become accessible for Cr (VI), results to the higher percentage of removal of the same. From Fig. 4, it was concluded that the percentage removal of Cr (VI) was increases from 20 to 98% whereas the metal uptake capacity (qe) was decreased from 9 to 2 mg/g, with the increase of adsorbent dose. The above two information were opposed to each other and in contrary to the above, with increases of initial concentration of adsorbent (0.25g to 4g/100 mL), the adsorption capacity declined because at low dose of adsorbent, the entire number of sorption sites, were exposed to adsorption so that the surface rapidly approaches toward saturation. In case of high dose of adsorbent (4g/100 mL) too many sorption sites remain unsaturated due to availability of excessive sorption sites which causes decline in adsorption capacity [74,75]. To get the optimised does, we had designed a two-step selection process (i) the samples which has higher uptake capacity and was found to be 0.25, 0.5 and 1.0 gm of adsorbent dose, (ii) further screening was done for those doses which have a higher removal capacity as compared to other ones. The final dose of adsorbent was selected as 1.0 gm.
Fig. 4.
Effect of dose on metal uptake and percentage removal of Cr (VI) by buffing dust (Initial concentration 100 mg/L; Contact time 240 min; agitation Speed 180 rpm).
3.4. Effect of initial concentration of Cr (VI)
To determine the effect of initial concentration of Cr (VI), the experiments were carried out at different concentrations ranging from 50 to 400 mg/L, keeping other experimental parameters such as agitation speed (180 rpm), contact period (4 h) and adsorbent dose (1g) constant. From Fig. 5, it is clear that percentage removal decreases with increase of Cr (VI) concentration. The available sites of adsorption become fewer at higher concentration of Cr (VI), and thus the percentage removal of metal ions decreases which indicates that adsorption depends upon the initial concentration [1,76]. The theory behind it is that the adsorbent dose is constant and by increasing the initial concentration of the solution, it limits the sorption sites available on the surface of the adsorbent and as a result the percentage removal decreases gradually [77].
Fig. 5.
Effect of initial concentration of Cr (VI) on percentage removal.
3.5. Adsorption isotherm
In order to investigate the suitability of sorption nature of the buffing dust by different process such as monolayer homogeneous adsorption (Langmuir), multilayer heterogeneous type of chemisorptive (Freundlich) or physicochemical adsorption (Temkin), the different isotherms were tested to recognize the best suitable model for the present study. According to the Langmuir isotherms, the values of constants qm and b were found to be 11.33 mg/g and 0.03301 L/mg, respectively (Table 1, Fig. 6 a). From the above result it may be concluded that the maximum uptake of Cr (VI) can be 11.33 mg by per gram of buffing dust adsorbent, if the process was homogeneous and occupied the whole surface in a monolayer fashion.
Table: 1.
Parameters of isotherm models.
| Isotherm model | Parameters | Value |
|---|---|---|
| Langmuir | R2 | 0.9915 |
| b | 0.03301 | |
| qm | 11.33 | |
| RL | 0.377 to 0.0917 | |
| Freundlich | R2 | 0.9877 |
| Kf | 1.718 | |
| 1/n | 0.3401 | |
| Temkin | R2 | 0.9812 |
| B | 2.2062 | |
| AT | 0.4579 |
Fig. 6.
(a) Langmuir, (b) Temkin and (c) Freundlich isotherm plot for removal of Cr (VI) by buffing dust (Time: 240 min, dose:1g/100 mL).
The value of RL should lie in between 0 and 1, for accepted adsorption phenomenon and in this study the value of the same was observed to be in between 0.377 and 0.0917 for different equilibrium concentration of the Cr (VI) after the adsorption. The parameters of Freundlich and Temkin were presented in Table 2. It may be noted that for the acceptance of any isotherm, the key criteria are the value of R2, which was found to be 0.9915, 0.9877 and 0.9812 for Langmuir, Freundlich, and Temkin models respectively.
Table: 2.
Kinetic parameters of adsorption by buffing dust of Cr (VI).
| Experimental | Pseudo first order (calculated) | Pseudo second order (calculated) | ||||
|---|---|---|---|---|---|---|
| qe (mg/g) | k1 (min−1) | qe (mg/g) | R2 | k2 (g/mg. min−1) | qe (mg/g) | R2 |
| 5.82 | 0.0157 | 2.038 | 0.9480 | 0.01405 | 6.06 | 0.9991 |
The comparison shown in the above table explains that with value R2 = 0.9915, Langmuir provided the best fit for chromium (VI) adsorption by buffing dust. The determination coefficient R2 for the Freundlich isotherm and Temkin isotherm are calculated and it is found as 0.9877 (Figs. 6c) and 0.9812 (Fig. 6b) respectively, which may not best suitable to choose of model in compression to Langmuir isotherm model.
To calculate the more effective compression of these three isotherms data, the residual root mean squared error (RMSE, Eq. (10)) statistical error function was calculated, and was found to be 0.2546, 0.3175 and 0.3758 for Langmuir, Freundlich and Temkin isotherm respectively. The obtained results conferred that the Langmuir isotherm was the best fitted model for the present adsorption process.
| (10) |
3.6. Kinetic study of adsorption
In order to investigate the kinetic behaviour, the experiment was carried out at different time. The pseudo first order (Fig. 7a) and pseudo second order (Fig. 7b) kinetics models were explored for the obtained results. From pseudo first model and pseudo second order models, it can be concluded that the coefficient of determination R2 for pseudo second order model was 0.9991, which was higher than pseudo first order model (R2 = 0.948, Table 2).
Fig. 7.
Kinetics for the removal of Cr (VI) by buffing dust (a) Pseudo first order and (b) Pseudo second order.
The adsorption capacity calculated by pseudo second order model (6.06 mg/g) was closer to experimental data (5.82 mg/g). This observation indicates that the pseudo second order kinetics model was best fitted model to explain the adsorption of Cr (VI) by the buffing dust. The comparison of the removal capacity of this adsorbent with other reported data are summarised in Table 3.
Table: 3.
Comparison of adsorption capacity of buffing dust for Cr (VI) with other adsorbents.
| Name of Adsorbent | Removal capacity (mg/g) | References |
|---|---|---|
| Sal saw dust | 9.55 | [34] |
| Treated waste newspaper | 59.88 | [39] |
| Coconut shell carbon | 10.88 | [78] |
| Peanut shell | 16.26 | [79] |
| Sugarcane bagasse | 1.76 | [80] |
| Maize corn cob | 0.28 | [81] |
| Modified groundnut shell | 131 | [82] |
| Rice husk activated magnetic bio char | 9.97 | [83] |
| Peanut husk magnetic bio char | 12.25 | [84] |
| Peels of pea (Pisum sativum) pod | 4.33 | [85] |
| Buffing dust | 11.33 (qm), 5.82 (qe) | present study |
4. Conclusion
In this paper the buffing dust has been used as adsorbent for the removal of hexavalent chromium and from the result it is clear that despite this adsorbent contains chrome compound, it has substantial capacity to removal of Cr (VI) from aqueous phase. The percentage removal was found as 90% for the contact time of 240 min at adsorbent dose 4 g/100 mL for 100 ppm of Cr (VI) solution. The Langmuir isotherm was best fitted for experimental data with regression value (R2) of 0.991 and maximum adsorption capacity was calculated as 11.33 mg/g. The kinetics model best explained by pseudo second order model with R2 value of 0.9991. Since Buffing dust is a tannery waste, it is easily accessible there and can be used to remove hexavalent chromium from chrome effluent. Therefore, the finding of the present investigation reveals the useful application of waste buffing dust which would be economical and significantly reduces the environmental contamination. Furthermore, this Cr containing buffing dust can be used to make leather board with significantly improved physical properties for the application of leather product industries.
Declarations
Author contribution statement
Manikant Kumar: Conceived and designed the experiments; Performed the experiments; Analyzed and interpreted the data; Wrote the paper.
N. S. Maurya: Conceived and designed the experiments; Performed the experiments; Wrote the paper.
Anshuman Singh: Conceived and designed the experiments; Analyzed and interpreted the data.
M.K. Rai: Performed the experiments; Analyzed and interpreted the data; Contributed reagents, materials, analysis tools or data.
Funding statement
This research did not receive any grant from funding agencies in public, commercial, or not for profit organisations.
Data availability statement
Data will be made available on request.
Competing interest statement
The authors declare no conflict of interest.
Acknowledgements
The authors are grateful to the Dr Sanjay Kumar (Head of department of pharmacy, Muzaffarpur Institute of Technology, Muzaffarpur) for his valuable suggestion for the improvement of the manuscript.
References
- 1.Sharma N., Sodhi K., Kumar M., Singh D. Heavy metals eco-toxicity with major concern to chromium and recent advancement in remediation technologies. Environ. Nanotechnol. Monit. Manag. 2020;15 [Google Scholar]
- 2.Monga A., Fulke A.B., Dasgupta D. Recent developments in essentiality of trivalent chromium and toxicity of hexavalent chromium: implications on human health and remediation strategies. J. Hazar. Mater. Adv. 2022;7 [Google Scholar]
- 3.DesMarias T.L., Costa M. Mechanisms of chromium-induced toxicity. Curr. Opin. Toxic. 2019;14:1–7. doi: 10.1016/j.cotox.2019.05.003. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 4.Saha R., Nandi R., Saha B. Sources and toxicity of hexavalent chromium. J. Coord. Chem. 2011;64(10):1782–1806. 2011. [Google Scholar]
- 5.Sah D., Verma P.K., Kumari K.M., Lakhani A. Chemical partitioning of fine particle-bound As, Cd, Cr, Ni, Co, Pb and assessment of associated cancer risk due to inhalation, ingestion and dermal exposure. Inhal. Toxicol. 2017;29(11):483–493. doi: 10.1080/08958378.2017.1406563. 2017. [DOI] [PubMed] [Google Scholar]
- 6.O'Flaherty E.J. A physiologically based model of chromium kinetics in the rat. Toxicol. Appl. Pharmacol. 1996;138:54–64. doi: 10.1006/taap.1996.0097. [DOI] [PubMed] [Google Scholar]
- 7.Guidotti L., Abad S.Q., Rodríguez-González P., Alonso J., Beone G.M. Quantification of Cr (VI) in soil samples from a contaminated area in northern Italy by isotope dilution mass spectrometry. Environ. Sci. Pollut. Control Ser. 2015;22(22):17569–17576. doi: 10.1007/s11356-015-4963-z. [DOI] [PubMed] [Google Scholar]
- 8.den Braver-Sewradj S.P., van Benthem J., Staal Y.C., Ezendam J., Piersma A.H., Hessel E.V. Occupational exposure to hexavalent chromium. Part II. Hazard assessment of carcinogenic effects. Regul. Toxicol. Pharmacol. 2021;126 doi: 10.1016/j.yrtph.2021.105045. [DOI] [PubMed] [Google Scholar]
- 9.Miretzky P., Cirelli A.F. Cr (VI) and Cr (III) removal from aqueous solution by raw and modified lignocellulosic materials: a review. J. Hazard Mater. 2010;180:1–19. doi: 10.1016/j.jhazmat.2010.04.060. [DOI] [PubMed] [Google Scholar]
- 10.Sharma A., Thakur K.K., Mehta P., Pathania D. Efficient adsorption of chlorpheniramine and hexavalent chromium (Cr (VI)) from water system using agronomic waste material. Sustain. Chem. Pharm. 2018;9:1–11. [Google Scholar]
- 11.Xia Q., Yang L., Hu K., Li K., Xiang J., Liu G., et al. Chromium cross-linking based immobilization of silver nanoparticle coating on leather surface with broad-spectrum antimicrobial activity and durability. ACS Appl. Mater. Interfaces. 2018;11:2352–2363. doi: 10.1021/acsami.8b17061. [DOI] [PubMed] [Google Scholar]
- 12.Mia M., Sayid A., Ahmad F., Rahman M. An overview of chromium removal techniques from tannery effluent. Appl. Water Sci. 2020;10:1–22. [Google Scholar]
- 13.Pradeep S., Sundaramoorthy S., Sathish M., Jayakumar G.C., Rathinam A., Madhan B., et al. Chromium-free and waterless vegetable-aluminium tanning system for sustainable leather manufacture. Chem. Eng. J. Adv. 2021;7 [Google Scholar]
- 14.Babu N.K.C., Asma K., Raghupathi A., Venba R., Ramesh R., Sadulla S. Screening of leather auxiliaries for their role in toxic hexavalent chromium formation in leather—posing potential health hazards to the users. J. Clean. Prod. 2005;13(12):1189–1195. [Google Scholar]
- 15.Sánchez A., Gisel M., Devouge-Boyer C., Hubert-Roux M., Afonso C., Mignot M. Chromium determination in leather and other matrices: a review. Crit. Rev. Anal. Chem. 2021:1–20. doi: 10.1080/10408347.2021.1890545. [DOI] [PubMed] [Google Scholar]
- 16.Verma B., Balomajumder C. Hexavalent chromium reduction from real electroplating wastewater by chemical precipitation. Bull. Chem. Soc. Ethiop. 2020;34(1):67–74. [Google Scholar]
- 17.Mahringer D., Zerelli S.S., Dippon U., Ruhl A.S. Pilot scale hexavalent chromium removal with reduction, coagulation, filtration and biological iron oxidation. Sep. Pur. Techn. 2020;253 [Google Scholar]
- 18.Wang G., Chang Q., Han X., Zhang M. Removal of Cr (VI) from aqueous solution by flocculant with the capacity of reduction and chelation. J. Hazard Mater. 2013;248:115–121. doi: 10.1016/j.jhazmat.2013.01.001. [DOI] [PubMed] [Google Scholar]
- 19.Mnif A., Bejaoui I., Mouelhi M., Hamrouni B. Hexavalent chromium removal from model water and car shock absorber factory effluent by nanofiltration and reverse osmosis membrane. Int. J. Analy. Chem. 2017;2017:7415708. doi: 10.1155/2017/7415708. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 20.Lakshmipathiraj P., Raju G.B., Basariya M.R., Parvathy S., Prabhakar S. Removal of Cr (VI) by electrochemical reduction. Sep. Pur. Techn. 2008;60:96–102. [Google Scholar]
- 21.Mouedhen G., Feki M., De Petris-Wery M., Ayedi H. Electrochemical removal of Cr (VI) from aqueous media using iron and aluminum as electrode materials: towards a better understanding of the involved phenomena. J. Hazard Mater. 2009;168:983–991. doi: 10.1016/j.jhazmat.2009.02.117. [DOI] [PubMed] [Google Scholar]
- 22.Khan S.U., Islam D.T., Farooqi I.H., Ayub S., Basheer F. Hexavalent chromium removal in an electrocoagulation column reactor: process optimization using CCD, adsorption kinetics and pH modulated sludge formation. Process Saf. Environ. Protect. 2019;122:118–130. [Google Scholar]
- 23.Cheballah K., Sahmoune A., Messaoudi K., Drouiche N., Lounici H. Simultaneous removal of hexavalent chromium and COD from industrial wastewater by bipolar electrocoagulation. Chem. Eng. Process: Process Intensif. 2015;96:94–99. [Google Scholar]
- 24.Wang H., Song X., Zhang H., Tan P., Kong F. Removal of hexavalent chromium in dual-chamber microbial fuel cells separated by different ion exchange membranes. J. Hazard Mater. 2020;384 doi: 10.1016/j.jhazmat.2019.121459. [DOI] [PubMed] [Google Scholar]
- 25.Masinire F., Adenuga D.O., Tichapondwa S.M., Chirwa E.M. Phytoremediation of Cr (VI) in wastewater using the vetiver grass (Chrysopogon zizanioides) Miner. Eng. 2021;172 [Google Scholar]
- 26.Mukherjee K., Nandi R., Saha D., Saha B. Surfactant assisted bioremediation of hexavalent chromium from contaminated water. Desalination Water Treat. 2015;53:746–751. [Google Scholar]
- 27.Kerur S., Bandekar S., Hanagadakar M.S., Nandi S.S., Ratnamala G., Hegde P.G. Removal of hexavalent Chromium-Industry treated water and Wastewater: a review. Mater. Today Proc. 2020;42:1112–1121. [Google Scholar]
- 28.Ahmad W., Qaiser S., Ullah R., Mohamed Jan B., Karakassides M.A., Salmas C.E., et al. Utilization of tires waste-derived magnetic-activated carbon for the removal of hexavalent chromium from wastewater. Materials. 2020;14:34. doi: 10.3390/ma14010034. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 29.Berihun D. Removal of chromium from industrial wastewater by adsorption using coffee husk. J. Mater. Sci. Eng. 2017;6:331. [Google Scholar]
- 30.Werkneh A.A., Habtu N.G., Beyene H.D. Removal of hexavalent chromium from tannery wastewater using activated carbon primed from sugarcane bagasse: adsorption/desorption studies. Am. J. Appl. Chem. 2014;2:128–135. [Google Scholar]
- 31.Chabaane L., Tahiri S., Albizane A., El Krati M., Cervera M.L., De la Guardia M. Immobilization of vegetable tannins on tannery chrome shavings and their use for the removal of hexavalent chromium from contaminated water. Chem. Eng. J. 2011;174:310–317. [Google Scholar]
- 32.Kumar A.S.K., Kakan S.S., Rajesh N. A novel amine impregnated graphene oxide adsorbent for the removal of hexavalent chromium. Chem. Eng. J. 2013;230:328–337. [Google Scholar]
- 33.Shukla S.S., Yu L.J., Dorris K.L., Shukla A. Removal of nickel from aqueous solutions by sawdust. J. Hazard Mater. 2005;121:243–246. doi: 10.1016/j.jhazmat.2004.11.025. [DOI] [PubMed] [Google Scholar]
- 34.Baral S.S., Das S.N., Rath P. Hexavalent chromium removal from aqueous solution by adsorption on treated sawdust. Biochem. Eng. J. 2006;31(3):216–222. [Google Scholar]
- 35.Hasan S.H., Singh K., Prakash O., Talat M., Ho Y. Removal of Cr (VI) from aqueous solutions using agricultural waste ‘maize bran. J. Hazard Mater. 2008;152:356–365. doi: 10.1016/j.jhazmat.2007.07.006. [DOI] [PubMed] [Google Scholar]
- 36.Ahluwalia S., Goyal D. Removal of heavy metals by waste tea leaves from aqueous solution. Eng. Life Sci. 2005;5:158–162. [Google Scholar]
- 37.Malik U.R., Hasany S.M., Subhani M.S. Sorptive potential of sunflower stem for Cr (III) ions from aqueous solutions and its kinetic and thermodynamic profile. Talanta. 2005;66:166–173. doi: 10.1016/j.talanta.2004.11.013. [DOI] [PubMed] [Google Scholar]
- 38.Mansour M., Ossman M., Farag H. Removal of Cd (II) ion from waste water by adsorption onto polyaniline coated on sawdust. Desalination. 2011;272:301–305. [Google Scholar]
- 39.Dehghani M.H., Sanaei D., Ali I., Bhatnagar A. Removal of chromium (VI) from aqueous solution using treated waste newspaper as a low-cost adsorbent: kinetic modeling and isotherm studies. J. Mol. Liq. 2016;215:671–679. [Google Scholar]
- 40.Dima J.B., Sequeiros C., Zaritzky N.E. Hexavalent chromium removal in contaminated water using reticulated chitosan micro/nanoparticles from seafood processing wastes. Chemosphere. 2015;141:100–111. doi: 10.1016/j.chemosphere.2015.06.030. [DOI] [PubMed] [Google Scholar]
- 41.Mthombeni N., Onyango M., Aoyi O. Adsorption of hexavalent chromium onto magnetic natural zeolite-polymer composite. J. Taiwan Inst. Chem. Eng. 2015;50:242–251. [Google Scholar]
- 42.Lee S.H., Jung C.H., Chung H., Lee M.Y., Yang J.-W. Removal of heavy metals from aqueous solution by apple residues. Process Biochem. 1998;33:205–211. [Google Scholar]
- 43.Huang D.-L., Chen G.-M., Zeng G.-M., Xu P., Yan M., Lai C., et al. Synthesis and application of modified zero-valent iron nanoparticles for removal of hexavalent chromium from wastewater. Water, Air Soil Poll. 2015;226:1–14. [Google Scholar]
- 44.Cheng Z., Fu F., Pang Y., Tang B., Lu J. Removal of phenol by acid-washed zero-valent aluminium in the presence of H2O2. Chem. Eng. J. 2015;260:284–290. [Google Scholar]
- 45.Fahim N., Barsoum B., Eid A., Khalil M. Removal of chromium (III) from tannery wastewater using activated carbon from sugar industrial waste. J. Hazard Mater. 2006;136:303–309. doi: 10.1016/j.jhazmat.2005.12.014. [DOI] [PubMed] [Google Scholar]
- 46.Jia X., Zhang Y., He Z., Chang F., Zhang H., Wågberg T., Hu G. Mesopore-rich badam-shell biochar for efficient adsorption of Cr (VI) from aqueous solution. J. Environ. Chem. Eng. 2021;9(4) [Google Scholar]
- 47.Ali S., Noureen S., Shakoor M.B., Haroon M.Y., Rizwan M., Jilani A. Comparative evaluation of wheat straw and press mud biochars for Cr (VI) elimination from contaminated aqueous solution. Environ. Technol. Innov. 2020;19 [Google Scholar]
- 48.Herath A., Layne C.A., Perez F., Hassan E.B., Pittman C.U., Jr., Mlsna T.E. KOH-activated high surface area Douglas Fir biochar for adsorbing aqueous Cr (VI), Pb (II) and Cd (II) Chemosphere. 2021;269 doi: 10.1016/j.chemosphere.2020.128409. [DOI] [PubMed] [Google Scholar]
- 49.Bai L., Su X., Feng J., Ma S. Preparation of sugarcane bagasse biochar/nano-iron oxide composite and mechanism of its Cr (VI) adsorption in water. J. Clean. Prod. 2021;320 [Google Scholar]
- 50.Nasseh N., Taghavi L., Barikbin B., Harifi-Mood A.R. The removal of Cr (VI) from aqueous solution by almond green hull waste material: kinetic and equilibrium studies. J. Water Reuse Desalin. 2017;7:449–460. [Google Scholar]
- 51.Lin Y.-J., Chen J.-J., Cao W.-Z., Persson K.M., Ouyang T., Zhang L., et al. Novel materials for Cr (VI) adsorption by magnetic titanium nanotubes coated phosphorene. J. Mol. Liq. 2019;287 [Google Scholar]
- 52.Shankar P., Thandapani G., Kumar V., Parappurath Narayanan S. Biomass Conversion and Biorefinery; 2022. Evaluation of Batch and Packed Bed Adsorption Column for Chromium (VI) Ion Removal from Aqueous Solution Using Chitosan-Silica–G–AM/orange Peel Hydrogel Composite; pp. 1–16. [Google Scholar]
- 53.Kumar P., Chauhan M. Adsorption of chromium (VI) from the synthetic aqueous solution using chemically modified dried water hyacinth roots. J. Environ. Chem. Eng. 2019;7 [Google Scholar]
- 54.Chwastowski J., Staroń P., Kołoczek H., Banach M. Adsorption of hexavalent chromium from aqueous solutions using Canadian peat and coconut fiber. J. Mol. Liq. 2017;248:981–989. [Google Scholar]
- 55.Alemu A., Lemma B., Gabbiye N., Alula M.T., Desta M.T. Removal of chromium (VI) from aqueous solution using vesicular basalt: a potential low cost wastewater treatment system. Heliyon. 2018;4 doi: 10.1016/j.heliyon.2018.e00682. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 56.Zhang X., Zhang L., Li A. Eucalyptus sawdust derived biochar generated by combining the hydrothermal carbonization and low concentration KOH modification for hexavalent chromium removal. J. Environ. Manag. 2018;206:989–998. doi: 10.1016/j.jenvman.2017.11.079. [DOI] [PubMed] [Google Scholar]
- 57.Sinha R., Kumar R., Abhishek K., Shang J., Bhattacharya S., Sengupta S., et al. Single-step synthesis of activated magnetic biochar derived from rice husk for hexavalent chromium adsorption: equilibrium mechanism, kinetics, and thermodynamics analysis. Groundwat. Sustain. Develop. 2022;18 [Google Scholar]
- 58.Swarnalatha S., Srinivasulu T., Srimurali M., Sekaran G. Safe disposal of toxic chrome buffing dust generated from leather industries. J. Hazard Mater. 2008;150(2):290–299. doi: 10.1016/j.jhazmat.2007.04.100. [DOI] [PubMed] [Google Scholar]
- 59.Senthil R., Hemalatha T., Manikandan R., Das B.N., Sastry T.P. Leather boards from buffing dust: a novel perspective. Clean Technol. Environ. Policy. 2015;17:571–576. [Google Scholar]
- 60.Sekaran G., Shanmugasundaram K., Mariappan M. Characterization and utilisation of buffing dust generated by the leather industry. J. Hazard Mater. 1998;63(1):53–68. [Google Scholar]
- 61.Wang L., Muthu P., Szczesna-Cordary D., Kawai M. Diversity and similarity of motor function and cross-bridge kinetics in papillary muscles of transgenic mice carrying myosin regulatory light chain mutations D166V and R58Q. J. Mol. Cell. Cardiol. 2013;62:153–163. doi: 10.1016/j.yjmcc.2013.05.012. [DOI] [PMC free article] [PubMed] [Google Scholar]
- 62.Vishali S., Mullai P. Analysis of two-parameter and three-parameter isotherms by nonlinear regression for the treatment of textile effluent using immobilized Trametes versicolor: comparison of various error functions. Desalination Water Treat. 2016;57:27061–27072. [Google Scholar]
- 63.Anirudhan T., Radhakrishnan P. Thermodynamics and kinetics of adsorption of Cu (II) from aqueous solutions onto a new cation exchanger derived from tamarind fruit shell. J. Chem. Therm. 2008;40(4):702–709. [Google Scholar]
- 64.Ghaedi M., Ansari A., Habibi M., Asghari A. Removal of malachite green from aqueous solution by zinc oxide nanoparticle loaded on activated carbon: kinetics and isotherm study. J. Ind. Eng. Chem. 2014;20(1):17–28. [Google Scholar]
- 65.Yang B., Yu C., Yu Q., Zhang X., Li Z., Lei L. N-doped carbon xerogels as adsorbents for the removal of heavy metal ions from aqueous solution. RSC Adv. 2015;5:7182–7191. [Google Scholar]
- 66.Lin J., Zhan S., Fang M., Qian X., Yang H. Adsorption of basic dye from aqueous solution onto fly ash. J. Environ. Manag. 2008;87:193–200. doi: 10.1016/j.jenvman.2007.01.001. [DOI] [PubMed] [Google Scholar]
- 67.Marzbali M.H., Esmaieli M., Abolghasemi H., Marzbali M.H. Tetracycline adsorption by H3PO4-activated carbon produced from apricot nut shells: a batch study. Process Saf. Environ. Protect. 2016;102:700–709. [Google Scholar]
- 68.Shen H., Pan S., Zhang Y., Huang X., Gong H. A new insight on the adsorption mechanism of amino-functionalized nano-Fe3O4 magnetic polymers in Cu (II), Cr (VI) co-existing water system. Chem. Eng. J. 2012;183:180–191. [Google Scholar]
- 69.Ren Z., Xu X., Wang X., Gao B., Yue Q., Song W., et al. FTIR, Raman, and XPS analysis during phosphate, nitrate and Cr (VI) removal by amine cross-linking biosorbent. J. Colloid Interface Sci. 2016;468:313–323. doi: 10.1016/j.jcis.2016.01.079. [DOI] [PubMed] [Google Scholar]
- 70.Elabbas S., Mandi L., Berrekhis F., Pons M.N., Leclerc J.P., Ouazzani N. Removal of Cr (III) from chrome tanning wastewater by adsorption using two natural carbonaceous materials: eggshell and powdered marble. J. Environ. Manag. 2016;166:589–595. doi: 10.1016/j.jenvman.2015.11.012. [DOI] [PubMed] [Google Scholar]
- 71.Herath A., Reid C., Perez F., Pittman C.U., Jr., Mlsna T.E. Biochar-supported polyaniline hybrid for aqueous chromium and nitrate adsorption. J. Environ. Manag. 2021;296 doi: 10.1016/j.jenvman.2021.113186. [DOI] [PubMed] [Google Scholar]
- 72.Tiadi N., Mohanty M., Mohanty C., Panda H.P.H. Studies on adsorption behavior of an industrial waste for removal of chromium from aqueous solution. South Afr. J. Chem. Eng. 2017;23:132–138. [Google Scholar]
- 73.Kumar A., Jena H.M. Adsorption of Cr (VI) from aqueous phase by high surface area activated carbon prepared by chemical activation with ZnCl2. Process Saf. Environ. Protect. 2017;109:63–71. [Google Scholar]
- 74.Yang J., Yu M., Chen W. Adsorption of hexavalent chromium from aqueous solution by activated carbon prepared from longan seed: kinetics, equilibrium and thermodynamics. J. Ind. Eng. Chem. 2015;21:414–422. [Google Scholar]
- 75.Enniya I., Rghioui L., Jourani A. Adsorption of hexavalent chromium in aqueous solution on activated carbon prepared from apple peels. Sustain. Chem. Pharm. 2018;7:9–16. [Google Scholar]
- 76.Nekouei F., Nekouei S., Tyagi I., Gupta V.K. Kinetic, thermodynamic and isotherm studies for acid blue 129 removal from liquids using copper oxide nanoparticle-modified activated carbon as a novel adsorbent. J. Mol. Liq. 2015;20:124–133. [Google Scholar]
- 77.Dawood S., Sen T.K., Phan C. Synthesis and characterisation of novel-activated carbon from waste biomass pine cone and its application in the removal of Congo red dye from aqueous solution by adsorption. Water, Air, Soil Pollut. 2014;225:1–16. [Google Scholar]
- 78.Alaerts J.G., Jitjaturunt V., Kelderman P. Use of coconut shell-based activated carbon for chromium (VI) removal. Water Sci. Technol. 1989;21(12):1701–1704. [Google Scholar]
- 79.Al-Othman Z.A., Ali R., Naushad M. Hexavalent chromium removal from aqueous medium by activated carbon prepared from peanut shell: adsorption kinetics, equilibrium and thermodynamic studies. Chem. Eng. J. 2012;184:238–247. [Google Scholar]
- 80.Aloma I.C., Rodriguez I., Calero M., Blazquez G. Biosorption of Cr6+ from aqueous solution by sugarcane bagasse. Desalination Water Treat. 2014;52:5912–5922. [Google Scholar]
- 81.Garg U.K., Kaur M.P., Garg V.K., Sud D. Removal of hexavalent chromium from aqueous solution by agricultural waste biomass. J. Hazard Mater. 2007;140:60–68. doi: 10.1016/j.jhazmat.2006.06.056. [DOI] [PubMed] [Google Scholar]
- 82.O Owalude S., Tella A.C. Removal of hexavalent chromium from aqueous solutions by adsorption on modified groundnut hull. Beni-suef Univer. J. Bas. Appl. Sci. 2016;5:377–388. [Google Scholar]
- 83.Sinha R., Kumar R., Abhishek K., Shang J., Bhattacharya S., Sengupta S., Kumar N., Singh R.K., Mallick J., Kar M., Sharma P. Groundwater for Sustainable Development; 2022. Single-step Synthesis of Activated Magnetic Biochar Derived from Rice Husk for Hexavalent Chromium Adsorption, Equilibrium Mechanism, Kinetics, and Thermodynamics Analysis. [Google Scholar]
- 84.Mahanty B., Mondal S. Synthesis of magnetic biochar using agricultural waste for the separation of Cr (VI) from aqueous solution. Arabian J. Sci. Eng. 2021;46(11):10803–10818. [Google Scholar]
- 85.Sharma P.K., Sharma, Ayub S., N Tripathi C. Isotherms describing physical adsorption of Cr (VI) from aqueous solution using various agricultural wastes as adsorbents. Cogent Eng. 2016;3(1) [Google Scholar]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Data Availability Statement
Data will be made available on request.








