A comparative study of removal of As(III) using Cascabela thevetia (Kaner) and Tinospora cordifolia (Giloy).

Rajendra Kumar¹ , Ashok Kumar Jha² ^* and Raghbendra Thakur³

¹ Department of Chemistry, P.B.S. College, Banka, Bihar India

² Department of Chemistry, T. M. Bhagalpur University, Bhagalpur, Bihar India

³ Atomic Minerals Directorate for Exploration and Research, Department of Atomic Energy, Bangalore, Karnataka India

Corresponding author Email: ashokjha39@gmail.com

Abstract

Bioremediation of arsenic by medicinal plants had been studied in the present paper. Cascabela thevetia (Kaner) having few anticancer properties and Tinospora cordifolia (Giloy) may adversely affect the health if grown on arsenic contaminated soil. Different initial concentrations of arsenic i.e. 5 ppm, and 2 ppm had been taken at different pH values of 2, 7, and 9 to find the optimum condition of maximum bioremediation using C. thevetia and T. cordifolia. The peaks in HPLC at 227 nm of the plants had shown the changes in peaks before and after treatment. The FTIR peaks also showed changes before and after adsorption. When an initial concentration of 5 ppm As(III) was treated with T. cordifolia at pH 7, the residual concentration was 0.15 ppm. Whereas the residual concentration with 2 ppm initial concentration of As(III) was 0.10 ppm at pH 7. The Maximum percentage removal using C. thevetia treated with the initial concentration of 5 ppm As(III) was 97% at pH 9. No considerable effect of pH had been observed on arsenic remediation. The experimental data best fitted the pseudo-second order reaction.

Keywords

Arsenic; Bioremediation; FTIR; HPLC; Remediation

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Kumar R, Jha A. K, Thakur R. A comparative study of removal of As(III) using Cascabela thevetia (Kaner) and Tinospora cordifolia (Giloy). Curr World Environ 2025;20(1).

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Kumar R, Jha A. K, Thakur R. A comparative study of removal of As(III) using Cascabela thevetia (Kaner) and Tinospora cordifolia (Giloy). Curr World Environ 2025;20(1).

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Publish History

Article Publishing History

Received:	2024-11-21
Accepted:	2025-02-13
Reviewed by:	Garima Gupta
Second Review by:	Rishikesh Singh
Final Approval by:	Dr. R K Aggarwal

Introduction

Arsenic, a metalloid, has adverse health effects causing hyperpigmentation and skin cancer. The Gangetic plain in general and of Bhagalpur in particular is severely affected with arsenic contamination and several causes of arsenicosis have been detected in the plain along with prostate cancer, liver cancer, and other cancers.¹ The increase in cancer cases in the Gangetic plain has been linked to various environmental factors out of which inorganic arsenicals has emerged as the major causative factor. The inorganic arsenicals such as monomethyl arsenous acid, dimethyl arsenous acid hinder the generation of adenosine-5^´triphosphate during oxidative phosphorylation. The binding of monomethylarsenous acid and dimethylarsenous acid takes place with cysteine residues in proteins. In addition, arsenic can inactivate around 200 enzymes.² One of the important reasons of escalating cancer patients in the Gangetic plain may be attributed to the large chunk of the population exposure to agrochemicals and consequent entry of heavy metals, pesticides, and arsenic into food chain.³ Pesticides’ exposure to the agro-based population causes long term health hazards due to non-biodegradibility.

The present work has been designed to study the uptake of arsenic by selected medicinal plants such as T. cordifolia and C. thevetia. The remediation potential of these medicinal plants has been investigated using different parameters. T. cordifolia has a large number of secondary metabolites which impart medicinal values to this plant.⁴ Alkaloids, steroids, diterpenoids lactones, and glycosides are few worth mentioning chemical constituents of Giloy.⁵ Owing to the presence of these compounds in the Giloy, it is used as antipyretic, antioxidant, antidiabetic, and hepato-protective. Nerium oleander (Kaner flower) contains gitoxigen neridiginoside, and adynerigenin. The flowers of C. thevetia may cause acute poisoning.⁶ These medicinal uses of C. thevetia are in the treatment of amenorrhea, jaundice, migraines, and cancer.⁷

Arsenic uptake has been studied with the biomass of leaves and stem of C. thevetia and T. cordifolia with different initial concentrations at different pH values. Optimum condition of remediation has been set during batch experiments. The experimental data have been analysed to see the best fit of adsorption isotherms. Kinetic studies have also been done to explain the results. Percentage removal and residual concentrations are calculated as per the equations given below

q_t = (C_i – C_t) . V / m ------------- (1)

where, C_i represents the initial concentration and C_t the final concentration of As(III). V represents the volume of solution in litre, and m represents the mass of adsorbent in g.

Percentage removal = ( C_i – C_t)/ C_i × 100 ---------------- (2)

Pseudo – first and second order models have been studied for removal of arsenic by T. cordifolia and C. thevetia. The removal efficiency of the adsorbent depends on several factors such as pH, adsorbent doses, initial concentration and contact time.⁸ Phytoremediation of arsenic by Withania somnifera and Aloe-vera has also been reported.⁹ Cymbopogon flexuosus (Lemon grass) has also been established as a potential remover of toxic heavy metals.¹⁰ The Ganga as well as Koshi river plains are arsenic contaminated which has been established in various studies.^11,12 Medicinal as well as aquatic plants grow in a natural way in these river plains. Bentonite minerals are also found in abundance in Rajmahal hills of Jharkhand. Several natural adsorbents such as medicinal plants, aquatic plants, and bentonites have emerged as potential detoxicants of arsenic and chromium.^13-15

Materials and Methods

C. thevetia and T. cordifolia have been collected from Acharya P. C. Ray Garden of University Department of Chemistry, T.M.B.U., Bhagalpur. The powdered biomass was stored in a bottle. Batch experiments have been done with fixed biomass of T. cordifolia and C. thevetia up to 15, 30, 45 and 60 minutes at pH 2, 7, and 9 to find the optimum adsorption condition. The pH has been changed to 2 and 9 by adding N/10 HCl and N/10 NaOH, respectively, in 100 ml As(III) solution and the pH was measured by pH meter Spectron model No. St -139. Similar experiments were repeated with different initial concentations of As (III) solution such as 2ppm, and 5 ppm. 1 g powdered biomass of T. cordifolia was added to 100 ml of 2 ppm and 5 ppm As(III) solutions at time intervals of 15, 30, 45 and 60 minutes, respectively and shaken on a magnetic stirrer at 220 rpm. A similar experiment was repeated with C. thevetia.

The residual concentrations obtained after treatment of As(III) solutions were estimated by Induced Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analyzer Perkin Elmer Avio 560 Max (Model ULTIMA-2, Horiba Jobin YVON, France). HPLC of powdered mass of C. thevetia and were done and HPLC of the powdered mass after treatment with As (III) solution was fixed at 227 nm, because of the fact that several constituents absorbed light at this wavelength. The FTIR of C. thevetia and T. cordifolia powders have been done before and after adsorption using KBr pellet. The model No of FTIR instrument is – Perkin Elmer Version 10.4.1, US.

Results

The maximum removal of arsenic with T. cordifolia takes place at a pH of 7 with initial concentrations of 2 ppm and 5 ppm arsenic solution as shown in Table 1. The maximum percentage removal for 2 ppm As(III) at pH 2 is 87.5% whereas at pH 7 it is 95%. For an initial concentration of 5 ppm, the maximum percentage removal is 98% at pH 7.

Table 1: Residual arsenic concentration after treatment with 1 g T. cordifolia.

S.N.	Initial concentration (in ppm)	Time (in minutes)	pH	Residual concentration (in ppm)	% Removal = C_i –C_t/C_i ×100
1	2	15	2	0.25	87.5
2	2	30	2	0.25	87.5
3	2	45	2	0.25	87.5
4	2	60	2	0.25	87.5
5	2	15	7	0.15	92.5
6	2	30	7	0.10	95
7	2	45	7	0.10	95
8	2	60	7	0.10	95
9	2	15	9	0.25	87.5
10	2	30	9	0.25	87.5
11	2	45	9	0.25	87.5
12	2	60	9	0.25	87.5
13	5	15	2	0.30	94
14	5	30	2	0.30	94
15	5	45	2	0.40	92
16	5	60	2	0.40	92
17	5	15	7	0.15	97
18	5	30	7	0.15	97
19	5	45	7	0.25	95
20	5	60	7	0.10	98
21	5	15	9	0.35	93
22	5	30	9	0.40	92
23	5	45	9	0.50	90
24	5	60	9	0.30	94

Table 2: Residual arsenic concentration after treatment with 1g C. thevetia.

S.N.	Initial concentration (in ppm)	Time (in minutes)	pH	Residual concentration (in ppm)	% Removal = C_i –C_t/C_i ×100
1	2	15	2	0.20	90
2	2	30	2	0.15	92.5
3	2	45	2	0.15	92.5
4	2	60	2	0.10	95
5	2	15	7	0.10	95
6	2	30	7	0.08	96
7	2	45	7	0.08	96
8	2	60	7	0.10	95
9	2	15	9	0.10	95
10	2	30	9	0.10	95
11	2	45	9	0.10	95
12	2	60	9	0.10	95
13	5	15	2	0.50	90
14	5	30	2	0.50	90
15	5	45	2	0.50	90
16	5	60	2	0.50	90
17	5	15	7	0.40	92
18	5	30	7	0.45	91
19	5	45	7	0.50	90
20	5	60	7	0.50	90
21	5	15	9	0.50	90
22	5	30	9	0.50	90
23	5	45	9	0.15	97
24	5	60	9	0.15	97

FTIR spectral peaks of T. cordifolia before and after adsorption indicated the adsorption of arsenic ( Figure 5 ) .

Similarly, FTIR spectra of C. thevetia have also been done before and after adsorption of arsenic to see the change in peaks (Fig. 6).

Now the percentage removal of arsenic after treatment with 1 g powder of T. cordifolia is calculated by using equation (2) and C_iand C_tdata taken from Table 1.

Similarly, percentage removal of arsenic by 1 g powder of C. thevetia was calculated and shown in Table 2.

In figure 7, the values of percentage removal of As(III) at pH 2 and 9 are the same as a result coincident lines are obtained in the graph.

Figures 7 and 8 show percentage removal of As(III) by T. cordifolia for initial concentrations of 2 ppm and 5 ppm whereas figures 9 and 10 show percentage removal of As(III) by C. thevetia at pH 2, 7 and 9.

Table 3: Values of C_t, Q_t , C _t / Q _t , log Q _t and log C _t at different time intervals at pH 2, 7 and 9 for As(III) removal by 1g powder of T. cordifolia.

S.N.	Initial concentration(C_i) (in ppm)	Time (in minutes)	pH	Residual concentration(C_t) (in ppm)	As(III) adsorbed (mg/L)	Q_t	C_t/Q_t	logC_t	logQ_t
1	2	15	2	0.25	1.75	0.175	1.429	-0.602	-0.757
2	2	30	2	0.25	1.75	0.175	1.429	-0.602	-0.757
3	2	45	2	0.25	1.75	0.175	1.429	-0.602	-0.757
4	2	60	2	0.25	1.75	0.175	1.429	-0.602	-0.757
5	2	15	7	0.15	1.85	0.185	0.811	-0.824	-0.733
6	2	30	7	0.10	1.90	0.190	0.526	-1	-0.721
7	2	45	7	0.10	1.90	0.190	0.526	-1	-0.721
8	2	60	7	0.10	1.90	0.190	0.526	-1	-0.721
9	2	15	9	0.25	1.75	0.175	1.429	-0.602	-0.757
10	2	30	9	0.25	1.75	0.175	1.429	-0.602	-0.757
11	2	45	9	0.25	1.75	0.175	1.429	-0.602	-0.757
12	2	60	9	0.25	1.75	0.175	1.429	-0.602	-0.757
13	5	15	2	0.30	4.70	0.470	0.638	-0.523	-0.328
14	5	30	2	0.30	4.70	0.470	0.638	-0.523	-0.328
15	5	45	2	0.40	4.60	0.460	0.870	-0.398	-0.337
16	5	60	2	0.40	4.60	0.460	0.870	-0.398	-0.337
17	5	15	7	0.15	4.85	0.485	0.309	- 0.824	-0.314
18	5	30	7	0.15	4.85	0.485	0.309	-0.824	-0.314
19	5	45	7	0.25	4.75	0.475	0.526	-0.602	-0.323
20	5	60	7	0.10	4.90	0.490	0.204	-1	-0.310
21	5	15	9	0.35	4.65	0.465	0.753	-0.456	-0.333
22	5	30	9	0.40	4.60	0.460	0.870	-0.398	-0.337
23	5	45	9	0.50	4.50	0.450	1.111	-0.301	-0.347
24	5	60	9	0.30	4.70	0.470	0.638	-0.523	-0.328

Kinetic adsorption data collected in Tables 3 and 4 for T. cordifolia and C. thevetia have been analysed for pseudo-first and second order kinetic model to see the mechanism of adsorption.

In figure 11, the values of log C_t are the same at pH 2 and 9. So, the lines coincide in the graph.

An extensive study of adsorption isotherms such as Langmuir, and Freundlich at initial concentrations of 2 and 5 ppm was done to arrive at a suitable mode of isotherm.

Table 4: Values of C_t, Q_t , C _t / Q _t , log C_t and log Q _t at different time intervals at pH 2, 7 and 9 for As(III) removal by 1g powder of C. thevetia.

S.N.	Initial concentration(C_i) (in ppm)	Time (in minutes)	pH	Residual concentration(C_t) (in ppm)	As(III) adsorbed(mg/L)	Q_t	C_t/Q_t	LogC_t	logQ_t
1	2	15	2	0.20	1.80	0.180	1.111	-0.699	-0.745
2	2	30	2	0.15	1.85	0.185	0.811	-0.854	-0.733
3	2	45	2	0.15	1.85	0.185	0.811	-0.852	-0.733
4	2	60	2	0.10	1.90	0.190	0.526	-1.000	-0.721
5	2	15	7	0.10	1.90	0.190	0.526	-1.000	-0.721
6	2	30	7	0.08	1.92	0.192	0.417	-1.10	-0.717
7	2	45	7	0.08	1.92	0.192	0.417	-1.10	-0.717
8	2	60	7	0.10	1.90	0.190	0.526	-1.000	-0.721
9	2	15	9	0.10	1.90	0.190	0.526	-1.000	-0.721
10	2	30	9	0.10	1.90	0.190	0.526	-1.000	-0.721
11		45	9	0.10	1.90	0.190	0.526	-1.000	-0.721
12	2	60	9	0.10	1.90	0.190	0.526	-1.000	-0.721
13	5	15	2	0.50	4.50	0.450	1.111	-0.301	-0.347
14	5	30	2	0.50	4.50	0.450	1.111	-0.301	-0.347
15	5	45	2	0.50	4.50	0.450	1.111	-0.301	-0.347
16	5	60	2	0.50	4.50	0.450	1.111	-0.301	-0.347
17	5	15	7	0.40	4.60	0.460	0.870	-0.398	-0.337
18	5	30	7	0.45	4.55	0.455	0.989	-0.347	-0.342
19	5	45	7	0.50	4.50	0.450	1.111	-0.301	-0.347
20	5	60	7	0.50	4.50	0.450	1.111	-0.301	0.347
21	5	15	9	0.50	4.50	0.450	1.111	-0.301	-0.347
22	5	30	9	0.50	4.50	0.450	1.111	-0.301	-0.347
23	5	45	9	0.15	4.85	0.485	0.309	-0.824	-0.314
24	5	60	9	0.15	4.85	0.485	0.309	-0.824	-0.314

Tables 3 and 4 show the values of C_t, Q_t , C_t/Q_t, logQ_t,

Discussion

On one hand the residual concentration of arsenic by T. cordifolia is 0.10 ppm at pH 7, on the other the residual concentration of arsenic by C. thevetia is 0.10 ppm at pH 2 with an initial concentration of 2 ppm arsenic solution and maximum removal percentage is 95% (Table 2). With an initial concentration of 5 ppm, the maximum removal percentage is 97% at pH 9. HPLC has been utilized to observe the peaks before and after adsorption. The wavelength for UV detection is 227 nm clearly showing the peaks of the analyte.

HPLC of treated and untreated T. cordifolia and C. thevetia could be referred as an indication of adsorption clearly observed by change of peaks (Fig. 1, 2, 3 and 4 ) at wavelength 227 nm. HPLC has been utilized to observe the peaks before and after adsorption. The wavelength for UV detection is 227 nm which clearly shows the peaks of the analyte.

Fourier transmission infrared (FTIR) spectroscopy was done to explore the adsorption of As(III) by T. cordifolia and C. thevetia. The presence of -OH and –COOH groups, and lignin in the plant biomass can be explained as cause of adsorption of As(III) on the surface. The changes in shifts and intensity clearly indicate the adsorption on the surface.

Figures 11 and 12 show pseudo-first order kinetic model for an initial concentration of 2 ppm and 5 ppm respectively for T. cordifolia which clearly indicates that the experimental data is not fit for pseudo – first order kinetics.

Figure 13 and 14 represent pseudo – second order model of adsorption of As(III) by T. cordifolia for an initial concentration of 2 ppm and 5 ppm respectively at pH 2, 7 and 9. The linearity of the graph clearly showed the pseudo-second order reaction.

Figures 15 and 16 show Langmuir adsorption isotherm for T. cordifolia at initial concentration of 2 ppm and 5 ppm and pH 2, 7 and 9.

Figures 17 and 18 show Freundlich adsorption isotherm for T. cordifolia. Langmuir adsorption isotherm is a better fit for experimental data for T. cordifolia.

Figures 19 and 20 show pseudo first order kinetics for adsorption by T. cordifolia for initial concentrations of 2 ppm and 5 ppm at pH 2, 7 and 9.

Figures: 21 and 22 show pseudo second order model for adsorption by C. thevetia clearly indicating that this model is the fit for C. thevetia.

Figure 23 and 24: show the plot of C_t/Q_t versus C_t for adsorption of As(III) by C. thevetia for initial concentrations 2 and 5 ppm at pH 2, 7 and 9.

Comparison

T. cordifolia and C. thevetia have been widely used as a folk and ayurvedic medicine. The maximum removal efficiency of As(III) by these medicinal plants have been evaluated up to 97% which is very large in comparison to other adsorbents.

Conclusion

The present study revealed that the removal of As(III) solution was the best fit with pseudo second order model. Langmuir adsorption model suited the data which confirmed monolayer adsorption. The adsorption of As(III) by T. cordifolia and C. thevetia appears to be a complex process which may get affected by intra-particle diffusion, slow chemical diffusion, and chemisorption. If the medicinal plant is grown on arsenic contaminated soil, the medicinal values might get adversely affected. The soil growing the medicinal plants should be free from As(III) to get maximum benefits.

Thus, pseudo-second order reaction and Langmuir adsorption isotherms completely describe the adsorption mechanism and are the best fit for them.

Acknowledgement

The authors would like to thank Prof. Alakesh Bisai, IISER Kolkata for providing SEM and EDAX facilities.

Funding Sources

The author(s) received no financial support for the research, authorship, and/or publication of this article.

Conflict of Interest

The authors do not have any conflict of interest.

Data Availability Statement

The manuscript incorporates all datasets produced or examined throughout this research study.

Ethics Statement

This research did not involve human participants, animal subjects or any material that requires ethical approval.

Informal Consent Statement

This study did not involve human participants, and therefore informal consent was not required.

Author Contributions

Rajendra Kumar contributed to the methodology

Ashok Kumar Jha supervised and contributed to the analysis of data and Raghbendra Thakur approved the daft.

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