Faculty Publications

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    Insights on the advanced processes for treatment of inorganic water pollutants
    (Elsevier, 2020) Mohan Balakrishnan, R.M.; Uddandarao, P.; Manirethan, V.; Raval, K.
    A remarkable increase in the discharge of inorganic pollutants globally from various sources such as mines, industries, or agricultural lands is a major threat to the environment. Development of novel methodologies to mitigate the effects caused by inorganic pollutants in water is crucial in addressing environmental issues. In this regard, various biological sources as nanosorbents and biosensors are venerated as superior entities for the detection and removal of inorganic contaminants. This chapter summarizes the utility of marine bacterial melanin- and fungal-based selenium nanoparticles for the adsorption and further reports endophytic fungal–based ZnS and PbS nanoparticles for the detection of inorganic pollutants from the aqueous systems; moreover, it gives a perspective on current challenges for the removal of contaminants. © 2020 Elsevier Inc. All rights reserved.
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    Kinetic and thermodynamic studies on the adsorption of heavy metals from aqueous solution by melanin nanopigment obtained from marine source: Pseudomonas stutzeri
    (Academic Press, 2018) Manirethan, V.; Raval, K.; Rajan, R.; Thaira, H.; Mohan Balakrishnan, R.M.
    The difficulty in removal of heavy metals at concentrations below 10 mg/L has led to the exploration of efficient adsorbents for removal of heavy metals. The adsorption capacity of biosynthesized melanin for Mercury (Hg(II)), Chromium (Cr(VI)), Lead (Pb(II)) and Copper (Cu(II)) was investigated at different operating conditions like pH, time, initial concentration and temperature. The heavy metals adsorption process was well illustrated by the Lagergren's pseudo-second-order kinetic model and the equilibrium data fitted excellently to Langmuir isotherm. Maximum adsorption capacity obtained from Langmuir isotherm for Hg(II) was 82.4 mg/g, Cr(VI) was 126.9 mg/g, Pb(II) was 147.5 mg/g and Cu(II) was 167.8 mg/g. The thermodynamic parameters revealed that the adsorption of heavy metals on melanin is favorable, spontaneous and endothermic in nature. Binding of heavy metals on melanin surface was proved by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Contemplating the results, biosynthesized melanin can be a potential adsorbent for efficient removal of Hg(II), Cr(VI), Pb(II) and Cu(II) ions from aqueous solution. © 2018 Elsevier Ltd
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    Melanin nano-pigments for heavy metal remediation from water
    (Taylor and Francis Inc. 325 Chestnut St, Suite 800 Philadelphia PA 19106, 2019) Thaira, H.; Raval, K.; Manirethan, V.; Mohan Balakrishnan, R.M.
    Melanins are water insoluble polyphenol compounds. The metal ion chelating property of natural melanin is exploited for removal of heavy metals from contaminated water. We optimized biosynthesis of melanin from marine bacterium using different growth media, media components, and operating conditions. Optimized medium yielded 513 mg/L melanin at 36 h of incubation, which was 3.15 times higher than the yield before optimization. Particle size analysis of the biosynthesized melanin indicated a size of 32 ± 0.98 nm. Preliminary investigation indicated that melanin nanoparticles could adsorb different heavy metals such as chromium, selenium, and lead from very low initial concentrations. © 2018, © 2018 Taylor & Francis.
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    Adsorptive removal of trivalent and pentavalent arsenic from aqueous solutions using iron and copper impregnated melanin extracted from the marine bacterium Pseudomonas stutzeri
    (Elsevier Ltd, 2020) Manirethan, V.; Raval, K.; Mohan Balakrishnan, R.M.
    The metalloid arsenic is one of the most conspicuous groundwater contaminants in the Indian subcontinent and its removal from aqueous medium is the main focus of this study. The study aims at functionalising melanin using iron and copper for the efficient removal of arsenic and rendering water fit for consumption. Melanin obtained from the marine bacteria Pseudomonas stutzeri was functionalised by iron impregnation (Fe-melanin) and copper impregnation (Cu-melanin). Morphological studies using FESEM portrayed the impregnated iron and copper granules on the surface of melanin, while XRD analysis confirmed the presence of Fe2O3 and CuO on melanin. Adsorption studies on As (V) and As (III) were conducted using Fe-melanin and Cu-melanin for different operating variables like pH, temperature and contact time. More than 99% per cent of As (III) and As (V) from water was removed at a pH range between 4 and 6 within 50 min in the case of Fe-melanin and 80 min for Cu-melanin. Adsorption equilibrium studies showed better fit with Langmuir adsorption isotherm and had good agreement with Redlich-Peterson's three-parameter model. The maximum adsorption capacities of Fe-melanin and Cu-melanin obtained from Langmuir adsorption model are 50.12 and 20.39 mg/g, respectively, for As (V) and similarly 39.98 and 19.52 mg/g, respectively, for As (III). Arsenic-binding to the functionalised melanin was confirmed using FT-IR and the XPS analysis. Reuse of the adsorbent was effectively done by desorbing the iron and copper together with the bound As (III) and As (V) and further re-impregnation of iron and copper in melanin. Re-functionalised melanin showed 99% adsorption efficiency up to four cycles of adsorption/desorption. A novel iron and copper impregnated melanin was synthesized to remove As (III) and As (V) from groundwater and the adsorption process was optimized. © 2019 Elsevier Ltd
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    Batch and continuous studies on the removal of heavy metals from aqueous solution using biosynthesised melanin-coated PVDF membranes
    (Springer, 2020) Manirethan, V.; Gupta, N.; Mohan Balakrishnan, R.M.; Raval, K.
    Heavy metals like mercury, chromium, lead and copper present in groundwater at lower concentrations cause severe health issues and can even be fatal when consumed. The biopigment/biopolymer melanin can be reaped from different sources like bacterium, fungus, and human hair. It has excellent heavy metal ion scavenging property and can be exploited for non-biological applications, substantially including water purification. In this work, melanin nanoparticles were derived from the marine bacterium Pseudomonas stutzeri and were coated onto hydrophobic polyvinylidene fluoride (PVDF) membrane as a support, for batch and continuous removal of heavy metal studies. Batch studies on the effect of pH, temperature and adsorbate dose and continuous adsorption studies on the effect of flow rate, adsorbate and adsorbent mass loadings were carried out by using biosynthesised melanin-coated PVDF membranes for the removal of Hg(II), Cr(VI), Pb(II) and Cu(II). Scanning electron microscope (SEM) images revealed the surface morphology, Fourier-transform infrared spectroscopy (FTIR) and energy-dispersive X-ray spectroscopy (EDS) deciphered the chemical characteristics of melanin-coated PVDF membranes before and after adsorption. Contact angle measurement confirmed the improvement in hydrophilicity of PVDF membrane upon coating with melanin. The maximum removal percentages of heavy metals achieved by melanin-coated PVDF membranes under batch mode operation were 87.6%, 88.45%, 91.8% and 95.8% for mercury, chromium, lead and copper, respectively optimised at 318 K and pH of 3 for chromium and 5 for other metals. However, the continuous mode of operation with a flow rate of 0.5 mL/min having 1 mg/L of heavy metal solution concentration exposed to 50 mg of melanin loading with a working volume of 200 mL showed better removal efficiencies compared with batch mode. The dynamic studies using Thomas and Yoon–Nelson models described the transient stage of the breakthrough curve and the model constants were calculated for column design and scale-up. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.
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    Batch and continuous studies on the removal of heavy metals using biosynthesised melanin impregnated activated carbon
    (Elsevier B.V., 2020) Manirethan, V.; Mohan Balakrishnan, R.M.
    The adversity associated with the removal of melanin nanoparticles after adsorbing heavy metals led to the development of a system involving activated carbon on which melanin was effectively impregnated. The melanin impregnated activated carbon was handily removed from the aqueous medium by simple filtration. The batch studies performed to scrutinise the optimum conditions for maximum adsorption concluded the contact time needed to attain equilibrium to be 90 min for all metals of study. Maximum adsorption of Cr (VI) was shown at pH 3 while Hg (II), Pb (II) and Cu (II) was adsorbed efficiently at pH 5. Increase in temperature favoured the adsorption process for all metals showing maximum removal at 328 K. Melanin impregnated activated carbon could adsorb 84.59% Hg (II), 86.6% Cr (VI), 91.1% Pb (II) and 93.8% Cu (II) from 5 mg/L heavy metal solution. Dynamic studies were conducted by varying the parameters like flow rate, inlet heavy metal concentration and adsorbent loading. Optimum conditions for a maximum breakthrough was obtained with a flow rate of 0.5 mL/min, heavy metal inlet concentration of 1 mg/L and adsorbent loading of 100 mg. Experimental data modelled in equilibrium isotherms showed the best fitting with the Thomas model when compared with the Adam–Boharts model using determined coefficient and error analysis. Efficient chemical desorption of Hg (II), Pb (II) and Cu (II) was obtained using 3N HCl and Cr (VI) using 1N citric acid. © 2020 Elsevier B.V.
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    Photocatalytic Degradation of Chlorpyrifos and Tetracycline in Aqueous Medium Using Silver Titanate Perovskite Nanoparticles
    (Springer Science and Business Media Deutschland GmbH, 2024) Joseph, A.; Raval, K.; Manirethan, V.
    Near-infrared (NIR) active silver titanate perovskite (AgTiO3)-based photocatalysis is a potential method for degrading organic pollutants due to its unique structural features, compositional flexibility, and affordability. Herein, we have synthesized novel NIR-active AgTiO3 nanoparticles with a low band gap of 0.92 eV via the hydrothermal method using Ananas comosus leave extract, which is a major agricultural waste worldwide. The produced AgTiO3 nanoparticles were characterized using Fourier Transform Infrared (FTIR) spectroscopy investigations, X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Energy dispersive X-ray spectroscopy (EDS). The photocatalytic activities of the AgTiO3 nanoparticles toward the degradation of tetracycline and chlorpyrifos under UV, visible, NIR, and solar light irradiation were carefully examined, and the photocatalytic mechanism was proposed using liquid chromatography-mass spectrometry (LC-MS) and high-performance liquid chromatography (HPLC). AgTiO3 nanoparticles completely degraded tetracycline and chlorpyrifos within 27 min and 21 min, respectively. The increased efficiency of AgTiO3 nanoparticles produced by green synthesis over conventional photocatalysts points to a potential advancement avenue for water treatment systems. Furthermore, using agricultural waste like leftover pineapple leaves not only lessens the impact on the environment but also solves the issue of cost when putting these technologies into practice on a larger scale. © The Author(s), under exclusive licence to Springer Nature Switzerland AG 2024.