Removal of Pb(II) ions from aqueous solution and industrial effluent using natural biosorbents

Purpose

The purpose of the research is to investigate the applicability of the low-cost natural biosorbents for the removal of Pb(II) ions from aqueous solution and effluent from battery industry.

Methods

Six different biosorbents namely rice straw, rice bran, rice husk, coconut shell, neem leaves, and hyacinth roots have been used for the removal of Pb(II) ions from aqueous solution in batch process. All the biosorbents were collected from local area near Kolkata, West Bengal, India. The removal efficiency was determined in batch experiments for each biosorbent.

Results

The biosorbents were characterized by SEM, FTIR, surface area, and point of zero charge. The sorption kinetic data was best described by pseudo-second-order model for all the biosorbents except rice husk which followed intraparticle diffusion model. Pb(II) ions adsorption process for rice straw, rice bran, and hyacinth roots were governed predominately by film diffusion, but in the case of rice husk, it was intraparticle diffusion. Film diffusion and intraparticle diffusion were equally responsible for the biosorption process onto coconut shell and neem leaves. The values of mass transfer coefficient indicated that the velocity of the adsorbate transport from the bulk to the solid phase was quite fast for all cases. Maximum monolayer sorption capacities onto the six natural sorbents studied were estimated from the Langmuir sorption model and compared with other natural sorbents used by other researchers. The Elovich model, the calculated values of effective diffusivity, and the sorption energy calculated by using the Dubinin?CRadushkevich isotherm were indicated that the sorption process was chemical in nature. The thermodynamic studies indicated that the adsorption processes were endothermic. FTIR studies were carried out to understand the type of functional groups responsible for Pb(II) ions binding process. Regeneration of biosorbents were carried out by desorption studies using HNO₃. Battery industry effluents were used for the application study to investigate applicability of the biosorbents.

Conclusion

The biosorbents can be utilized as low-cost sorbents for the removal of Pb(II) ions from wastewater.     

Efficient biosorption of chromium(VI) ion by dry Araucaria leaves

Background

In this paper, batch removal of hexavalent chromium from aqueous solutions by Araucaria heterophylla leaves was investigated. The batch experiments were conducted to study the adsorption of metal species and effect of different pH, contact time, metal concentration, biosorbent concentration, and adsorption capacity.

Method

Freundlich and Langmuir??s isotherm model were used to describe the adsorption behavior, and the experimental results fitted Freundlich model well.

Results

The adsorption efficiency observed for all chromium concentrations, i.e., 1, 3, 5, and 10?mg/L was 100% and the equilibrium was achieved in 30?min for 1 and 3?mg/L, whereas for 5 and 10?mg/L, it was less than 60?min. FTIR spectra was taken to identify functional groups involved in the biosorption.

Conclusion

Thus, Araucaria leaves can be considered as one of the cheap and efficient biosorbent for toxic hexavalent chromium removal from natural or wastewaters.     

Biosorption of Cr(VI) by free and immobilized Pediastrum boryanum biomass: equilibrium, kinetic, and thermodynamic studies

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.     

Evaluation of the individuality of white rot macro fungus for the decolorization of synthetic dye

Introduction

A biosorbent was developed by simple dried Agaricus bisporus (SDAB) and effectively used for the biosorption of cationic dyes, Crystal Violet and Brilliant Green.

Materials and methods

For the evaluation of the biosorbent system, all the batch equilibrium parameters like pH, biomass dose, contact time, and temperature were optimized to determine the decolorization efficiency of the biosorbent. The maximum yields of dye removal were achieved at pH 4.0 for Crystal Violet (CV) and pH 5.0 for Brilliant Green (BG), which are closer to their natural pH also.

Result and discussion

Equilibrium was established at 60 and 40 min for CV and BG, respectively. Pseudo first-order, pseudo second-order, and intraparticle-diffusion kinetic models were studied at different temperatures. Isotherm models such as Freundlich, Langmuir, and Dubinin–Radushkevich were also studied. Biosorption processes were successfully described by Langmuir isotherm model and the pseudo second-order kinetic model.

Conclusions

The biosorption capacity of A. bisporus over CV and BG were found as 21.74 and 12.16 mg gm^?1. Thermodynamic parameters indicated that the CV and BG dye adsorption onto A. bisporus is spontaneous and exothermic in the single and ternary systems. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were used for the surface morphology, crystalline structure of biosorbent, and dye–biosorbent interaction, respectively. This analysis of the biosorption data confirmed that these biosorption processes are ecofriendly and economical. Thus, this biomass system may be useful for the removal of contaminating cationic dyes.     

Biosorption of cadmium(II) and copper(II) ions from aqueous solution by core of Artocarpus odoratissimus

Purpose

This research is on the evaluation of biosorption capability of the core of Artocarpus odoratissimus (Tarap), grown in Brunei Darussalam, towards Cd(II) and Cu(II) ions present in synthetic solutions, and to characterize the surface of Tarap particles.

Methods

Thermogravimetric analysis and surface titrations were conducted to characterize the surface of dried Tarap core particles. Atomic absorption spectroscopic measurements were conducted to determine the extent of removal of Cd(II) and Cu(II) under different experimental conditions.

Results

Mass reductions associated with many exothermic reaction peaks were observed beyond 200°C up to 650°C indicating the combustion of organic matter in Tarap. Dried particles of core of Tarap bear a negative surface charge promoting strong interaction towards positively charged ions, such as Cu(II) and Cd(II). Biosorption of the two metal ions on Tarap, which is relatively high beyond pH?=?4, occurs within a short period of exposure time. The extent of biosorption is enhanced by acid treatment of the biosorbent, and further it does not significantly depend on the presence of nonreacting ions up to an ionic strength of 2.0?M.

Conclusion

Strong attraction between each metal ion and the biosorbent is attributed to the negative surface charge on the biosorbent within a broad pH range. Acid treatment of the biosorbent improves sorption characteristics, suggesting that ion exchange plays an important role in the metal ion??biosorbent interaction process.     

Characterization and lead(II), cadmium(II), nickel(II) biosorption of dried marine brown macro algae Cystoseira barbata

Purpose

The objectives of this research are to identify the functional groups and determine corresponding pK _a values of the acidic sites on dried brown algae Cystoseira barbata using FTIR and potentiometric titrations, and to investigate the biosorption ability of biomass towards divalent nickel, cadmium, and lead ions. Adsorption was studied as a function of solution pH and contact time, and experimental data were evaluated by the Langmuir isotherm model.

Methods

CaCl₂ pretreatment was applied to the sorbent for enhancing the metal uptake capacity. The effect of solution pH on biosorption equilibrium was investigated in the pH range of 1.5?C5.0. Individual as well as competitive adsorption capacity of the sorbent were studied for metal cations and mixtures.

Results

The retention of the tested metal ions was mostly influenced from pH in the range of 1.5?C2.5, then stayed almost constant up to 5.0, while Ni(II) uptake showed the highest variation with pH. Potentiometric titrations were performed to find the number of strong and weak acidic groups and their acidity constants. The density of strong and weak acidic functional groups in the biomass were found to be 0.9 and 2.26?mmol/g, respectively. The FTIR spectra of the sorbent samples indicated various functionalities on the biomass surface including carboxyl, hydroxyl, and amino and sulphonate groups which are responsible for the binding of metal ions.

Conclusions

The capacity of the biomass for single metal ions (around 1?mmol/g) was increased to 1.3?mmol/g in competitive adsorption, Pb(II) showing the highest Langmuir intensity constant. Considering its extremely high abundance and low cost, C. barbata may be potentially important in metal ion removal from contaminated water and industrial effluents.     

Equilibrium, kinetic and thermodynamic studies on the biosorption of reactive acid dye on Enteromorpha flexuosa and Gracilaria corticata

Purpose

Biosorption is an emerging, eco-friendly and economical method for treating the wastewater effluents. Compared to many other biological materials, algae biomass proved to be the better biosorbent due to the presence of cell wall polymers in them.

Methods

Algal biomasses namely Enteromorpha flexuosa and Gracilaria corticata were dried, crushed and used as biosorbents. Ponceau S, a diazo dye was used as a model adsorbate for the biosorption studies. The biosorbents were characterized by Scanning Electron Microscopy, FT-IR and zero point charge. Batch studies were performed by varying pH, biosorbent dosage and initial dye concentrations. Adsorption isotherms, kinetic and thermodynamic analyses were carried out. The effect of electrolytes was also studied. Batch desorption studies were also carried out using various reagents.

Results

Isotherm data were tested with Langmuir and Freundlich isotherm models and the results suggested that the Freundlich isotherm fitted the data well. Kinetic studies were performed with varying initial dye concentrations and the data were incorporated with pseudo first-order and pseudo second-order kinetic equations and was found that the studied biosorption processes followed pseudo second-order kinetic equation. Thermodynamic parameters were evaluated at three different temperatures 293?K, 300?K and 313?K. About 95% of the dye could be desorbed from both the biosorbents.

Conclusion

Both the algal biomasses had heterogeneous surfaces and followed pseudo second-order chemical kinetics. Thermodynamic parameters proved that the biosorption by both the biomasses were spontaneous, feasible and endothermic processes. Desorption studies proved the worth of the algal biomasses as biosorbents in industrial level.     

Equilibrium, kinetic, and thermodynamic biosorption of Pb(II), Cr(III), and Cd(II) ions by dead anaerobic biomass from synthetic wastewater

Purpose

Heavy metals are toxic pollutants released into the environment as a result of different industrial activities. Biosorption of heavy metals from aqueous solutions is a new technology for the treatment of industrial wastewater. The aim of the present research is to highlight the basic biosorption theory to heavy metal removal.

Materials and methods

Heterogeneous cultures mostly dried anaerobic bacteria, yeast (fungi), and protozoa were used as low-cost material to remove metallic cations Pb(II), Cr(III), and Cd(II) from synthetic wastewater. Competitive biosorption of these metals was studied.

Results

The main biosorption mechanisms were complexation and physical adsorption onto natural active functional groups. It is observed that biosorption of these metals was a surface process. The main functional groups involved in these processes were hydroxyl (–OH) and carboxylic groups (C=O) with 37, 52, and 31 and 21, 14, and 34 % removal of Pb(II), Cr(III), and Cd(II), respectively. Langmuir was the best model for a single system. While extended Langmuir was the best model for binary and ternary metal systems. The maximum uptake capacities were 54.92, 34.78, and 29.99 mg/g and pore diffusion coefficients were 7.23, 3.15, and 2.76?×?10^?11 m²/s for Pb(II), Cr(III), and Cd(II), respectively. Optimum pH was found to be 4. Pseudo-second-order was the best model to predict the kinetic process. Biosorption process was exothermic and physical in nature.

Conclusions

Pb(II) offers the strongest component that is able to displace Cr(III) and Cd(II) from their sites, while Cd(II) ions are the weakest adsorbed component.     

Biosorption of antimony(V) by freshwater cyanobacteria Microcystis from Lake Taihu,China: effects of pH and competitive ions

There is limited knowledge available on metalloid biosorption by freshwater algae. In this study, biosorption properties of anionic Sb(OH) ₆ ^? by naturally occurring cyanobacteria Microcystis were investigated as a function of initial pH, biosorbent dosage, contact time, and addition sequences of competitive ions, and their binding mechanisms were discussed. The biosorption process was fast and equilibrium was reached at 2 h. Sb(V) biosorption decreased with the increase of pH and the optimum pH range was 2.5–3.0, which corresponded with the changes of surface charges of the cell wall of Microcystis. The biosorption data satisfactorily followed the Freundlich model. The simultaneous addition of H₂PO₄ ^? and Ca²⁺ enhanced Sb(V) biosorption, while NO₃ ^? greatly inhibited the biosorption, compared with single Sb(V) addition. The initial addition of the competitive ions reduced Sb(V) biosorption at higher Sb(V) concentrations, compared with simultaneous addition. A fraction of biosorbed Sb(V) was replaced by the competitive ions which were added subsequently, and the exchange only occurred at higher concentrations of Sb(V). 1.0 mol/L HCl demonstrated the highest desorption efficiency. Speciation analyses indicated that no reduction of Sb(V) into Sb(III) occurred. Based on the results of zeta potential and attenuated total reflection infrared spectroscopy spectra, Sb(OH) ₆ ^? bound to the biomass through electrostatic attraction and surface complexation, and amino, carboxyl, and hydroxyl groups were involved in the biosorption process. The study suggest that Microcystis from cyanobacteria blooms could be used as a potential biosorbent to remove Sb(V) from effluents at environmentally relevant concentrations (≤10.0 mg/L).     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Arsenic accumulation and speciation in the submerged macrophyte Ceratophyllum demersum L.

Introduction

Ceratophyllum demersum L. is a widespread submerged macrophyte in aquatic environments.

Methods

Simulation experiments were conducted in the laboratory to investigate arsenic (As) accumulation, speciation, and efflux of C. demersum exposed to arsenate and arsenite solutions.

Results

Plant shoots showed a significant accumulation of As with a maximum of 862 and 963???g?As?g^?1 dry weight after 4?days of exposure to 10???M arsenate and arsenite, respectively. Regardless of whether arsenate or arsenite was supplied to the plants, arsenite was the predominant species in plant shoots. Furthermore, a dramatically higher influx rate of arsenate compared with arsenite was observed in C. demersum exposed to As solutions without the addition of phosphate (P). Arsenate uptake was considerably inhibited by P in this study, suggesting that arsenate is taken up by C. demersum via the phosphate transporters. However, arsenite uptake was unaffected by P and markedly reduced in the presence of glycerol and antimonite (Sb), indicating arsenite shares the aquaporin transport pathway. In addition, C. demersum rapidly reduces arsenate to arsenite in the shoot of the plant and extrudes most of them (>60?%) to the external solutions. The efflux of arsenite was much higher than that of arsenate; the former is supposed to be both active and passive processes, and the latter through passive leakage.

Conclusion

C. demersum is a strong As accumulator and an interesting model plant to study As uptake and metabolism due to the lack of a root-to-shoot translocation barrier.     

Evaluation of different isotherm models,kinetic, thermodynamic,and copper biosorption efficiency of Lobaria pulmonaria (L.) Hoffm.

The biosorption characteristics of Cu(II) ions from aqueous solution using Lobaria pulmonaria (L.) Hoffm. biomass were investigated. The biosorption efficiency of Cu(II) onto biomass was significantly influenced by the operating parameters. The maximum biosorption efficiency of L. pulmonaria was 65.3% at 10 mg/L initial metal concentration for 5 g/L lichen biomass dosage. The biosorption of Cu(II) ions onto biomass fits the Langmuir isotherm model and the pseudo-second-order kinetic model well. The thermodynamic parameters indicate the feasibility and exothermic and spontaneous nature of the biosorption. The effective desorption achieved with HCl was 96%. Information on the nature of possible interactions between the functional groups of the L. pulmonaria biomass and Cu(II) ions was obtained via Fourier transform infrared (FTIR) spectroscopy. The results indicated that the carboxyl (–COOH) and hydroxyl (–OH) groups of the biomass were mainly involved in the biosorption of Cu(II) onto L. pulmonaria biomass. The L. pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities.

Implications: Lobaria pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities. To the best of our knowledge, this is the first paper on the biosorption Cu by L. pulmonaria.     

Highly efficient decolorization of Malachite Green by a novel Micrococcus sp. strain BD15

Purpose

Malachite Green (MG) is used for a variety of applications but is also known to be carcinogenic and mutagenic. In this study, a novel Micrococcus sp. (strain BD15) was observed to efficiently decolorize MG. The purposes of this study were to explore the optimal conditions for decolorization and to evaluate the potential use of this strain for MG decolorization.

Methods

Optical microscope and UV?Cvisible analyses were carried out to determine whether the decolorization was due to biosorption or biodegradation. A Plackett?CBurman design was employed to investigate the effect of various parameters on decolorization, and response surface methodology was then used to explore the optimal decolorization conditions. Kinetics analysis and antimicrobial activity tests were also performed.

Results

The results indicated that the decolorization by the strain was mainly due to biodegradation. Concentrations of MG, urea, and yeast extract and inoculum size had significantly positive effects on MG decolorization, while concentrations of CuCl₂ and MgCl₂, and temperature had significantly negative effects. The interaction between different parameters could significantly affect decolorization, and the optimal conditions for decolorization were 1.0 g/L urea, 0.9 g/L yeast extract, 100 mg/L MG, 0.1 g/L inoculums (dry weight), and incubation at 25.2°C. Under the optimal conditions, 96.9% of MG was removed by the strain within 1 h, which represents highly efficient microbial decolorization. Moreover, the kinetic data for decolorization fit a second-order model well, and the strain showed a good MG detoxification capability.

Conclusion

Based on the results of this study, we propose Micrococcus sp. strain BD15 as an excellent candidate strain for MG removal from wastewater.     

Aquatic ecotoxicity assessment of a new natural formicide

Background, aim and scope

Agrochemicals could reach aquatic ecosystems and damage ecosystem functionality. Natural formicide could be an alternative to use in comparison with the more toxic formicides available on the market. Thus, the objective of this study was to assess the ecotoxicity of the new natural formicide Macex? with a battery of classical aquatic ecotoxicity tests.

Material and methods

Bacteria (Aliivibrio fischeri), algae (Pseudokirchneriella subcapitata), hydra (Hydra attenuata), daphnids (Daphnia magna), and fish (Danio rerio) tests were performed in accordance with international standardized methodologies.

Results

In the range of formicide concentrations tested (0.03 to 2.0?g?L^?1) EC₅₀ values varied from 0.49 to >2.0?g?L^?1, with P. subcapitata being the most sensitive species and H. attenuata and D. rerio the most tolerant species to this product in aqueous solutions.

Conclusions

This new formicide preparation can be classed as a product of low toxicity compared to the aquatic ecotoxicity of the most common commercialized formicides.     

Removal of mercury(II) from aqueous solutions using the leaves of the Rambai tree (Baccaurea motleyana)

This study was undertaken to evaluate the biosorption potential of a natural, low-cost biosorbent, Rambai leaves (Baccaurea motleyana), to remove trace amounts of Hg(II) from aqueous solutions. It was found that the amount of Hg(II) biosorption by Rambai leaves increased with initial metal ion concentration, contact time, and solution pH but decreased as the amount of biosorbent increased. The maximum biosorption capacity was 121.95 mg/g for an initial concentration range of 5 to 120 ppb. Overall, kinetic studies showed that the Hg(II) biosorption process followed pseudo-second-order kinetics based on pseudo-first-order and intraparticle diffusion models. Isotherm data revealed that the biosorption process followed both Freundlich and Langmuir isotherms. The value of separation factor, R(L), from the Langmuir equation and rate of biosorption, n, from the Freundlich model also indicated favorable adsorption.     

Biosorption of arsenic in drinking water by submerged plant: Hydrilla verticilata

To evaluate the biosorption efficacy of submerged aquatic plant Hydrilla verticilata for arsenic uptake from drinking water. H. verticillata, a submerged aquatic plant was utilized successfully for arsenic uptake from aqueous solution. Batch studies with various parameters viz. pH, sorbent dose, contact time, initial metal ion concentration, and temperature were carried out. Data were utilized to plot Lagergren graph along with pseudo-second-order graphs for kinetic studies to estimate the removal efficacy and to determine the nature of reaction. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) have been performed for characterization of metals on biomass. The study showed 96.35 % maximum absorption of arsenic by H. verticilata at initial concentration of 100 ppb with 0.5 g of biomass/100 ml for 5 h contact time at pH?6.0 with 150 rpm agitation rate. Data followed Langmuir isotherm showing sorption to be monolayer on homogeneous surface of biosorbent. The negative values of ΔG° indicated spontaneous nature; whereas ΔH° indicates exothermic nature of system and negative value of ?S° entropy change correspond to a decrease in the degree of freedom to the adsorbed species followed by pseudo-second-order adsorption kinetics. FTIR and SEM results showed apparent changes in functional group regions after metal chelation and the changes in surface morphology of biosorbent. This is a comparatively more effective, economic, easily available, and environmentally safe source for arsenic uptake from solution due to its high biosorption efficacy than other biosorbents already used.     

Copper chitosan nanocomposite: synthesis, characterization, and application in removal of organophosphorous pesticide from agricultural runoff

Purpose

Removal of malathion from agricultural runoff was studied using novel copper-coated chitosan nanocomposite (CuCH)??a biopolymeric waste obtained from marine industry.

Methods

Synthesis and characterization of the adsorbent using different spectral techniques like Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer, Emmett, and Teller surface analyzer have been carried out. Equilibrium studies have been carried out to optimize the dose rate, pH, and the reaction time. Parathion and methyl parathion removal were also evaluated by CuCH in the batch mode. Using gas chromatography?Cmass spectrometry (GC?CMS) and FTIR studies suitable mechanism for adsorption has been suggested.

Results

The particle size of the adsorbent ranged from 700 to 750?nm. The surface area was found to be 20?m²?g^-1 with a pore volume of 0.11?cc?g^-1. The maximum adsorption capacity of malathion by CuCH was found to be 322.6?±?3.5?mg?g^-1 at an optimum pH of 2.0. Presence of copper ions enhanced the adsorption capacity of the adsorbent. The reaction was found to follow pseudo second-order kinetics with a rate constant of 0.53?g?mg^-1?min^-1. Evidence from FTIR indicated that copper ions form a dithionate complex with malathion during the adsorption stage. The adsorbent was found to remove malathion completely from spiked concentration of 2?mg?l^-1 in the agricultural run-off samples. It was also found that CuCH removed other organophospurous pesticides like methyl parathion and parathion under prevailing conditions.

Conclusions

The results indicated that CuCH could be applied for the removal of organophosphorous pesticides.     

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies

Background, aim, scope

Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst.

Materials and methods

Ferrous sulfate (FeSO₄·7H₂O), sulfuric acid (36?N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50?cm and diameter 6?cm, were fabricated with PVC while one reactor was packed with MAC of mass 150?g and other without MAC served as control.

Results and discussion

The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89?kJ/mol, respectively. The thermodynamic parameters ??G, ??H, and ??S were calculated for the oxidation processes using Van??t Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV?Cvisible spectroscopy, and cyclic voltammetry.

Conclusions

The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time?C4?h, and H₂O₂/FeSO₄·7H₂O in the molar ratio of 2:1.