Phyto-assisted synthesis of CuO/industrial waste derived biochar composite for adsorptive removal of doxycycline hydrochloride and recycling of spent biochar as green energy storage device.

The highest exposure of Endocrine disrupting compounds (EDC) into the water bodies as a result of extensive production and application of Covid-19 related drugs is a growing concern now a days. Herein, a novel nanocomposite material was developed by impregnating green synthesized copper oxide nanoparticles on the porous surface of fabric waste derived biochar to eliminate the concerned EDCs along with a sustainable disposal strategy for the spent adsorbent. Morphological characterizations by Field emission scanning electron microscopy confirmed the formation of hierarchical porous structured material. X-ray analysis revealed presence of both amorphous nature of biochar matrix as well as the crystalline nature attributed from monodispersion of copper oxide nanoparticles onto biochar surface. Batch sorption study showed removal of doxycycline hydrochloride (DOX) of >97% after 2 h at pH 7, 30 mg L-1 initial concentration of DOX and 2 g L-1 of adsorbent dose at room temperature after a two-step optimization process. Spectroscopic study and Raman shift suggested that pore filling, strong complexation and electrostatic interactions maximise the adsorption of DOX in the CuO/biochar composite as compared to the pristine biochar. However disposal of spent adsorbent is a crucial aspect for the environment and therefore, a sustainable recycling strategy for DOX loaded adsorbent as electrode material has been proposed for the first time in this study. Maximum specific capacitance value was observed in the range of 221.9-297.3 F g-1 for the DOX loaded nanocomposite at 1 mV s-1 comparable with other reported heteroatom-doped carbonaceous material as electrode. Therefore the excellent adsorption capacity of green synthesized CuO/biochar composite and its recycling after DOX adsorption can be recommended as a sustainable solution for mitigation of pharmaceuticals from wastewater. A detail study on degradation of DOX into eco-friendly products and its cost-effectiveness would be beneficial to suggest appropriate mitigation strategy for such compounds.

Sustainable conversion of textile industry cotton waste into P-dopped biochar for removal of dyes from textile effluent and valorisation of spent biochar into soil conditioner towards circular economy.

Effective immobilization of industrial waste into biochar development could be one of the most promising technologies for solid waste management to achieve circular economy. In this study, post-industrial cotton textile waste (PICTW), a cellulose rich industrial waste, was subjected to slow pyrolysis to develop a surface engineered biochar through phosphoric acid impregnation. Biochar produced at 500 °C designated as PICTWB500 showed a maximum methylene blue number (240 mg g-1) with remarkable specific surface area of 1498 m2 g-1. FESEM, FTIR, XRD and Raman spectra analysis were performed to investigate the surface texture and functionalities developed in the biochar. Adsorption efficiency of the biochar was assessed using drimarene red, blue, violet, and black dyes as model dye pollutants in batch mode at different biochar dose, pH and contact time. The maximum monolayer adsorption capacity was obtained in the range 285-325 mg g-1 for different dyes, determined from Langmuir adsorption model. The kinetic behaviour was more favourable with the pseudo second-order model. The recycling ability of PICTWB500 was proven to be effective up to 6th cycle without compromising its adsorption efficiency significantly. This study demonstrated an excellent adsorption capability of the biochar in dye laden real textile effluent and recycling of spent biochar as a precursor of bio compost. Hence, this study established a dual win strategy for waste utilization in textile industry using a closed loop approach with substantial techno-economic feasibility that may have potential applications.

Performance assessment of the indigenous ceramic UF membrane in bioreactor process for highly polluted tannery wastewater treatment.

The present study evaluates the performance of an indigenously developed ceramic ultrafiltration (UF) membrane in a lab-scale membrane bioreactor (MBR) process to treat real tannery effluent with varying organic loading (1500-6000 mg/L). UF membrane was prepared by the coating of bentonite clay on tubular clay-alumina macroporous support. The membrane surface was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET adsorption-desorption, contact angle measurement, and atomic force microscopy. In the side-stream MBR process, sewage sludge from a local sewage treatment plant was used as an activated sludge source with a constant sludge retention time of 30 days. Membrane filtration was performed in cross-flow mode using a single-channel membrane module. Artificial neural network (ANN) modeling tool was used to analyze the influence of various independent input variables, namely, the hydraulic retention time (4-10 h), mixed liquor suspended solid (MLSS) concentration (2-8 g/L), and influent COD concentration (1500-6000 mg/L) on COD removal (%) with feed-forward backpropagation method. Membrane study was done at a transmembrane pressure of 4.3 bar and feed flow rate of 7.5 L/min to observe the flux declination and fouling of the UF membrane with time. Average COD and BOD concentrations obtained in the treated effluent were 147.56 and 31 mg/L, respectively, and chromium concentration was < 0.1 mg/L; thus, treated effluent quality was found to be suitable for industrial recycling purposes apart from the safe environmental discharge. An in-depth study was undertaken to understand the removal mechanism in the MBR process, nature and extent of membrane fouling, changes in the morphology of the UF membrane, surface wettability, and surface topology by detailed surface characterization of the membrane pre- and post-filtration.

Arthrospira sp. mediated bioremediation of gray water in ceramic membrane based photobioreactor: process optimization by response surface methodology.

Direct discharge of raw domestic sewage enriched with nitrogenous and phosphorous compounds into the water bodies causes eutrophication and other environmental hazards with detrimental impacts on public and ecosystem health. The present study focuses on phycoremediation of gray water with Arthrospira sp. using an innovative hydrophobic ceramic membrane-based photobioreactor system integrated with CO2 biofixation and biodiesel production, aiming for green technology development. Surfactant and oil-rich gray water collected from the domestic kitchen was used wherein, chloride, sulfate, and surfactant concentrations were statistically optimized using response surface methodology (RSM), considering maximum microalgal growth rate as a response for the design. Ideal concentrations (mg/L) of working parameters were found to be 7.91 (sulfate), 880.49 (chloride), and 144.02 (surfactant), respectively to achieve optimum growth rate of 0.43 gdwt/L/day. Enhancement of growth rate of targeted microalgae by 150% with suitable CO2 (19.5%) supply and illumination in the photobioreactor affirms its efficient operation. Additionally, harvested microalgal biomass obtained from the process showed a biodiesel content of around 5.33% (dry weight). The microalgal treatment enabled about 96.82, 87.5, and 99.8% reductions in BOD, COD, and TOC, respectively, indicating the potential of the process in pollutant assimilation and recycling of such wastewater along with value-added product generation.

The study elucidated the application of indigenously designed and devised ceramic membranes in an algal photobioreactor for viable production of Arthrospira sp. employing gray water, aided by photosynthetic CO₂ sequestration and microalgal biorefinery. A highly encouraging result was achieved in the microalgal process under optimized culture conditions with >95% removal of organics. It may be stressed here that the process ran effectively without any elaborate arrangement of external aeration, thereby reducing the investment and operating costs to the minimum.

Ceramic membrane-based ultrafiltration combined with adsorption by waste derived biochar for textile effluent treatment and management of spent biochar.

PURPOSE: Effluents produced in the textile industries are important sources of water pollution due to the presence of toxic dyes, auxiliary chemicals, organic substances etc. Recycling of such industrial wastewater is one major aspect of sustainable water management; hence present study is focused on an eco-friendly process development for reclamation of higher loading textile wastewater. METHOD: Industrial effluent samples with varying loading were collected from textile processing units located in and around Kolkata city. Vegetable waste collected from local market was utilized to prepare an efficient biochar for elimination of the recalcitrant dyes. Prior to adsorption, ceramic ultrafiltration (UF) process was used for reduction of the organic loading and other suspended and dissolved components. RESULTS: A remarkably high BET surface area of 1216 m2g-1 and enhanced pore volume of 1.139 cm3g-1 was observed for biochar. The maximum adsorption capacity obtained from the Langmuir isotherm was about 300 mg.g-1. The combined process facilitated >99% removal of dyes and 77-80% removal of chemical oxygen demand (COD) from the various samples of effluent. The treated effluent was found suitable to discharge or reuse in other purposes. About 95% of dye recovery was achieved during biochar regeneration with acetone solution. The dye loaded spent biochar was composted with dry leaves and garden soil as bulking agent. Prepared compost could achieve the recommended parameters with high nutritional value after 45 days. CONCLUSIONS: The overall study showed potential of the proposed process towards treatment of toxic dye loaded textile effluent in an environment friendly and sustainable approach.

Removal of As(V), Cr(VI) and Cu(II) using novel amine functionalized composite nanofiltration membranes fabricated on ceramic tubular substrate.

Novel amine functionalized composite membranes were prepared over tubular ceramic substrate using facile dip-coating and cross-flow filtration approach. The two fabricated membranes, P-60S and P-60S-EDTA with polyethyleneimine (PEI) and EDTA-modified PEI as functional layers respectively, were characterized in terms of EDX, FTIR, XPS, FESEM, AFM and contact angle analyses which confirmed their stable physical and chemical structure for use in high pressure application. Clean water permeability and MWCO study revealed the superior permeability and rejection efficiency of the P-60S-EDTA compared to the P-60S membrane. Incorporation of bulky EDTA molecules in the membrane functional layer simultaneously decreased pore size and increased membrane hydrophilicity. The removal of As(V), Cr(VI) and Cu(II) heavy metals by both membranes were found to be highly pH dependent and overall rejection improved in case of P-60S-EDTA membrane [99.82% for Cu(II), 96.75% for As(V) and 97.22% for Cr(VI)]. Interestingly, rejection of As(V) and Cr(VI) was significantly improved in presence of Cu(II) due to volume resistance provided by EDTA-Cu(II) complex towards the passage of other heavy metal ions. Excellent stability of P-60S-EDTA membrane in continuous operation of 36 h in both ideal and practical water environment suggests its promising application in real field heavy metal contaminated waste water treatment.

Portable and rapid arsenic speciation in synthetic and natural waters by an As(V)-selective chemisorbent, validated against anodic stripping voltammetry.

Inorganic arsenic speciation, i.e. the differentiation between arsenite and arsenate, is an important step for any program aiming to address the global issue of arsenic contaminated groundwater, whether for monitoring purposes or the development of new water treatment regimes. Reliable speciation by easy-to-use, portable and cost-effective analytical techniques is still challenging for both synthetic and natural waters. Here we demonstrate the first application of an As(V)-selective chemisorbent material for simple and portable speciation of arsenic using handheld syringes, enabling high sample throughput with minimal set-up costs. We first show that ImpAs efficiently removes As(V) from a variety of synthetic groundwaters with a single treatment, whilst As(III) is not retained. We then exemplify the potential of ImpAs for simple and fast speciation by determining rate constants for the photooxidation of As(III) in the presence of a TiO2 photocatalyst. Finally, we successfully speciate natural waters spiked with a mix of As(III) and As(V) in both Indian and UK groundwaters with less than 5 mg L-1 dissolved iron. Experimental results using ImpAs agreed with anodic stripping voltammetry (ASV), a benchmark portable technique, with analysis conditions optimised here for the groundwaters of South Asia. This new analytical tool is simple, portable and fast, and should find applications within the overall multi-disciplinary remediation effort that is taking place to tackle this worldwide arsenic problem.

Development of graphene oxide/chitosan composite membrane on ceramic support for atrazine remediation by MBR process.

Graphene oxide (GO)-based composite ultrafiltration (UF) membranes were prepared on macroporous ceramic support tubes following a new way. Chitosan was used as an intermediate matrix between the substrate and GO coating. It has hydroxyl and amine groups, which enhances its film forming capacity with hydrophilic GO. This led us to use them as precursors for membrane development. Process efficiency of the prepared UF membrane was assessed in terms of the removal of toxic pesticide atrazine in side-stream membrane bioreactor (MBR) processes. Response surface methodology (RSM) was used to optimize the atrazine biodegradation efficiency. Enhanced atrazine removal of > 95% was obtained in the MBR treatment at the optimized conditions. Hermia's model equations were applied to analyze the mechanism of membrane fouling in the UF-MBR system. The influencing parameters were studied in details and pneumatic backpulsing was applied to minimize fouling in the UF-MBR system by statistical analysis. Mixed liquor suspended solids (MLSS) was found to affect both atrazine biodegradation and membrane fouling; hence, its effect was thoroughly analyzed. The developed process hence proved to be highly proficient in terms of such organic pesticides removal for long-term operations.

Surface Modification of Naturally Available Biomass for Enhancement of Heavy Metal Removal Efficiency, Upscaling Prospects, and Management Aspects of Spent Biosorbents: A Review.

Heavy metal pollution in water emerges as a severe socio-environmental problem originating primarily from the discharge of industrial wastewater. In view of the toxic, non-biodegradable, and persistent nature of most of the heavy metal ions, remediation of such components becomes an absolute necessity. Biosorption is an emerging tool for bioremediation that has gained momentum for employing low-cost biological materials with effective metal binding capacities. Even though biological materials possess excellent metal adsorption abilities, they show poor mechanical strength and low rigidity. Other disadvantages include solid-liquid separation problems, possible biomass swelling, lower efficiency for regeneration or reuse, and frequent development of high pressure drop in the column mode that limits its applications under real conditions. To improve the biosorption efficiency, biomasses need to be modified with a simple technique for selective/multi-metal adsorption. This review is intended to cover discussion on biomass modification for enhanced biosorption efficiency, mechanism studies using various instrumental/analytical techniques, and future direction for research and development including the fate of spent biosorbent. In most of the previously published researches, difficulty of the process in scaling up has not been addressed. The current article outlines the application potential of biosorbents in the development of hybrid technology integrated with membrane processes for water and wastewater treatment in industrial scale.

Anabaena sp. mediated bio-oxidation of arsenite to arsenate in synthetic arsenic (III) solution: Process optimization by response surface methodology.

Blue green algae Anabaena sp. was cultivated in synthetic arsenite solution to investigate its bio-oxidation potential for arsenic species. Response surface methodology (RSM) was employed based on a 3-level full factorial design considering four factors, viz. initial arsenic (III) concentration, algal dose, temperature and time. Bio-oxidation (%) of arsenic (III) was considered as response for the design. The study revealed that about 100% conversion of As (III) to As (V) was obtained for initial As (III) concentration of 2.5-7.5 mg/L at 30 °C for 72 h of exposure using 3 g/L of algal dose signifying a unique bio-oxidation potential of Anabaena sp. The dissolved CO2 (DCO2) and oxygen (DO) concentration in solution was monitored during the process and based on the data, a probable mechanism was proposed wherein algal cell acts like a catalytic membrane surface and expedites the bio-oxidation process. Bioaccumulation of arsenic, as well as, surface adsorption on algal cell was found considerably low. Lipid content of algal biomass grown in arsenite solution was found slightly lower than that of algae grown in synthetic media. Toxicity effects on algal cells due to arsenic exposure were evaluated in terms of comet assay and chlorophyll a content which indicated DNA damage to some extent along with very little decrease in chlorophyll a content. In summary, the present study explored the potential application of Anabaena sp. as an ecofriendly and sustainable option for detoxification of arsenic contaminated natural water with value-added product generation.

Potential of biosorbent developed from fruit peel of Trewia nudiflora for removal of hexavalent chromium from synthetic and industrial effluent: Analyzing phytotoxicity in germinating Vigna seeds.

Chromium (VI) removal efficiency of a biosorbent prepared from fruit peel of Trewia nudiflora plant was studied. The effect of pH, sorbent dose, initial metal concentration and temperature was studied with synthetic Cr⁺6 solution in batch mode. About 278 mg/g of Cr⁺6 sorption was obtained at 293 K at an optimum pH of 2.0 and biosorbent dose of 0.75 g/L. Equilibrium sorption data with varying initial concentration of Cr⁺6 (22-248 mg/L) at three different temperatures (293-313 K) were analyzed by various isotherms. Biosorption kinetics and thermodynamics were described using standard model equations. Encouraging results were obtained by the application of the biosorptive treatment for removal of Cr⁺6 from wastewater collected from common effluent treatment plant of tannery industry. In addition, C⁺6r desorption behavior was studied on different systems. Biosorbent was characterized by FESEM, FT-IR and XRD, etc. Effect of the biosorptive treatement with respect to the phytotoxicity of Cr⁺6 was analyzed by studying the seed germination behavior and enzyme activity of a pulse seed (Vigna radiata L.). Different concentrations of Cr⁺6 solution in both synthetic medium, as well as, in tannery effluent was employed and the results were compared with that of biosorbent treated medium. The study showed that due to efficient removal of Cr⁺6 from aqueous phase, considerable enhancement of seed germination, as well as, increase in root length was obtained for the biosorbent treated solutions which were close to that of the control values. Significant decrease (P < 0.01) in POD activity was observed in seeds irrigated with biosorbent treated wastewater compared to untreated wastewater. The study showed that the novel biosorbent prepared might be utilized for abatement of heavy metal toxicity, i.e., Cr⁺6 from industrial effluent.

Treatment of textile dyehouse effluent using ceramic membrane based process in combination with chemical pretreatment.

Treatment of highly concentrated dyebath effluent and comparatively dilute composite effluent having mixture of various reactive dyes collected from a cotton fabric dyeing unit was undertaken in the present study. Ceramic microfiltration membrane prepared from a cost effective composition of alumina and clay was used. Prior to microfiltration, a chemical pretreatment was carried out with aluminium sulphate in combination with a polymeric retention aid. An optimum dose of 100 mg/L of aluminium sulphate and 1 ml/L of a commercial flocculant Afilan RAMF was found effective for dye removal (> 98%) from the synthetic solutions of reactive dyes with initial concentration of 150 mg/L in both the single component and two component systems. In the microfiltration study, effect of operating pressure in the permeate flux was observed for both the pretreated and untreated effluents and permeate samples were analyzed for dye concentration, COD, turbidity, TSS, etc. during constant pressure filtration. About 98-99% removal of dyes was obtained in the combined process with COD reduction of 54-64%.

As(III) oxidation by MnO2 coated PEEK-WC nanostructured capsules.

PEEK-WC nanostructured capsules were prepared by the phase inversion technique and used as support for the coating of a manganese dioxide layer. The coating was done by a chemical treatment of the capsules followed by a thermal one. The presence of the MnO(2) layer was confirmed by scanning electron microscopy (SEM), back scattering electron (BSE), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analysis. The produced capsules were, then, tested for As(III) oxidation in batch. The experiments consisted in treating 165 ml of As(III) solution with 1g of coated capsules at fixed temperature (15°C) and pH (5.7-5.8). In particular, the efficiency of the system was investigated for different As(III) concentrations (0.1, 0.3, 0.7 and 1 ppm). For feeds at lower As(III) content (0.1-0.3 ppm), tests lasted for 8h, while prolonged runs (up to 48 h) were carried out on more concentrated solutions (0.7 and 1 ppm). The produced capsules were able to oxidize As(III) into As(V) leading to complete conversion after 3 and 4h for feed concentrations of 0.1 and 0.3 ppm, respectively.