Management of tannery waste effluents towards the reclamation of clean water using an integrated membrane system: A state-of-the-art review.

Tanning and other leather processing methods utilize a large amount of freshwater, dyes, chemicals, and salts and produce toxic waste, raising questions regarding their environmental sensitivity and eco-friendly nature. Total suspended solids, total dissolved solids, chemical oxygen demand, and ions such as chromium, sulfate, and chloride turn tannery wastewater exceedingly toxic for any living species. Therefore, it is imperative to treat tannery effluent, and existing plants must be examined and upgraded to keep up with recent technological developments. Different conventional techniques to treat tannery wastewater have been reported based on their pollutant removal efficiencies, advantages, and disadvantages. Research on photo-assisted catalyst-enhanced deterioration has inferred that both homogeneous and heterogeneous catalysis can be established as green initiatives, the latter being more efficient at degrading organic pollutants. However, the scientific community experiences significant problems developing a feasible treatment technique owing to the long degradation times and low removal efficiency. Hence, there is a chance for an improved solution to the problem of treating tannery wastewater through the development of a hybrid technology that uses flocculation as the primary treatment, a unique integrated photo-catalyst in a precision-designed reactor as the secondary method, and finally, membrane-based tertiary treatment to recover the spent catalyst and reclaimable water. This review gives an understanding of the progressive advancement of a cutting-edge membrane-based system for the management of tanning industrial waste effluents towards the reclamation of clean water. Adaptable routes toward sludge disposal and the reviews on techno-economic assessments have been shown in detail, strengthening the scale-up confidence for implementing such innovative hybrid systems.

Arsenic Uptake and Accumulation in Okra (Abelmoschus esculentus) as Affected by Different Arsenical Speciation.

Experimental investigations were conducted to evaluate the toxic effects of different arsenic (As) species such as arsenite (As(III)), arsenate (As(V)) and dimethylarsinic acid (DMA) on the growth of okra (Abelmoschus esculentus). The present study describes the changes in the growth, yield and accumulation characteristics of okra plants spiked with 20 and 50 mg kg(-1) of As(III), As(V) and DMA. As species negatively affected the yield and growth of the plant.The availability of arsenic compounds in the aerial parts decreased in the order As(V) > As(III) > DMA and in the roots observed as As(III) > As(V) > DMA. The results showed that except As(V), okra accumulated As(III) and DMA mainly in its roots with limited transport to shoots. Thus the plant has the capacity to tolerate As stress and can be considered as a resistive variety. The study also reveals that removal of As by boiling the vegetables with excess of water is not possible.

Cyanide removal from industrial wastewater by cross-flow nanofiltration: transport modeling and economic evaluation.

A modeling and simulation study, along with an economic analysis, was carried out for the separation of cyanide from industrial wastewater using a flat sheet cross-flow nanofiltration membrane module. With the addition of a pre-microfiltration step, nanofiltration was carried out using real coke wastewater under different operating conditions. Under the optimum operating pressure of 13 bars and a pH of 10.0, a rate of more than 95% separation of cyanide was achieved. That model predictions agreed very well with the experimental findings, as is evident in the Willmott d-index value (> 0.95) and relative error (< 0.1). Studies were carried out with industrial wastewater instead of a synthetic solution, and an economic analysis was also done, considering the capacity of a running coking plant. The findings are likely to be very useful in the scale-up and design of industrial plants for the treatment of cyanide-bearing wastewater.

Membrane-integrated hybrid system for the effective treatment of ammoniacal wastewater of coke-making plant: a volume reduction approach.

Nanofiltration (NF) of ammoniacal wastewater containing phenol and cyanide has been investigated for effective separation of these hazardous pollutants and for the subsequent downstream chemical treatment resulting in valuable by-product generation. Four different types of composite polyamide commercial NF membranes (Sepro, USA) were tested under different operating conditions including transmembrane pressure and recovery rate (RR). At a transmembrane pressure of 15 bar, the achieved rejection of cyanide and phenol were 95% and 93%, respectively (concentrated stream) when the permeate contained 85% of ammonium-N. A high flux of 120 L m-2 h-1 was achieved during NF at a concentrated mode, with a volumetric cross-flow rate of 800 L h-1 at a pH of 10.0. The RR was 60% for the NF 1 membrane. Fenton's reagents (7.0 and 3.75 g L-1 H202 and FeSO4 . 7H20, respectively) were used to degrade more than 99% of pollutants present in the concentrated stream. In the permeate side, 97% of NH4+ -N was precipitated out as struvite by using Mg2+ : NH4 : PO+4 in 1:1:1 molar ratio at pH 9.0.

Removal of phenol from coke-oven wastewater by cross-flow nanofiltration membranes.

This study investigated the phenol rejection characteristics of some nanofiltration membranes during treatment of coke wastewater. Four different types of composite polyamide commercial nanofiltration membranes (Sepro, USA) were tested under different operating conditions including transmembrane pressure, pH and recovery rate. When pressure was increased from 4 to 16 bars, the percentage of rejection of phenol in the permeate increased from 72.5% to 97.7% while yielding a high flux of 118 litres per square meter per hour(LMH) at a volumetric cross flow rate of 800 litres per hour at pH 10 (in recirculation mode) in case of NF1 membrane. The effect of recovery rate on the rejection coefficient of phenol and flux was also studied in concentrated mode and found that a recovery rate of up 55% nanofiltration was successfully operated without much decline of flux and rejection coefficient. Finally, nanofiltration had great efficiency in phenol removal from industrial wastewater and was considered suitable regarding its operation.

A single functionalized graphene nanocomposite in cross flow module for removal of multiple toxic anionic contaminants from drinking water.

Polyether sulfone (PES)-based thin-film nanofiltration (TFN) membranes embedded with ferric hydroxide (FeIII(OH)x) functionalized graphene oxide (GO) nanoparticles were fabricated through interfacial polymerization for a generalized application in removal of a plethora of anionic and toxic water contaminants. Following the most relevant characterization, the newly synthesized membranes were fitted in a novel flat sheet cross-flow module, for experimental investigation on purification of live contaminated groundwater collected from different affected areas. The separation performances of the membranes in the flat sheet cross-flow module demonstrated that GOF membranes had higher selectivity for monovalent and divalent salt rejections than pristine GO membranes. Furthermore, both membranes were tested for simultaneously removing widely occurring hazardous ions of heavy metals and metalloids in groundwater, such as arsenic, selenium, chromium, and fluoride. Compared to the pristine GO and the reported membranes in the literature, the GOF membrane exhibited remarkable performance in terms of rejection efficiency (Cr (VI): 97.2%, Se (IV): 96.6%, As(V): 96.3%, F- 88.4%) and sustained flux of 184 LMH (Lm-2 h-1) at an optimum transmembrane pressure of 16 bar. The investigated membrane module equipped with the GOF membrane proved to be a low-cost system with higher anionic rejection and sustained high flux at a comprehensive pH range, as evident over long hours of study vis-à-vis reported systems.

A critical review on biogas production from edible and non-edible oil cakes.

The circular economy is at the core of sustainable development. The generation of biogas from the massive quantity of agricultural waste biomass is one of the critical drivers of the circular economy. Biogas has enormous renewable energy potential and has multitudes of applications in today's energy-intensive society. Oil cakes, a known Agri-waste, are the by-product of oil processing, and are rich in nutrients. The edible oil cakes mostly have been used as a cattle feed; however, non-edible oil cakes do not find many applications. Their production is continuously escalating as non-edible oils are increasingly used in biodiesel production. Recently, there is a lot of emphasis on biogas production from these oil cakes. This paper reviews in detail biogas production from both edible and non-edible oil cakes. Chemical composition and various other applications of the cakes are also reviewed in brief. The survey illustrates that multiple parameters such as inoculum sources, co-digestion and reactor design affect the biogas production. All those factors, along with biogas upgrading and the economy of the process, are reviewed. Finally, future research opportunities are suggested to improve the viability of the biogas production from oil cakes.

Feasibility assessment of bioethanol production from humic acid-assisted alkaline pretreated Kentucky bluegrass (Poa pratensis L.) followed by downstream enrichment using direct contact membrane distillation.

The effective fractionation of structural components of abundantly available lignocellulosic biomass is essential to unlock its full biorefinery potential. In this study, the feasibility of humic acid on the pretreatment of Kentucky bluegrass biomass in alkaline condition was assessed to separate 70.1% lignin and hydrolyzable biocomponents. The humic acid-assisted delignification followed by enzymatic saccharification yielded 0.55 g/g of reducing sugars from 7.5% (w/v) pretreated biomass loading and 16 FPU/g of cellulase. Yeast fermentation of the biomass hydrolysate produced 76.6% (w/w) ethanol, which was subsequently separated and concentrated using direct contact membrane distillation. The hydrophobic microporous flat-sheet membrane housed in a rectangular-shaped crossflow module and counter-current mode of flow of the feed (hot) and distillate (cold) streams yielded a flux of 11.6 kg EtOH/m2/24 h. A modular, compact, flexible, and eco-friendly membrane-integrated hybrid approach is used for the first time to effectively valorize Kentucky bluegrass biomass for sustainable production of biofuel.

Synergy of biofuel production with waste remediation along with value-added co-products recovery through microalgae cultivation: A review of membrane-integrated green approach.

Development of advanced biofuels such as bioethanol and biodiesel from renewable resources is critical for the earth's sustainable management and to slow down the global climate change by partial replacement of gasoline and diesel in the transport sector. Being a diverse group of aquatic micro-organisms, algae are the most prominent resources on the planet, distributed in an aquatic system, a potential source of bioenergy, biomass and secondary metabolites. Microalgae-based biofuel production is widely accepted as non-food fuel sources and better choice for achieving goals of incorporation of a clean fuel source into the transportation sector. The present review article provides a comprehensive literature survey as well as a novel approach on the application of microalgae for their simultaneous cultivation and bioremediation of high nutrient containing wastewater. In addition to that, merits and demerits of different existing conventional techniques for microalgae culture reactors, harvesting of algal biomass, oil recovery, use of different catalysts for transesterification reactions and other by-products recovery have been discussed and compared with the membrane-based system to find out the best optimal conditions for higher biomass as well as lipid yield. This article also deals with the use of a tailor-made membrane in an appropriate module that can be used in upstream and downstream processes during algal-based biofuels production. Such membrane-integrated system has the potential of low-cost and eco-friendly separation, purification and concentration enrichment of biodiesel as well as other valuable algal by-products which can bring the high degree of process intensification for scale-up at the industrial stage.

Purifying arsenic and fluoride-contaminated water by a novel graphene-based nanocomposite membrane of enhanced selectivity and sustained flux.

A novel graphene-based nanocomposite membrane was synthesized by interfacial polymerization (IP) through chemical bonding of the graphene oxide (GO) layer to polyethersulfone surface. Detailed characterization of the composite membrane through AFM, SEM, ATR-FTIR, XRD analysis, and Raman spectroscopy indicates strong potential of the membrane in highly selective removal of the toxic contaminants like arsenic and fluoride while permeating the essential minerals like calcium and magnesium. This makes the membrane suitable for production of safe drinking water from contaminated water. The membrane applied in a flat-sheet cross-flow module succeeded in removal of more than 98% arsenic and around 80% fluoride from contaminated water while selectively retaining the useful calcium and magnesium minerals in drinking water. A sustained pure water flux of around 150 LMH (liter per square meter per hour) during operation over long hours (> 150 h) with only 3-5% drop in flux indicates antifouling character of the membrane module.

Removal of arsenic from drinking water by chemical precipitation--a modeling and simulation study of the physical-chemical processes.

A dynamic mathematical model was developed for removal of arsenic from drinking water by chemical coagulation-precipitation and was validated experimentally in a bench-scale set-up. While examining arsenic removal efficiency of the scheme under different operating conditions, coagulant dose, pH and degree of oxidation were found to have pronounced impact. Removal efficiency of 91-92% was achieved for synthetic feed water spiked with 1 mg/L arsenic and pre-oxidized by potassium permanganate at optimum pH and coagulant dose. Model predictions corroborated well with the experimental findings (the overall correlation coefficient being 0.9895) indicating the capability of the model in predicting performance of such a treatment plant under different operating conditions. Menu-driven, user-friendly Visual Basic software developed in the study will be very handy in quick performance analysis. The simulation is expected to be very useful in full-scale design and operation of the treatment plants for removal of arsenic from drinking water.

A flux-enhancing forward osmosis-nanofiltration integrated treatment system for the tannery wastewater reclamation.

Effective treatment of tannery wastewater prior to discharge to the environment as per environmental regulations remains a big challenge despite efforts to bring down the concentrations of the pollutants which are often quite high as measured in terms of chemical oxygen demand (7800 mg/L), total dissolved solids (5400 mg/L), chloride (4260 mg/L), sulphides (250 mg/L) and chromium. A pilot-scale forward osmosis and nanofiltration integrated closed loop system was developed for continuous reclamation of clean water from tannery wastewater at a rate of 52-55 L/m2/h at 1.6 bar pressure. The low-cost draw solution was 0.8 M NaCl solution. Continuous recovery for recycling the draw solute was done by nanofiltration of diluted draw solution at an operating pressure of 12 bar and volumetric cross-flow rate of 700 L/h. Fouling study revealed that the specific flat-sheet design of cross-flow forward osmosis module with counter current flow of feed and draw solution prevents the build-up of concentration polarization, thus enabling long-term filtration in continuous mode of operation without significant membrane fouling. This study culminates in the development of a compact, efficient and low-cost industrial wastewater treatment and reclamation technology.

Performance analysis and optimization of an advanced pharmaceutical wastewater treatment plant through a visual basic software tool (PWWT.VB).

A user-friendly, menu-driven simulation software tool has been developed for the first time to optimize and analyze the system performance of an advanced continuous membrane-integrated pharmaceutical wastewater treatment plant. The software allows pre-analysis and manipulation of input data which helps in optimization and shows the software performance visually on a graphical platform. Moreover, the software helps the user to "visualize" the effects of the operating parameters through its model-predicted output profiles. The software is based on a dynamic mathematical model, developed for a systematically integrated forward osmosis-nanofiltration process for removal of toxic organic compounds from pharmaceutical wastewater. The model-predicted values have been observed to corroborate well with the extensive experimental investigations which were found to be consistent under varying operating conditions like operating pressure, operating flow rate, and draw solute concentration. Low values of the relative error (RE = 0.09) and high values of Willmott-d-index (d will = 0.981) reflected a high degree of accuracy and reliability of the software. This software is likely to be a very efficient tool for system design or simulation of an advanced membrane-integrated treatment plant for hazardous wastewater.

Dynamic modelling of a forward osmosis-nanofiltration integrated process for treating hazardous wastewater.

Dynamic modelling and simulation of a nanofiltration-forward osmosis integrated complete system was done along with economic evaluation to pave the way for scale up of such a system for treating hazardous pharmaceutical wastes. The system operated in a closed loop not only protects surface water from the onslaught of hazardous industrial wastewater but also saves on cost of fresh water by turning wastewater recyclable at affordable price. The success of dynamic modelling in capturing the relevant transport phenomena is well reflected in high overall correlation coefficient value (R 2 > 0.98), low relative error (<0.1) and Willmott d-index (<0.95). The system could remove more than 97.5 % chemical oxygen demand (COD) from real pharmaceutical wastewater having initial COD value as high as 3500 mg/L while ensuring operation of the forward osmosis loop at a reasonably high flux of 56-58 l per square meter per hour.

Assessing the feasibility of N and P recovery by struvite precipitation from nutrient-rich wastewater: a review.

Literature on recovery of nitrogen and phosphorous from wastewater in the form of value-added struvite fertilizer has been critically reviewed towards the evolution of a sustainable management strategy. Presence of nitrogen and phosphorus is widespread in both domestic as well as industrial wastewater streams such as swine wastewater, landfill leachate, urine waste, dairy manure, coke wastewater, and beverage wastewater. Where these nitrogen and phosphorus compounds cause eutrophication of water bodies and considered as harmful discharges to the environment, they can be turned useful through simple chemical conversion into struvite (MgNH4PO4·6H2O). In extensive studies on wastewater treatment, aspects of recovery of valuable materials remain dispersed. In the present article, almost all relevant aspects of sources of raw materials, chemistry and technology of struvite production, and its detailed characterization have been captured in a systematic and classified way so as to help in planning and designing an integrated scheme of struvite production through conversion of nitrogen and phosphorus components of waste streams. The study will help in formulating a new waste management strategy in this context by shifting focus from removal to recovery of nutrients from waste streams.

Fermentative production of poly (γ-glutamic acid) from renewable carbon source and downstream purification through a continuous membrane-integrated hybrid process.

Experimental investigations were carried out on continuous and direct production of poly-(γ-glutamic acid) in a hybrid reactor system that integrated conventional fermentative production step with membrane-based downstream separation and purification. Novelty of the integrated system lies in high degree of purity, conversion, yield and productivity of poly-(γ-glutamic acid) through elimination of substrate-product inhibitions of traditional batch production system. This new system is compact, flexible, eco-friendly and largely fouling-free ensuring steady and continuous production of poly-(γ-glutamic acid) directly from a renewable carbon source at the rate of 0.91 g/L/h. Cross-flow microfiltration membrane modules ensured almost complete separation and recycle of cells without much fouling problem. Well-screened ultrafiltration membrane module helped to concentrate poly-(γ-glutamic acid) while ensuring recovery and recycle of 96% unconverted carbon source resulting in yield of 0.6g/g along with high product purity.

Membrane-integrated physico-chemical treatment of coke-oven wastewater: transport modelling and economic evaluation.

A modelling and simulation study with economic evaluation was carried out for an advanced membrane-integrated hybrid treatment process that ensures reuse of water with recovery of ammoniacal nitrogen as struvite from coke-oven wastewater. Linearized transport model was developed based on extended Nernst-Plank and concentration polarization modulus equation. Effects of pH, transmembrane pressure and cross-flow rate of interest on membrane charge density, solute rejection and solvent flux were investigated. The membrane module was successful in yielding a pure water flux as high as 120 L m(-2) h(-1) removing more than 95 and 96% of the cyanide and phenol, respectively, while permeating more than 90% NH4 (+)-N at a transmembrane pressure of only 15 × 10(2) KPa and at a pH of 10 for a volumetric cross-flow rate of 800 L h(-1). The Fenton's reagents were used to degrade more than 99% of pollutants present in the concentrated stream. The developed model could successfully predict the plant performance as reflected in the very low relative error (0.01-0.12) and overall high correlation coefficient (R(2) > 0.96). Economic analysis indicated that such a membrane-integrated hybrid system could be quite promising in coke wastewater treatment at low cost i.e. $0.934/m(2) of wastewater.

Purifying fluoride-contaminated water by a novel forward osmosis design with enhanced flux under reduced concentration polarization.

For purifying fluoride-contaminated water, a new forward osmosis scheme in horizontal flat-sheet cross flow module was designed and investigated. Effects of pressure, cross flow rate, draw solution and alignment of membrane module on separation and flux were studied. Concentration polarization and reverse salt diffusion got significantly reduced in the new hydrodynamic regime. This resulted in less membrane fouling, better solute separation and higher pure water flux than in a conventional module. The entire scheme was completed in two stages-an upstream forward osmosis for separating pure water from contaminated water and a downstream nanofiltration operation for continuous recovery and recycle of draw solute. Synchronization of these two stages of operation resulted in a continuous, steady-state process. From a set of commercial membranes, two polyamide composite membranes were screened out for the upstream and downstream filtrations. A 0.3-M NaCl solution was found to be the best one for forward osmosis draw solution. Potable water with less than 1% residual fluoride could be produced at a high flux of 60-62 L m(-2) h(-1) whereas more than 99% draw solute could be recovered and recycled in the downstream nanofiltration stage from where flux was 62-65 L m(-2) h(-1).

Investigations on the antiretroviral activity of carbon nanotubes using computational molecular approach.

Carbon nanotubes are the interesting class of materials with wide range of applications. They have excellent physical, chemical and electrical properties. Numerous reports were made on the antiviral activities of carbon nanotubes. However the mechanism of antiviral action is still in infancy. Herein we report, our recent novel findings on the molecular interactions of carbon nanotubes with the three key target proteins of HIV using computational chemistry approach. Armchair, chiral and zigzag CNTs were modeled and used as ligands for the interaction studies. The structure of the key proteins involved in HIV mediated infection namely HIV- Vpr, Nef and Gag proteins were collected from the PDB database. The docking studies were performed to quantify the interaction of the CNT with the three different disease targets. Results showed that the carbon nanotubes had high binding affinity to these proteins which confirms the antagonistic molecular interaction of carbon nanotubes to the disease targets. The modeled armchair carbon nanotubes had the binding affinities of -12.4 Kcal/mole, -20 Kcal/mole and -11.7 Kcal/mole with the Vpr, Nef and Gag proteins of HIV. Chiral CNTs also had the maximum affinity of -16.4 Kcal/mole to Nef. The binding affinity of chiral CNTs to Vpr and Gag was found to be -10.9 Kcal/mole and -10.3 Kcal/mole respectively. The zigzag CNTs had the binding affinity of -11.1 Kcal/mole with Vpr, -18.3 Kcal/mole with Nef and -10.9 with Gag respectively. The strong molecular interactions suggest the efficacy of CNTs for targeting the HIV mediated retroviral infections.

A membrane-integrated advanced scheme for treatment of industrial wastewater: dynamic modeling towards scale up.

Modeling and simulation was carried out for an advanced membrane-integrated hybrid treatment process that ensures reuse of water with conversion and recovery of ammoniacal nitrogen as value-added struvite fertilizer from coke wastewater. While toxic cyanide was largely removed in a pre-chemical treatment unit using Fenton's reagents under optimized conditions, more than 95% of NH4(+)-N could be recovered as a valuable by-product called struvite through addition of appropriate doses of magnesium and phosphate salts. Water could be turned reusable through a polishing treatment by nanofiltration membranes in a largely fouling free membrane module following a biodegradation step. Mathematical modeling of such an integrated process was done with Haldane-Andrew approach for the associated microbial degradation of phenol by Pseudomonas putida. Residual NH4(+) was degraded by nitrification and denitrification following the modified Monod kinetics. The model could successfully predict the plant performance as reflected in reasonably low relative error (0.03-0.18) and high Willmott d-index (>0.98).