Efficient removal of mercury (II) from water by use of cryogels and comparison to commercial adsorbents under environmentally relevant conditions.

Mercury is a toxic element, which can be found in air, water and soil in several inorganic and organic forms. Mercury pollution comes from a variety of industrial sources, including vinyl-chloride, pulp and paper, fertilizers and pharmaceuticals industry, gold mining and cement production. Gels have increasingly attracted the interest over the past decades and one of the investigated applications is the fast removal of organic substances, metals and other cations and anions from water. In this work, two types of cryogels were synthesized at sub-zero temperature by free-radical polymerization technique, characterized by using a set of complimentary methods and used for the removal of mercury from aqueous solutions of different chemistry. Kinetics and equilibrium studies were performed in ultra-pure water solutions in order to study the mechanisms in the presence nitrate and chloride ions. The cryogels exhibited excellent efficiency towards mercury removal from all model solutions. Moreover, the cryogels were tested in different water matrixes (tap, river and sea water) and compared to commercial adsorbents (activated carbon, strong acid resin and zeolite Y). Cryogels were able to remove mercury much faster than commercial adsorbents with the exception of seawater where activated carbon was superior.

Experimental study of zeolitic diffusion by use of a concentration-dependent surface diffusion model.

Surface diffusivity in adsorption and ion exchange processes is probably the most important property studied expensively in the literature but some aspects, especially its dependence on solid phase concentration, is still an open subject to discussion. In this study a new concentration-dependent surface diffusion model, equipped with a flexible double selectivity equilibrium relationship is applied on the removal of Pb2+, Cr3+, Fe3+ and Cu2+ from aqueous solutions using a natural zeolite. The model incorporates the Chen-Yang surface diffusivity correlation able to deal with positive and negative dependence with surface coverage. The double selectivity equilibrium relationship successfully represents the experimental equilibrium data, which follow Langmurian isotherm type for Pb2+, sigmoidal for Cr3+ and Fe3+ and linear for Cu2+. The concentration-dependent surface diffusion model was compared with the constant diffusivity surface diffusion model and found to be moderately more accurate but considerably more useful as it provides more insights into the diffusion mechanism. The application of the model resulted in an average deviation of 8.56 ± 6.74% from the experimental data and an average solid phase diffusion coefficients between 10-9 and 10-10 cm2/s. The results showed that the diffusion of metal ions in the zeolite structure is unhindered following the surface diffusion mass transfer mechanism.

Removal of iodide from water using silver nanoparticles-impregnated synthetic zeolites.

Synthetic zeolite-based Ag-nanocomposites were synthesized, characterized and used to remove iodide from aqueous solutions. The results showed high removal efficiency (up to 94.85%) and the formation silver iodide which is stable into the material. The maximum achieved adsorption capacity of the nanocomposites was between 19.54 and 20.44mg/g. The removal mechanism was meticulously studied by taking into account both water chemistry and surface interactions backed by multiple characterization techniques, such as XRD, XRF, SEM/EDX, TEM and BET. The qualitative and quantitative examination of pre- and post-adsorption of nanocomposite samples proved that the anchored silver iodide was formed via oxidation of initial silver nanoparticles followed by reaction with iodide to form a stable crystalline precipitate on the surface of the materials. A diffusion-based adsorption model indicated that the controlling mechanism is a slow intraparticle surface diffusion with diffusion coefficients in the range of 0.37-1.72×10-13cm2/s. The investigation of competing and co-existing anions (Cl-, Br-, CO32-, and CrO42-) on the removal efficiency of iodide demonstrated a negligible effect showing a kinetically favorable precipitation reaction of iodide over other anions.

Synthetic sodalite doped with silver nanoparticles: Characterization and mercury (II) removal from aqueous solutions.

In this work, a novel silver nanoparticles-doped synthetic sodalitic composite was synthesized and characterized using advanced characterization methods, namely TEM-EDS, XRD, SEM, XRF, BET, zeta potential, and particle size analysis. The synthesized nanocomposite was used for the removal of Hg2+ from 10 ppm aqueous solutions of initial pH equal to 2. The results showed that the sodalitic nanocomposites removed up to 98.65% of Hg2+, which is ∼16% and 70% higher than the removal achieved by sodalite and parent coal fly ash, respectively. The findings revealed that the Hg2+ removal mechanism is a multifaceted mechanism that predominantly involves adsorption, precipitation and Hg-Ag amalgamation. The study of the anions effect (Cl-, NO3-, C2H3O2-, and SO42-) indicated that the Hg2+ uptake is comparatively higher when Cl- anions co-exist with Hg2+ in the solution.

Variable diffusivity homogeneous surface diffusion model and analysis of merits and fallacies of simplified adsorption kinetics equations.

Adsorption and ion exchange phenomena are encountered in several separation processes, which in turn, are of vital importance across various industries. Although the literature on adsorption kinetics modeling is rich, the majority of the models employed are empirical, based on chemical reaction kinetics or oversimplified versions of diffusion models. In this paper, the fifteen most popular simplified adsorption kinetics equations are presented and discussed. A new versatile variable-diffusivity two-phase homogeneous diffusion model is presented and used to evaluate the analytical adsorption models. Aspects of ion exchange kinetics are also addressed.

Comparative environmental assessment of alternative waste management strategies in developing regions: A case study in Kazakhstan.

The management of municipal solid waste in the Republic of Kazakhstan is still in its infancy. This situation poses a potential threat to the environment and public health and, therefore, it is necessary to introduce improved management schemes in the country. In this study, the life cycle assessment methodology was followed to evaluate the potential environmental benefits of implementing alternative management schemes based on low-waste generation and renewable energy production. The current situation of the capital city Astana was considered as the base case. Environmental results showed that air emissions in terms of landfill gases are the major contributor to climate change impacts, while landfill disposal of the non-recovered fraction of recyclable materials was responsible for the highest impacts in the other categories (especially land use). However, the reuse of recycled materials largely offsets the related environmental burdens, along with energy generation. In comparative terms, it was demonstrated that the proposed waste management scenarios are more environmentally friendly than current practices (S0), mainly owing to the credits associated with the valorisation of renewable energy (S2) and recovered materials (S3). Consequently, the evaluation showed that greater efforts should be made to exploit the energy potential of organic fraction, together with higher recycling rates, to move towards lower environmental impacts associated with municipal solid waste management.

Synthetic coal fly ash-derived zeolites doped with silver nanoparticles for mercury (II) removal from water.

Coal fly ash-derived zeolites have attracted considerable interest in the last decade due to their use in several environmental applications such as the removal of dyes and heavy metals from aqueous solutions. In this work, coal fly ash-derived zeolites and silver nanoparticles-impregnated zeolites (nanocomposites) were synthesized and characterized by TEM/EDX, SEM/EDX, XRD, XRF, porosimetry (BET), particle size analysis (PSA) and zeta potential measurements. The synthesized materials were used for the removal of Hg2+ from aqueous solutions. The results demonstrated that nanocomposites can remove 99% of Hg2+, up to 10% and 90% higher than the removal achieved by the zeolite and the parent fly ash, respectively. Leaching studies further demonstrated the superiority of the nanocomposite over the parent materials. The Hg2+ removal mechanism is complex, involving adsorption, surface precipitation and amalgamation.

Investigating the inhibitory effect of cyanide, phenol and 4-nitrophenol on the activated sludge process employed for the treatment of petroleum wastewater.

In this work, the inhibitory effect of cyanide, phenol and 4-nitrophenol on the activated sludge process was investigated. The inhibition of the aerobic oxidation of organic matter, nitrification and denitrification were examined in batch reactors by measuring the specific oxygen uptake rate (sOUR), the specific ammonium uptake rate (sAUR) and the specific nitrogen uptake rate (sNUR) respectively. The tested cyanide, phenol and 4-nitrophenol concentrations were 0.2-1.7 mg/L, 4.8-73.1 mg/L and 8.2-73.0 mg/L respectively. Cyanide was highly toxic as it significantly (>50%) inhibited the activity of autotrophic biomass, heterotrophic biomass under aerobic conditions and denitrifiers even at relatively low concentrations (1.0-1.7 mgCN-/L). The determination of the half maximum inhibitory concentration (IC50) confirmed this, since for cyanide IC50 values were very low for the examined bioprocesses (<1.5 mg/L). On the other hand, the IC50 values for phenol and 4-nitrophenol were much higher (>25 mg/L) for the tested bioprocesses since appreciable concentrations were required to accomplish significant inhibition. The autotrophic bacteria were more sensitive to phenol than the aerobic heterotrophs. The denitrifiers were found to be very resistant to phenol.

Effects of operating conditions on the removal of heavy metals by zeolite in fixed bed reactors.

This work investigates the effects of flow rate (5-15 Bed Volumes/h), particle size (0.8-1.7 mm), concentration (0.005-0.02 N) and Na(+)-enrichment of natural clinoptilolite on the removal efficiency of Pb2+, Cu2+, Fe3+ and Cr3+ in aqueous solutions. Ion exchange is performed in an upflow fixed bed reactor. The removal efficiency is increased with decreasing flow rate, particle size and concentration and is improved by a factor of 2-10, depending on the specific metal. The modification of the natural sample is favorable, leading to an increase of removal efficiency by 32-100%. For the experimental conditions examined, removal efficiency order is the following: Pb2+ > Cr3+ > Fe3+ > or = Cu2+. Finally, the operation is influenced by the studied parameters, following the order: concentration > volumetric flow > rate > particle size > modification of the material.

Studies on the pretreatment of zeolite clinoptilolite in packed beds.

The effect of volumetric flow rate, ranging from 5 to 45 Bed Volumes per hour (BV h(-1)) and temperature, ranging from 25 to 59 degrees C, during pretreatment of clinoptilolite on its effective capacity has been investigated. Pretreatment tests have been performed in an upflow ion exchange bed. Increased temperatures were found to increase the effective capacity of clinoptilolite. Effective capacity was maximal at low volumetric flow rates, indicating an influence of contact time and complete saturation of the zeolite bed at flow rates lower than 10 BV h(-1). Furthermore, a comparison between upflow and downflow operation at the same operating conditions showed that better results are obtained in upflow conditions, probably due to the better wetting of the material and the absence of liquid maldistribution.

Equilibrium and kinetic ion exchange studies of Pb2+, Cr3+, Fe3+ and Cu2+ on natural clinoptilolite.

In the present study ion exchange of Pb2+, Cu2+, Fe3+ and Cr3+ on natural clinoptilolite is examined at 27 +/- 1 degree C and initial concentration of 10 meq/dm3. Equilibrium is favorable for Pb2+, unfavorable for Cu2+ and sigmoid for Cr3+ and Fe3+. Selectivity series deduced from equilibrium isotherms is Pb2+ > Cr3+ > Fe3+ > Cu2+, while when maximum exchange levels (MELs) are considered, selectivity series is Pb2+ > Cr3+ approximately = Cu2+ > or = Fe3+. Cu2+ manifests the higher value of diffusion coefficient in the clinoptilolite particles among the metals studied, equal to 1.40 x 10(-9) cm2/s. According to the fixed bed experiments the upflow rate (5-15 Bed Volumes (BV)) is influencing the breakthrough point for all metals studied. The breakthrough point varies between 12.3 BV for Pb2+ and 1.18 for Cu2+. Flow rate is also influencing the operating capacity, giving values between 0.433 meq/g(clinoptilolite) for Pb2+ and 0.053 for Fe3+. Breakthrough point values confirm the selectivity order deduced from the equilibrium isotherms, while operating capacity values confirm the selectivity order deduced from MEL experiments.

Pretreatment of natural clinoptilolite in a laboratory-scale ion exchange packed bed.

The impact of the operational and chemical conditions of pretreatment upon the effective capacity of clinoptilolite has been investigated. Pretreatment tests have been performed in an ion exchange packed bed. The parameters examined for the pretreatment solution were the volumetric flow rate, the concentration, the total volume and the pH; and for washing after pretreatment the volume of washing water used. An optimal flow rate and a minimum concentration were determined, for a pretreatment that leads to a high effective capacity of the material, while pH adjustment did not result in a higher effective capacity and one washing (10 bed volumes) after pretreatment was found to be sufficient. Furthermore, the water quality (use of tap water) as well as the surface dust of the original material (about 5% w/w) did not alter its effective capacity.

Effects of pretreatment on physical and ion exchange properties of natural clinoptilolite.

Four pretreatment procedures have been applied to natural clinoptilolite to establish the influence of the pretreatment process on the properties of the material under investigation. Modification of material properties is imposed for its use in wastewater treatment via ion exchange processes. Batch pretreatment procedures as well as continuous flow column have been studied by using sodium chloride, sodium hydroxide and nitric acid solutions in deionized water. Measurements of the effective capacity, the diffusion coefficient in the solid state and examination of the crystal structure have been employed to assess the effect of each specific pretreatment on the material under test. The effective capacity is improved in all cases, by a factor of 2.4 to 3.6, while the diffusion coefficient values depend strongly on the type of pretreatment used and fall in the range of 0.03-1.37 x 10(-8) cm2s-2 at 20 degrees C. The crystal structure remains unaltered as evidenced by XRD measurements.