Evina Katsou

A review on zinc and nickel adsorption on natural and modified zeolite, bentonite and vermiculite: Examination of process parameters, kinetics and isotherms

Adsorption and ion exchange can be effectively employed for the treatment of metal-contaminated wastewater streams. The use of low-cost materials as sorbents increases the competitive advantage of the process. Natural and modified minerals have been extensively employed for the removal of nickel and zinc from water and wastewater. This work critically reviews existing knowledge and research on the uptake of nickel and zinc by natural and modified zeolite, bentonite and vermiculite. It focuses on the examination of different parameters affecting the process, system kinetics and equilibrium conditions. The process parameters under investigation are the initial metal concentration, ionic strength, solution pH, adsorbent type, grain size and concentration, temperature, agitation speed, presence of competing ions in the solution and type of adsorbate. The systems performance is evaluated with respect to the overall metal removal and the adsorption capacity. Furthermore, research works comparing the process kinetics with existing reaction kinetic and diffusion models are reviewed as well as works examining the performance of isotherm models against the experimental equilibrium data.

Industrial wastewater pre-treatment for heavy metal reduction by employing a sorbent-assisted ultrafiltration system

This work examined the adoption of a sorbent-assisted ultrafiltration (UF) system for the reduction of Pb(II), Cu(II), Zn(II) and Ni(II) from industrial wastewater. In such a system metals were removed via several processes which included precipitation through the formation of hydroxides, formation of precipitates/complexes among the metal ions and the wastewater compounds, adsorption of metals onto minerals (bentonite, zeolite, vermiculite) and retention of insoluble metal species by the UF membranes. At pH=6 the metal removal sequence obtained by the UF system was Pb(II)>Cu(II)>Zn(II)>Ni(II) in mg g⁻¹ with significant amount of lead and copper being removed due to chemical precipitation and formation of precipitates/complexes with wastewater compounds. At this pH, zinc and nickel adsorption onto minerals was significant, particularly when bentonite and vermiculite were employed as adsorbents. Metal adsorption onto zeolite and bentonite followed the sequence Zn(II)>Ni(II)>Cu(II)>Pb(II), while for vermiculite the sequence was Ni(II)>Zn(II)>Cu(II)>Pb(II) in mg g⁻¹. The low amount of Pb(II) and Cu(II) adsorbed by minerals was attributed to the low available lead and copper concentration. At pH=9 the adoption of UF could effectively reduce heavy metals to very low levels. The same was observed at pH=8, provided that minerals were added. The prevailing metal removal process was the formation of precipitates/complexes with wastewater compounds.

Regeneration of natural zeolite polluted by lead and zinc in wastewater treatment systems

The aim of this work was to investigate the potential regeneration of natural zeolite which had been contaminated with lead and zinc contained in aqueous solutions, treated secondary effluent and primary treated wastewater. Several desorbing solutions were examined for the removal of Pb(II) and Zn(II) from zeolite and the highest desorption efficiency was obtained for 3M KCl and 1M KCl, respectively. The desorption process depended on the type and concentration of the desorbing solution, the metal being desorbed, the mineral selectivity towards the metal and the composition of the liquid medium where the adsorption process had taken place. Successive regeneration cycles resulted in the reduction of desorption efficiency by more than 50% after 9 and 4 cycles for lead and zinc, respectively. Kinetics examination showed that desorption was slower than adsorption, while metal ions which had been easily adsorbed were difficult to be desorbed. Adsorption was characterized by a three-stage diffusion process, while desorption followed a two-stage diffusion process.

Performance of a membrane bioreactor used for the treatment of wastewater contaminated with heavy metals

In this work the performance of a Membrane bioreactor (MBR) was assessed for the removal of 3-15 mg/l of copper, lead, nickel and zinc from wastewater. The average removal efficiencies accomplished by the MBR system were 80% for Cu(II), 98% for Pb(II), 50% for Ni(II) and 77% for Zn(II). The addition of 5 g/l vermiculite into the biological reactor enhanced metal removal to 88% for copper, 85% for zinc and 60% for nickel due to adsorption of metal ions on the mineral, while it reduced biomass inhibition and increased biomass growth. The metal ions remaining in soluble form penetrated into the permeate, while those attached to sludge flocs were effectively retained by the ultrafiltration membranes. The average heterotrophic biomass inhibition was 50%, while it reduced to 29% when lower metal concentrations were fed into the reactor in the presence of vermiculite. The respective autotrophic biomass inhibition was 70% and 36%. The presence of heavy metals and vermiculite in the mixed liquor adversely impacted on membrane fouling.

Assessment of metal removal, biomass activity and RO concentrate treatment in an MBR–RO system

This work investigated the removal of metals from wastewater using a combined Membrane Bioreactor-Reverse Osmosis (MBR-RO) system. The concentrate produced by the RO system was treated by a fixed bed column packed with zeolite. The average metal removal accomplished by the MBR treating municipal wastewater was Cu(90%), Fe(85%), Mn(82%), Cr(80%), Zn(75%), Pb(73%), Ni(67%), Mg(61%), Ca(57%), Na(30%) and K(21%), with trivalent and divalent metals being more effectively removed than monovalent ones. The metal removal achieved by the MBR system treating wastewater spiked with Cu, Pb, Ni and Zn (4-12 mg L(-1) of each metal) was Pb(96%)>Cu(85%)>Zn(78%)>Ni(48%). The combined MBR-RO system enhanced metal removal from municipal wastewater to the levels of >90.9->99.8%, while for wastewater spiked with heavy metals the removal efficiencies were >98.4%. Fixed bed column packed with zeolite was effective for the removal of Cu, Pb and Zn from the RO concentrate, while Ni removal was satisfactory only at the initial stages of column operation. The presence of heavy metals increased inorganic fouling.

A review on nitrous oxide (N2O) emissions during biological nutrient removal from municipal wastewater and sludge reject water

Nitrous oxide (N2O) is an important pollutant which is emitted during the biological nutrient removal (BNR) processes of wastewater treatment. Since it has a greenhouse effect which is 265 times higher than carbon dioxide, even relatively small amounts can result in a significant carbon footprint. Biological nitrogen (N) removal conventionally occurs with nitrification/denitrification, yet also through advanced processes such as nitritation/denitritation and completely autotrophic N-removal. The microbial pathways leading to the N2O emission include hydroxylamine oxidation and nitrifier denitrification, both activated by ammonia oxidizing bacteria, and heterotrophic denitrification. In this work, a critical review of the existing literature on N2O emissions during BNR is presented focusing on the most contributing parameters. Various factors increasing the N2O emissions either per se or combined are identified: low dissolved oxygen, high nitrite accumulation, low chemical oxygen demand to nitrogen ratio, slow growth of denitrifying bacteria, uncontrolled pH and temperature. However, there is no common pattern in reporting the N2O generation amongst the cited studies, a fact that complicates its evaluation. When simulating N2O emissions, all microbial pathways along with the potential contribution of abiotic N2O production during wastewater treatment at different dissolved oxygen/nitrite levels should be considered. The undeniable validation of the robustness of such models calls for reliable quantification techniques which simultaneously describe dissolved and gaseous N2O dynamics. Thus, the choice of the N-removal process, the optimal selection of operational parameters and the establishment of validated dynamic models combining multiple N2O pathways are essential for studying the emissions mitigation.

Biological nutrients removal from the supernatant originating from the anaerobic digestion of the organic fraction of municipal solid waste

Abstract This study critically evaluates the biological processes and techniques applied to remove nitrogen and phosphorus from the anaerobic supernatant produced from the treatment of the organic fraction of municipal solid waste (OFMSW) and from its co-digestion with other biodegradable organic waste (BOW) streams. The wide application of anaerobic digestion for the treatment of several organic waste streams results in the production of high quantities of anaerobic effluents. Such effluents are characterized by high nutrient content, because organic and particulate nitrogen and phosphorus are hydrolyzed in the anaerobic digestion process. Consequently, adequate post-treatment is required in order to comply with the existing land application and discharge legislation in the European Union countries. This may include physicochemical and biological processes, with the latter being more advantageous due to their lower cost. Nitrogen removal is accomplished through the conventional nitrification/denitrification, nitritation/denitritation and the complete autotrophic nitrogen removal process; the latter is accomplished by nitritation coupled with the anoxic ammonium oxidation process. As anaerobic digestion effluents are characterized by low COD/TKN ratio, conventional denitrification/nitrification is not an attractive option; short-cut nitrogen removal processes are more promising. Both suspended and attached growth processes have been employed to treat the anaerobic supernatant. Specifically, the sequencing batch reactor, the membrane bioreactor, the conventional activated sludge and the moving bed biofilm reactor processes have been investigated. Physicochemical phosphorus removal via struvite precipitation has been extensively examined. Enhanced biological phosphorus removal from the anaerobic supernatant can take place through the sequencing anaerobic/aerobic process. More recently, denitrifying phosphorus removal via nitrite or nitrate has been explored. The removal of phosphorus from the anaerobic supernatant of OFMSW is an interesting research topic that has not yet been explored. At the moment, standardization in the design of facilities that treat anaerobic supernatant produced from the treatment of OFMSW is still under development. To move toward this direction, it is first necessary to assess the performance of alternative treatment options. It study concentrates existing data regarding the characteristics of the anaerobic supernatant produced from the treatment of OFMSW and from their co-digestion with other BOW. This provides data documenting the effect of the anaerobic digestion operating conditions on the supernatant quality and critically evaluates alternative options for the post-treatment of the liquid fraction produced from the anaerobic digestion process.

Examination of zinc uptake in a combined system using sludge, minerals and ultrafiltration membranes.

This work investigates the feasibility of zinc removal from wastewater with the use of ultrafiltration (UF) membranes combined with natural minerals and sludge. Activated sludge obtained from a membrane bioreactor (MBR) was enriched with initial zinc concentration of 320 mg/L and specific concentrations of zeolite, bentonite and vermiculite. The mixture was agitated and placed inside a batch ultrafiltration unit where the filtration process took place. The effect of several parameters on zinc removal was investigated including the mineral type, quantity and grain size, the metal-mineral contact time and the associated kinetics, the pH value, the zinc initial concentration and sludge mixed liquor suspended solids (MLSS) concentration. The ultrafiltration membranes without any mineral addition were able to remove 38-78% of zinc ions due to biosorption on sludge flocs. The addition of minerals increased the Zn(II) removal efficiencies reaching in some cases more than 90%. Bentonite was the most effective mineral in zinc removal followed by vermiculite. Alkaline pH values favoured zinc removal due to enhanced chemical precipitation. A three-stage adsorption process was identified where the boundary layer diffusion process was followed by a two-stage intraparticle diffusion process. Powder size vermiculite was more effective than granular vermiculite in zinc removal. Minerals also resulted in membrane fouling mitigation since the membrane permeability drop was reduced. The combined sludge-mineral-ultrafiltration system can be effectively employed for the treatment of industrial wastewater.

Copper removal from sludge permeate with ultrafiltration membranes using zeolite, bentonite and vermiculite as adsorbents

The aim of this work is to examine copper removal from sludge permeate with the use of low-cost minerals of Mediterranean origin combined with ultrafiltration membranes. The minerals used were zeolite (clinoptilolite), bentonite and vermiculite. Activated sludge was enriched with 0.01 N (317.7 ppm) of Cu(II). Fixed concentrations of minerals were added to sludge and the pH value was adjusted at 5.5. The mixture was agitated for 2 hours at 800 rpm at room temperature and was then filtered through a batch ultrafiltration system for 1 hour. This experiment was repeated, for comparison purposes, with sludge enriched with 0.01 N of Cu(II) with no mineral addition. The results showed that ultrafiltration membranes with no mineral addition were able to remove a significant amount of copper with removal efficiencies ranging from 59.4-78.3%. The addition of 10 g/l and 20 g/l of bentonite combined with ultrafiltration membranes resulted in removal efficiencies of 94.9% and 99.4% respectively and that of 10 g/l and 20 g/l of vermiculite in removal efficiencies of 93.8% and 96.8%, respectively. The ion exchange capacity of minerals followed the order bentonite > vermiculite > zeolite. Furthermore, membrane fouling was investigated. The addition of zeolite and bentonite reduced membrane fouling, while the addition of vermiculite did not impact on fouling. The use of low-cost minerals in combination with ultrafiltration membranes can be employed to treat industrial wastewater, resulting in a final effluent with very low copper concentrations.

Leaching properties of slag generated by a gasification/vitrification unit: The role of pH, particle size, contact time and cooling method used

The environmental impact from the operation of thermal waste treatment facilities mainly originates from the air emissions, as well as the generated solid residues. The objective of this paper is to examine the slag residue generated by a demonstration plasma gasification/vitrification unit and investigate the composition, the leaching properties of the slag under different conditions, as well as the role of the cooling method used. The influence of pH, particle size and contact time on the leachability of heavy metals are discussed. The main outcome is that the vitrified slag is characterized as inert and stable and can be safely disposed at landfills or used in the construction sector. Finally, the water-cooled slag showed better resistance in relation to heavy metal leachability compared to the air-cooled slag.