Removal of Pharmaceutical Residues from Water and Wastewater Using Dielectric Barrier Discharge Methods-A Review.

Persistent pharmaceutical pollutants (PPPs) have been identified as potential endocrine disruptors that mimic growth hormones when consumed at nanogram per litre to microgram per litre concentrations. Their occurrence in potable water remains a great threat to human health. Different conventional technologies developed for their removal from wastewater have failed to achieve complete mineralisation. Advanced oxidation technologies such as dielectric barrier discharges (DBDs) based on free radical mechanisms have been identified to completely decompose PPPs. Due to the existence of pharmaceuticals as mixtures in wastewater and the recalcitrance of their degradation intermediate by-products, no single advanced oxidation technology has been able to eliminate pharmaceutical xenobiotics. This review paper provides an update on the sources, occurrence, and types of pharmaceuticals in wastewater by emphasising different DBD configurations previously and currently utilised for pharmaceuticals degradation under different experimental conditions. The performance of the DBD geometries was evaluated considering various factors including treatment time, initial concentration, half-life time, degradation efficiency and the energy yield (G50) required to degrade half of the pollutant concentration. The review showed that the efficacy of the DBD systems on the removal of pharmaceutical compounds depends not only on these parameters but also on the nature/type of the pollutant.

Synthesis of zeolite NaA membrane from fused fly ash extract.

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.

Leaching and antimicrobial properties of silver nanoparticles loaded onto natural zeolite clinoptilolite by ion exchange and wet impregnation.

This study aimed to compare the leaching and antimicrobial properties of silver that was loaded onto the natural zeolite clinoptilolite by ion exchange and wet impregnation. Silver ions were reduced using sodium borohydride (NaBH4). The leaching of silver from the prepared silver-clinoptilolite (Ag-EHC) nanocomposite samples and their antimicrobial activity on Escherichia coli Epi 300 were investigated. It was observed that the percentage of silver loaded onto EHC depended on the loading procedure and the concentration of silver precursor used. Up to 87% of silver was loaded onto EHC by wet impregnation. The size of synthesized silver nanoparticles varied between 8.71-72.67 nm and 7.93-73.91 nm when silver was loaded by ion exchange and wet impregnation, respectively. The antimicrobial activity of the prepared nanocomposite samples was related to the concentration of silver precursor used, the leaching rate and the size of silver nanoparticles obtained after reduction. However, only in the case of the nanocomposite sample (Ag-WEHC) obtained after loading 43.80 ± 1.90 µg of Ag per gram zeolite through wet impregnation was the leaching rate lower than 0.1 mg L-1 limit recommended by WHO, with an acceptable microbial killing effect.

Degradation of organic pollutants and microorganisms from wastewater using different dielectric barrier discharge configurations--a critical review.

The growing global drinking water crisis requires the development of novel advanced, sustainable, and cost-effective water treatment technologies to supplement the existing conventional methods. One such technology is advanced oxidation based on dielectric barrier discharge (DBD). DBD such as single and double planar and single and double cylindrical dielectric barrier configurations have been utilized for efficient degradation of recalcitrant organic pollutants. The overall performance of the different DBD system varies and depends on several factors. Therefore, this review was compiled to give an overview of different DBD configurations vis-a-viz their applications and the in situ mechanism of generation of free reactive species for water and wastewater treatment. Our survey of the literature indicated that application of double cylindrical dielectric barrier configuration represents an ideal and viable route for achieving greater water and wastewater purification efficiency.

Distributional Fate of Elements during the Synthesis of Zeolites from South African Coal Fly Ash.

The synthesis of zeolites from South African coal fly ash has been deemed a viable solution to the growing economical strain caused by the disposal of ash in the country. Two synthesis routes have been studied thus far namely the 2-step method and the fusion assisted process. Fly ash contains several elements originating from coal which is incorporated in the ash during combustion. It is vital to determine the final destination of these elements in order to unveil optimization opportunities for scale-up purposes. The aim of this study was to perform a material balance study on both synthesis routes to determine the distributional fate of these elements during the synthesis of zeolites. Zeolites were first synthesized by means of the two synthesis routes. The composition of all raw materials and products were determined after which an overall and elemental balance were performed. Results indicated that in the 2-step method almost all elements were concentrated in the solid zeolite product while during the fusion assisted route the elements mostly report to the solid waste. Toxic elements such as Pb, Hg, Al, As and Nb were found in both the supernatant waste and washing water resulting from each synthesis route. It has also been seen that large quantities of Si and Al are wasted in the supernatant waste. It is highly recommended that the opportunity to recycle this liquid waste be investigated for scale-up purposes. Results also indicate that efficiency whereby Si and Al are extracted from fused ash is exceptionally poor and should be optimized.

Fly ash-brine interactions: removal of major and trace elements from brine.

Fly ash and brine contain major and trace elements such as Na, Cl, Ca, SO(4), K, Mg, P, Si, Al, Fe, Mn, Cr, V and Ti in significant quantities. This study focuses on the leachability of species from fly ash and the removal of major and trace species from brine as the two waste streams interact. Another objective is to evaluate the effect of the interactions on the brine quality. Batch reaction tests were carried out on two different fly ashes and brine at different L/S ratios and different reaction times, and the supernatant analysed for major and trace species. Chemical analysis revealed that the unreacted brine solution contained high concentration of species such as Na, K, Ca, Mg, Cl and SO(4), while species such as As, Ba, Cd, Co, Cr, Mn, Pb and Ti were present in trace quantities. Analysis of the supernatants after the batch reaction tests (fly ash-brine interaction experiments) revealed that major species such as Na, Mg, Cl and SO(4), and trace elements such as As, Co, Pb, Zn, Ni and Cu were significantly removed from the brine solution while Ca, Ba, Sr, Cr and Mo were leached into the brine solution from the fly ashes. The removal of species from the brine solution was most prominent at L/S ratio 1:1. This indicates that the L/S ratio of the ash-brine system has a significant effect on the release of species from fly ash or the removal of species from brine solution. The final pH of the fly ash-brine solutions and the contact times were also observed to have a significant effect on the leaching from fly ash as well as the removal of major and trace species from the brine. The study also showed that some contaminant species can be removed from brine solution using fly ash.

Leaching characteristics of selected South African fly ashes: effect of pH on the release of major and trace species.

Fly ash samples from two South African coal-fired power stations were subjected to different leaching tests under alkaline and acidic conditions in an attempt to assess the effect of pH on the leachability of species from the fly ashes and also assess the potential impact of the fly ashes disposal on groundwater and the receiving environment. To achieve this, German Standard leaching (DIN-S4) and Acid Neutralization Capacity (ANC) tests were employed. Mineralogical characterization of the fresh fly ashes revealed mullite and quartz as the major mineral phases with minor peaks of CaO and calcite. Chemical characterization by X-ray fluorescence (XRF) spectrometry revealed that the two fly ashes are similar, and consist of SiO(2), Al(2)O(3), Fe(2)O(3) and CaO as the main components with Cr, Co, Ni, Cu, Zn, V and Pb as minor components. Ca, Mg, Na, K and SO(4) were significantly leached into solution under the two leaching conditions with the total amounts in ANC leachates higher than that of DIN-S4. This indicates that a large fraction of the soluble salts in unweathered fly ash are easily leached. These species represents the fraction that can be flushed off initially from the surface of ash particles on contacting the ash with water. Al and Si were only observed in the leachates of the ANC test. Results obtained from the total acid-digestion and DIN-S4 leaching test indicated some toxic elements in the fly ashes are not easily solubilized. The amounts of toxic trace elements such as As, Se, Cd, Cr and Pb leached out of the fly ashes when in contact with de-mineralized water (DIN-S4 test) were low and below the Target Water Quality Range (TWQR) of South Africa. This is explained by their low concentrations in the fly ashes and their solubility dependence on the pH of the leaching solution. However the amounts of some minor elements such as B, Mn, Fe, As and Se leached out at lower pH ranging between 10 to 4 (ANC test) were slightly higher than the TWQR, an indication that the pH of the leaching solution plays a significant role on the leaching of species in fly ash. The high concentrations of the toxic elements released from the fly ashes at lower pH gives an indication that the disposal of the fly ash could have adverse effects on the receiving environment if the pH of the solution contacting the ashes is not properly monitored. The study indicated that on contact with water in a disposal scenario fly ash will release high amounts of soluble species.