Effects of Alkaline Cleaning Agents on the Long-Term Performance and Aging of Polyethersulfone Ultrafiltration Membranes Applied for Treatment of Car Wash Wastewater.

The commercial ultrafiltration polyethersulfone (PES) membranes (10 and 100 kDa) blended with polyvinylpyrrolidone (PVP) were applied for the filtration of car wash wastewater. Periodical membrane rinsing with water did not prevent fouling and a decrease in permeate flux was observed. Fouling was reduced by washing the membranes with cleaning agents, which are used in car washes to clean wheels and remove insects. In addition to surfactants, these agents contain NaOH, hence the pH value of cleaning solutions was over 11. Long-term contact with such solutions resulted in the removal of PVP from the membrane matrix and an increase in pore size. The PES membranes were soaked in an alkaline solution (pH = 11.5) for 20 months, after which the 200 kDa dextran rejection decreased from 95% to 80%. To compare with the static degradation conditions, 8 weeks of alkaline agent filtration was realized, after which the dextran (200 kDa) rejection decreased below 50%. This indicated that the cross-flow of alkaline agents can accelerate the removal of components building the membrane matrix. Despite membrane degradation, the separation efficiency (the rejection of chemical oxygen demand-COD, turbidity, and surfactants) during the treatment of synthetic car wash wastewater was similar to that obtained for pristine membranes.

Hybrid system coupling ozonation and nanofiltration with functionalized catalytic ceramic membrane for ibuprofen removal.

The investigations on the removal of ibuprofen (IBU) in a hybrid system coupling ozonation and nanofiltration with functionalized catalytic ceramic membrane are presented. The gaseous ozone into feed water in concentration of 11 g Nm-3 was supplied. Positive influence of catalytic ozonation on ibuprofen decomposition was observed. The application of catalytic nanofiltration membrane led to the ibuprofen removal of 91% after the first 15 min from the beginning of the O3/NF process, while at the same time, for the pristine membrane, it was equal to 76%. The investigations revealed incomplete degradation of drug under pH 3 after 2 h, i.e., 89%. On the other hand, the addition of inorganic salts did not affect the catalytic ibuprofen removal efficiency. Under acidic pH, the highest permeate flux decline (26%) was noted, whereas no differences between permeate flux measured under natural and alkaline conditions were observed. During the treatment process, three IBU by-products were detected, which significantly affected the permeate toxicity; however, after 2 h of catalytic nanofiltration, the product of treatment process was found as non-toxic.

Enhancement of Inhibition of the Pseudomonas sp. Biofilm Formation on Bacterial Cellulose-Based Wound Dressing by the Combined Action of Alginate Lyase and Gentamicin.

Bacterial biofilms generally contribute to chronic infections, including wound infections. Due to the antibiotic resistance mechanisms protecting bacteria living in the biofilm, they are a serious problem in the wound healing process. To accelerate the wound healing process and avoid bacterial infection, it is necessary to select the appropriate dressing material. In this study, the promising therapeutic properties of alginate lyase (AlgL) immobilised on BC membranes for protecting wounds from Pseudomonas aeruginosa infection were investigated. The AlgL was immobilised on never dried BC pellicles via physical adsorption. The maximum adsorption capacity of AlgL was 6.0 mg/g of dry BC, and the equilibrium was reached after 2 h. The adsorption kinetics was studied, and it has been proven that the adsorption was consistent with Langmuir isotherm. In addition, the impact of enzyme immobilisation on bacterial biofilm stability and the effect of simultaneous immobilisation of AlgL and gentamicin on the viability of bacterial cells was investigated. The obtained results showed that the AlgL immobilisation significantly reduced the amount of polysaccharides component of the P. aeruginosa biofilm. Moreover, the biofilm disruption by AlgL immobilised on BC membranes exhibited synergism with the gentamicin, resulting in 86.5% more dead P. aeruginosa PAO-1 cells.

Stimulated generation of photobiogas by morphologically tuned nanostructured ZnO and ZnO/TiO2.

The photocatalytic degradation (PCD) of ethanol in an inert atmosphere on catalysis was explored in a lab-scale experiment. A morphologically tuned nanostructured controlled ZnO and ZnO/TiO2 nanocomposites were synthesized using a simple hydrothermal process under the control of several functionally capping agents marking a milestone in photocatalysis. It is possible that this could be modified to produce photobiogas out of organic dye pollution. The photocatalysts were characterized by the use of X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer, Emmett, and Teller (BET) surface area analyzer, Scanning electron microscope (SEM-EDX), and UV-Vis absorption spectroscopy. The photocatalytic activity of the ZnO and ZnO-TiO2 composite nanostructures was evaluated for the photodegradation of the Tartrazine (Tr) dye aqueous solution. Where the composite matrix exhibits higher photocatalytic activity than pure ZnO nanomaterials as a result of the synergistic interaction between ZnO and TiO2 particles. This is mainly due to its higher surface area than pure ZnO. Moreover, the photocatalytic activity of the tuned nanostructured materials is found to be enhanced by the effect of the capping agent and controlling the morphology. This increase is accompanied by a significant shift in surface shape and band gap energy. According to the findings, the designed morphologies of pure ZnO photocatalyst impacted the formation of photobiogas from the photocatalytic decomposition of ethanol as a model of organic pollutants in wastewater. However, when using composite ZnO/TiO2 photocatalysts, the rate of CH4 formation is significantly lower than when using ZnO photocatalysts alone. This may be attributed to the synergetic effect between ZnO and TiO2 particles which leads to a remarkable reduction in the newly formed band gap energy. This may result in a fast rate of recombination between the photogenerated charge carriers (e- and h+).

Influence of Polymer Solvents on the Properties of Halloysite-Modified Polyethersulfone Membranes Prepared by Wet Phase Inversion.

Ultrafiltration polyethersulfone (PES) membranes were prepared by wet phase inversion. Commercial halloysite nanotubes (HNTs) in the quantities of 0.5 wt% vs. PES (15 wt%) were introduced into the casting solution containing the polymer and different solvents: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), or 1-methyl-2-pyrrolidinone (NMP). The type of solvent influenced the membranes' morphology and topography, as well as permeability, separation characteristics, and antifouling and antibacterial properties. The membranes prepared using DMA exhibited the loosest cross-section structure with the thinnest skin and the roughest surface, while the densest and smoothest were the DMF-based membranes. The advanced contact angles were visibly lower in the case of the membranes prepared using DMF compared to the other solvents. The highest water permeability was observed for the DMA-based membranes, however, the most significant effect of the modification with HNTs was found for the NMP-based series. Regardless of the solvent, the introduction of HNTs resulted in an improvement of the separation properties of membranes. A noticeable enhancement of antifouling performance upon application of HNTs was found only in the case of DMF-based membranes. The study of the antibacterial properties showed that the increase in surface roughness had a positive effect on the inhibition of E. coli growth.

Treatment of laundry wastewater by solar photo-Fenton process at pilot plant scale.

Laundry sector consumes a huge amount of water which is usually discharged as wastewater instead of being reused. The application of biological treatment of laundry wastewater coupled with post-treatment utilizing advanced oxidation processes creates a possibility to recycle water to the washing process. However, the investigations on such systems are very limited. In the present work, a novel approach of post-treatment of laundry wastewater utilizing solar photo-Fenton operated at a pilot scale in a compound parabolic collector (CPC) photoreactor is proposed. Sodium dodecyl sulfate (SDS) was used as a representative of surfactants applied in the laundry system. The effect of feed matrix was investigated using distilled water as a reference matrix and synthetic wastewater simulating the composition of biologically pre-treated laundry wastewater. Different concentrations of H2O2 (50-400 mg/L) and ferrous iron (2.75-10 mg/L) were assayed. For comparison purpose, experiments at neutral pH using ethylenediamine-N,N'-disuccinic acid (EDDS) as an iron complexing agent were carried out. A high SDS removal efficiency was obtained under both neutral and acidic pH, reaching 89% and 96%, respectively, in just 8 min. However, the remaining organic load originating from EDDS needs application of further post-treatment steps. Therefore, the solar photo-Fenton operated under acidic pH was found to be a more promising approach of post-treatment of laundry wastewater aimed at its reuse.

Hybrid System Coupling Moving Bed Bioreactor with UV/O3 Oxidation and Membrane Separation Units for Treatment of Industrial Laundry Wastewater.

This paper describes the investigations on the possibilities of treatment of wastewater generated in an industrial laundry with application of a combined biological-photooxidation- membrane system aimed at water recycle and reuse. The two treatment schemes were compared: 1) scheme A consisting of a treatment in a moving bed biological reactor (MBBR) followed by microfiltration (MF) and nanofiltration (NF), and 2) scheme B comprising MBBR followed by oxidation by photolysis enhanced with in situ generated O3 (UV/O3) after which MF and NF were applied. The removal efficiency in MBBR reached 95-97% for the biochemical oxygen demand; 90-93% for the chemical oxygen demand and 89-99% for an anionic and a nonionic surfactants. The application of UV/O3 system allowed to decrease the content of the total organic carbon by 68% after 36 h of operation with a mineralization rate of 0.36 mg/L·h. Due to UV/O3 pretreatment, a significant mitigation of membrane fouling in the case of both MF and NF processes was achieved. The MF permeate flux in the system B was over two times higher compared to that in the system A. Based on the obtained results it was concluded that the laundry wastewater pretreated in the MBBR-UV/O3-MF-NF system could be recycled to any stage of the laundry process.

Influence of Preparation Procedure on Physicochemical and Antibacterial Properties of Titanate Nanotubes Modified with Silver.

Silver nanoparticles (NPs) are effective antibacterial agents; however, aggregation of NPs and uncontrolled release of Ag+ affect their efficiency and may pose a risk to the environment. To overcome these disadvantages, immobilization of Ag onto titanate nanotubes (TNTs) was investigated. This paper describes the physicochemical and antibacterial properties of silver incorporated titanate nanotubes (Ag/TNTs) prepared using five procedures and containing different Ag amounts (0.11-30.85 wt.%). The methods were (i) sol-gel followed by a hydrothermal process; (ii) photodeposition under ambient conditions; (iii) photodeposition under an inert atmosphere; (iv) NaBH4 reduction; and (v) electroless deposition after activation of TNTs with Sn2+. Depending on the synthesis procedure, the presence of metallic Ag NPs, AgO or AgCl was observed. The electroless method led to an additional deposition of SnO2 NPs. The antibacterial properties of Ag/TNTs were analyzed as a function of Ag content and released against Escherichia coli and Staphylococcus epidermidis. The best bactericidal properties exhibited Ag/TNTs prepared through the photodeposition process due to the higher interaction of exposed Ag NPs with bacteria. An increase of Ag loading resulted in improvement of antibacterial activity of Ag/TNTs although no direct correlation between silver content or release and inhibition of bacterial growth was found.

Investigations on the Properties and Performance of Mixed-Matrix Polyethersulfone Membranes Modified with Halloysite Nanotubes.

Ultrafiltration (UF) polyethersulfone (PES) membranes were prepared by wet phase inversion method. Commercial halloysite nanotubes (HNTs) in the amount of 0.5-4 wt % vs PES (15 wt %) were introduced into the casting solution containing the polymer and N,N-dimethylformamide as a solvent. The morphology, physicochemical properties and performance of the membranes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), zeta potential, porosity and contact angle analyses, as well as permeability measurements. Moreover, the antifouling properties of the membranes were evaluated during UF of a model solution of bovine serum albumin (BSA). The research revealed a positive influence of modification with HNTs on hydrophilicity, water permeability and antifouling properties of the PES membranes. The most significant improvement of permeability was obtained in case of the membrane containing 2 wt % of HNTs, whereas the highest fouling resistance was observed for 0.5 wt % HNTs content. It was found that a good dispersion of HNTs can be obtained only at loadings below 2 wt %. Based on the results a relation between severity of membrane fouling and surface roughness was proved. Moreover, an increase of the roughness of the modified membranes was found to be accompanied by an increase of isoelectric point values.

The application of moving bed bio-reactor (MBBR) in commercial laundry wastewater treatment.

Large, laboratory scale biological treatment tests of real industrial wastewater, generated in a large industrial laundry facility, was conducted from October 2014 to January 2015. This research sought to develop laundry wastewater treatment technology which included tests of a two-stage Moving Bed Bio Reactor (MBBR); this had two reactors, was filled with carriers Kaldnes K5 (specific area - 800 m2/m3) and were realized in aerobic condition. Operating on site, in the laundry, reactors were fed actual wastewater from the laundry retention tank. The laundry wastewater contained mainly surfactants and impurities originating from washed fabrics; a solution of urea to supplement nitrogen content and a solution of acid to correct pH were added. The daily flow of raw wastewater Qd varied from 0.6-1.0 m3/d. Wastewater quality indicators showed that the reduction of pollutants was obtained: BOD5 by 95-98%, COD by 89-94%, the sum of anionic and nonionic surfactants by 85-96%. The quality of the purified wastewater after the start-up period met legal requirements regarding the standards for wastewater discharged into the environment.

A system coupling hybrid biological method with UV/O3 oxidation and membrane separation for treatment and reuse of industrial laundry wastewater.

The possibilities of application of a three-step system combining hybrid biological treatment followed by advanced UV/O3 oxidation with in situ generated O3 and membrane separation (ultrafiltration (UF) and nanofiltration (NF)) to treat and reuse the wastewater from an industrial laundry are presented. By the application of a hybrid moving bed biofilm reactor (HMBBR), the total organic carbon concentration was reduced for about 90 %. However, since the HMBBR effluent still contained organic contaminants as well as high concentrations of inorganic ions and exhibited significant turbidity (8.2 NTU), its further treatment before a possible reuse in the laundry was necessary. The UV/O3 pretreatment prior to UF was found to be an efficient method of the membrane fouling alleviation. During UF, the turbidity of wastewater was reduced below 0.3 NTU. To remove the inorganic salts, the UF permeate was further treated during NF. The NF permeate exhibited very low conductivity (27-75 µS/cm) and contained only small amounts of Ca(2+) and Mg(2+); thus ,it could be reused at any stage of the laundry process.

Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

Decomposition of 3-chlorophenol on nitrogen modified TiO2 photocatalysts.

Photocatalytic activity of nitrogen modified TiO(2) calcined at temperatures of 100-350°C toward 3-chlorophenol (3-CP) degradation was studied. In the experiments the fluorescent UV lamp and the incandescent lamp emitting mainly Vis light were applied. The degradation efficiency was evaluated on a basis of changes of 3-CP, total organic carbon and Cl(-) concentration. A significant improvement of the photoactivity of the N-modified photocatalysts compared to the reference sample was observed. The rate of 3-CP degradation increased with the calcination temperature, and the highest efficiency was achieved for TiO(2) annealed at 350°C. After 5h of UV irradiation in the presence of TiO(2)/N-350 and reference TiO(2) the 3-CP concentration decreased for 77% and 36%, respectively. The 3-CP removal after 24h of Vis irradiation was 30% and 12% for the N-modified and reference samples, respectively. The 3-CP decomposition and mineralization were greatly influenced by pH of the solution, achieving the highest rate at pH 7 for the modified photocatalysts. An increase of the calcination temperature resulted in an increase of the rate of OH formation. The photocatalytic activity of the N-modified TiO(2) remained unchanged during repeated photocatalytic degradation cycles.

Application of carbon-coated TiO2 for decomposition of methylene blue in a photocatalytic membrane reactor.

An application of carbon-coated TiO(2) for decomposition of methylene blue (MB) in a photocatalytic membrane reactor (PMR), coupling photocatalysis and direct contact membrane distillation (DCMD) was investigated. Moreover, photodegradation of a model pollutant in a batch reactor without membrane distillation (MD) was also examined. Carbon-modified TiO(2) catalysts containing different amount of carbon and commercially available TiO(2) (ST-01) were used in this study. The carbon-coated catalyst prepared from a mixture of ST-01 and polyvinyl alcohol in the mass ratio of 70/30 was the most effective in degradation of MB from all of the photocatalysts applied. Photodecomposition of MB on the recovered photocatalysts was lower than on the fresh ones. The photodegradation of MB in the PMR was slower than in the batch reactor, what probably resulted from shorter time of exposure of the catalyst particles to UV irradiation. The MD process could be successfully applied for separation of photocatalyst and by-products from the feed solution.

Studies on the effect of humic acids and phenol on adsorption-ultrafiltration process performance.

Application of pressure-driven membrane processes, such as ultrafiltration (UF) and microfiltration (MF) for surface water treatment have become very popular during last decades. Membrane fouling by humic substances (HS) is one of the major limiting factors in these processes. In order to alleviate the unfavorable effects of the presence of HS in the feed on the process performance UF and MF are often combined with adsorption on powdered activated carbon (PAC). The main goal of the present study was to evaluate the effect of humic acid (HA) on membrane fouling during UF. Moreover, the effect of PAC addition to the feed on UF process, especially on flux decline was determined. The applicability of the adsorption-ultrafiltration (PAC/UF) system to purification of water containing low (phenol) and high molecular (HA) was also investigated. Three different polymer UF membranes, prepared from polysulfone (PSF), cellulose acetate (CA) or polyacrylonitrile (PAN) were applied. It was found that the membranes prepared from PSF and CA are very susceptible to fouling caused by HA. The permeate flux decreased for ca. 50% during UF of HA solution through the PSF membrane and for ca. 45%-through the CA membrane. In the case of the PAN membrane, a negligible effect of HA on the flux was observed. On the basis of the FTIR spectra it was found that the drop in the permeate flux through these membranes may result from interactions between the negatively charged functional groups present on the membrane surface, such as carboxyl groups (CA) and sulfone groups (PSF) with HA, which results in coating of the membrane surface with HA. When PAC was added to the feed containing HA, the permeate flux through the CA and PAN membranes was maintained on a practically unchanged level. However, in case of the PSF membrane, a 50% drop in the permeate flux in comparison with the flux value, when process was conducted without PAC addition was observed. That was supposed to be due to attractive forces among hydrophobic PAC particles, HA molecules and PSF membrane surface. The performed studies showed that the application of PAC/UF system was very effective in the removal of organic substances having both, low and high molecular weights. The role of PAC suspended in a feed in the PAC/UF system is the adsorption of low molecular organic compounds, which cannot be removed by UF alone.

Removal of organic matter from water by PAC/UF system.

The laboratory-scale ultrafiltration (UF) experiments were conducted to determine the effect of the presence of powdered activated carbon (PAC) on the UF process performance, in terms of flux decline and the possibilities of membranes cleaning during backwashing. Poly(vinylidene fluoride) membranes formed by the phase inversion technique were used in the UF experiments. A model solution was prepared as a mixture of humic acids (HA) and phenol in concentration of 10 and 1 mg l(-1), respectively. Commercial powdered activated carbons CWZ 11 and CWZ 30 (Gryfskand Sp. z o. o., Hajnówka, Poland) were used as the adsorbents. PAC dosage was in the range of 10-100 mg PAC l(-1). The process was carried out in the cross-flow system. It was found that PAC addition to the distilled water leads to a small drop in the permeate flux, regardless of PAC dose and its type. Although PAC particles are too large to block the membrane pores inside, they deposit on the membrane surface and partially can plug the surface pores. The experimental results demonstrate that the backwashing process applied in combined PAC/UF system was especially effective when PAC dosages were <20mg PAC l(-1). However, a similar permeate flux was maintained for all carbon dosages used and reached the value of about 1 m3 m(-2) d(-1). Moreover, no further drop in the permeate flux for PAC addition to the solution containing foulants (HA) was observed. Effectiveness of the removal of HA and phenol from the model solutions was also investigated. In the PAC/UF system HA were removed in about 90%, whereas the complete removal of phenol was achieved for PAC dosage equal to 100 mg l(-1).