Advanced (bio)fouling resistant surface modification of PTFE hollow-fiber membranes for water treatment.

Membrane surface treatment to modify anti-(bio)fouling resistivity plays a key role in membrane technology. This paper reports on the successful use of air-stimulated surface polymerization of dopamine hydrochloride incorporated ZnO nanoparticles (ZnO NPs) for impeding the intrinsic hydrophobicity and low anti-(bio)fouling resistivity of polytetrafluoroethylene (PTFE) hollow-fiber membranes (HFMs). The study involved the use of pristine and polydopamine (Pdopa) coated PTFE HFMs, both with and without the presence of an air supply and added ZnO NPs. Zeta potential measurements were performed to evaluate the dispersion stability of ZnO NPs prior to immobilization, while morphological characterization and time-dependency of the Pdopa growth layer were illustrated through scanning electron microscopy. Pdopa surface polymerization and ZnO NPs immobilization were confirmed using FT-IR and EDX spectroscopy. Transformation of the PTFE HFM surface features to superhydrophilic was demonstrated through water contact angle analysis and the stability of immobilized ZnO NPs assessed by ICP analysis. Anti-fouling criteria and (bio)fouling resistivity performance of the surface-modified membranes were assessed through flux recovery determination of bovine serum albumin in dead-end filtration as well as dynamic-contact-condition microbial evaluation against Staphylococcus spp. and Escherichia coli, respectively. The filtration recovery ratio and antimicrobial results suggested promising surface modification impacts on the anti-fouling properties of PTFE HFM. As such, the method represents the first successful use of air-stimulated Pdopa coating incorporating ZnO NPs to induce superhydrophilic PTFE HFM surface modification. Such a method can be extended to the other membranes associated with water treatment processes.

Recovery of Hydrochloric Acid from Industrial Wastewater by Diffusion Dialysis Using a Spiral-Wound Module.

In the present study, the possibility of using a spiral-wound diffusion dialysis module was studied for the separation of hydrochloric acid and Zn2+, Ni2+, Cr3+, and Fe2+ salts. Diffusion dialysis recovered 68% of free HCl from the spent pickling solution contaminated with heavy-metal-ion salts. A higher volumetric flowrate of the stripping medium recovered a more significant portion of free acid, namely, 77%. Transition metals (Fe, Ni, Cr) apart from Zn were rejected by >85%. Low retention of Zn (35%) relates to the diffusion of negatively charged chloro complexes through the anion-exchange membrane. The mechanical and transport properties of dialysis FAD-PET membrane under accelerated degradation conditions was investigated. Long-term tests coupled with the economic study have verified that diffusion dialysis is a suitable method for the treatment of spent acids, the salts of which are well soluble in water. Calculations predict significant annual OPEX savings, approximately up to 58%, favouring diffusion dialysis for implementation into wastewater management.

Chemical Cleaning Process of Polymeric Nanofibrous Membranes.

Membrane fouling is one of the most significant issues to overcome in membrane-based technologies as it causes a decrease in the membrane flux and increases operational costs. This study investigates the effect of common chemical cleaning agents on polymeric nanofibrous membranes (PNM) prepared by polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), and polyamide 6 (PA6) nanofibers. Common alkaline and acid membrane cleaners were selected as the chemical cleaning agents. Membrane surface morphology was investigated. The PAN PNM were selected and fouled by engine oil and then cleaned by the different chemical cleaning agents at various ratios. The SEM results indicated that the use of chemical agents had some effects on the surface of the nanofibrous membranes. Moreover, alkaline cleaning of the fouled membrane using the Triton X 100 surfactant showed a two to five times higher flux recovery than without using a surfactant. Among the tested chemical agents, the highest flux recovery rate was obtained by a binary solution of 5% sodium hydroxide + Triton for alkaline cleaning, and an individual solution of 1% citric acid for acidic cleaning. The results presented here provide one of the first investigations into the chemical cleaning of nanofiber membranes.

Lactose Mother Liquor Stream Valorisation Using an Effective Electrodialytic Process.

The integrated electrodialysis (ED) process supports valorisation of a lactose-rich side stream from the dairy industry, creating an important source of milk sugar used in various branches of the industry. This work focuses on the optimization of the downstream processes before the crystallization of lactose. The process line includes a pre-treatment and desalination by ED of the industrial waste solution of the lactose mother liquor (LML). The LML was diluted to 25% total solids to overcome hydraulic issues with the ED desalination process. Two different levels of electrical conductivity reduction (70% and 90%) of the LML solutions were applied to decrease the mineral components and organic acids of the LML samples. The ED performance parameters such as ash transfer rate (J), the specific capacity (CF) of the ED and specific electric energy consumption (E) were determined and the influence of the LML solution on the monopolar ion-exchange membranes has been investigated. A higher degree of desalination is associated with higher electric energy consumption (by 50%) and lower specific capacity (by 40%). A noticeable decrease (by 12.8%) in the resistance of the anion exchange membranes was measured after the trials whereas the resistance of the cation exchange membranes remained practically unchanged. Any deposition of the alkaline earth metals on the membrane surface was not observed.

Recovery of Spent Sulphuric Acid by Diffusion Dialysis Using a Spiral Wound Module.

In this study, we assess the effects of volumetric flow and feed temperature on the performance of a spiral-wound module for the recovery of free acid using diffusion dialysis. Performance was evaluated using a set of equations based on mass balance under steady-state conditions that describe the free acid yield, rejection factors of metal ions and stream purity, along with chemical analysis of the outlet streams. The results indicated that an increase in the volumetric flow rate of water increased free acid yield from 88% to 93%, but decreased Cu2+ and Fe2+ ion rejection from 95% to 90% and 91% to 86%, respectively. Increasing feed temperature up to 40 °C resulted in an increase in acid flux of 9%, and a reduction in Cu2+ and Fe2+ ion rejection by 2-3%. Following diffusion dialysis, the only evidence of membrane degradation was a slight drop in permselectivity and an increase in diffusion acid and salt permeability. Results obtained from the laboratory tests used in a basic economic study showed that the payback time of the membrane-based regeneration unit is approximately one year.

Application of nanofiber carriers for sampling of microbial biomass from contaminated groundwater.

Sampling of microbial biomass is crucial for understanding and controlling remediation processes ongoing at contaminated sites in general, particularly when molecular genetic analyses are employed. In this study, fiber-based carriers with a nanofiber layer were developed and tested as a method to sample microbial biomass in groundwater for molecular genetic analysis. Nanofiber carriers, varying in the shape and the linear density of nanofibers, were examined throughout a 27-month monitoring period in groundwater contaminated with benzene, toluene, ethylbenzene and xylene isomers (BTEX), and chlorinated ethenes. The effect of carrier shape and nanofiber layer density on the microbial surface colonization and composition of the microbial biofilm was determined using real-time PCR and next-generation sequencing (NGS) analysis. Differences in microbial community composition between nanofiber carriers, groundwater, and soil samples were also analyzed to assess the applicability of carriers for biomass sampling at contaminated sites. The nanofiber carriers showed their applicability as a sampling tool, particularly because of their easy manipulation that facilitates DNA isolation. The majority of taxa (Proteobacteria, Firmicutes, and Bacteroidetes) present on the carrier surfaces were also detected in the groundwater. Moreover, the microbial community on all nanofiber carriers reflected the changes in the chemical composition of groundwater. Although the carrier characteristics (shape, nanofiber layer) did not substantially influence the microbial community on the carrier surface, the circular and planar carriers with a nanofiber layer displayed faster microbial surface colonization. However, the circular carrier was the most suitable for biomass sampling in groundwater because of its high contact area and because it does not require pre-treatment prior to DNA extraction.

Modification of a hollow-fibre polyethersulfone membrane using silver nanoparticles formed in situ for biofouling prevention.

Biofouling represents a serious problem limiting the widespread application of membrane technology. Therefore, the aim of this study was to develop and verify a new modification method based on the in situ formation of silver nanoparticles and their incorporation into a membrane polymer to prevent biofouling. The modification method consisted of soaking a commercial hollow-fibre polyethersulfone membrane in a solution of silver ions, diffusion of ions into the membrane polymer, and their reduction using ascorbic acid. Such a modified membrane displayed a lower tendency towards biofouling, exhibiting an about 15% higher permeability compared to an unmodified membrane when filtering actual wastewater treatment plant effluent. The modification also led to the formation of stable silver nanoparticles (mostly in the range of 25-50 nm) homogenously distributed on the surface of the hollow-fibres. This resulted in higher surface hydrophilicity (the water contact angle decreased from 91° to 86°) contributing to the biofouling prevention. The modified membrane also showed high stability, as only 2.1% of the total silver leached after 8 h of filtration. Moreover, no changes in the original membrane cross-section structure or separation properties were observed. Besides the improved antibiofouling properties of the modified membrane, the main advantage of the developed method is its simplicity, short reaction time, absence of high energy-consuming initiation, and the possibility to apply it on site, thus even with commercial membrane modules. It will increase the application potential of membranes in the field of wastewater treatment.

Assessment of biodegradation potential at a site contaminated by a mixture of BTEX, chlorinated pollutants and pharmaceuticals using passive sampling methods - Case study.

The present study describes a pilot remediation test of a co-mingled plume containing BTEX, chlorinated pollutants and pharmaceuticals. Remediation was attempted using a combination of various approaches, including a pump and treat system applying an advanced oxidation process and targeted direct push injections of calcium peroxide. The remediation process was monitored intensively and extensively throughout the pilot test using various conventional and passive sampling methods, including next-generation amplicon sequencing. The results showed that the injection of oxygen-saturated treated water with residual hydrogen peroxide and elevated temperature enhanced the in situ removal of monoaromatics and chlorinated pollutants. In particular, in combination with the injection of calcium peroxide, the conditions facilitated the in situ bacterial biodegradation of the pollutants. The mean groundwater concentration of benzene decreased from 1349µg·L-1 prior to the test to 3µg·L-1 within 3months after the calcium peroxide injections; additionally, monochlorobenzene decreased from 1545µg·L-1 to 36µg·L-1, and toluene decreased from 143µg·L-1 to 2µg·L-1. Furthermore, significant degradation of the contaminants bound to the soil matrix in less permeable zones was observed. Based on a developed 3D model, 90% of toluene and 88% of chlorobenzene bound to the soil were removed during the pilot test, and benzene was removed almost completely. On the other hand, the psychopharmaceuticals were effectively removed by the employed advanced oxidation process only from the treated water, and their concentration in groundwater remained stagnant due to inflow from the surroundings and their absence of in situ degradation. The employment of passive sampling techniques, including passive diffusion bags (PDB) for volatile organic pollutants and their respective transformation products, polar organic compound integrative samplers (POCIS) for the pharmaceuticals and in situ soil microcosms for microbial community analysis, was proven to be suitable for monitoring remediation in saturated zones.

Influence of Sample Temperature for Measurement Accuracy with FT-NIR Spectroscopy.

This study monitored the influence of milk samples temperature on the measuring accuracy of FT-NIR spectroscopy in milk content analysis. Reference methods were used to determine dry matter, fat, protein, and lactose content in cow's milk. Milk samples were measured in reflectance mode on an integrating sphere with the use of a compression cuvette and a transflectance cuvette, ensuring a beam trajectory length of h = 0.2 mm. The samples were measured at 18, 20, 22, 24, and 40°C, and analyses were performed at 100 scans at a resolution of 8 cm-1. The measurements were influenced by the temperatures of the samples during the evaluation of all analyzed constituents (P < 0.05). Our results confirmed that the accurate determination of milk constituents requires maintaining, during analysis, the temperature conditions of the samples and the conditions for which the spectrophotometer calibration was designed.

Performance of an anaerobic membrane bioreactor for pharmaceutical wastewater treatment.

Anaerobic treatment of wastewater and waste organic solvents originating from the pharmaceutical and chemical industries was tested in a pilot anaerobic membrane bioreactor, which was operated for 580days under different operational conditions. The goal was to test the long-term treatment efficiency and identify inhibitory factors. The highest COD removal of up to 97% was observed when the influent concentration was increased by the addition of methanol (up to 25gL-1 as COD). Varying and generally lower COD removal efficiency (around 78%) was observed when the anaerobic membrane bioreactor was operated with incoming pharmaceutical wastewater as sole carbon source. The addition of waste organic solvents (>2.5gL-1 as COD) to the influent led to low COD removal efficiency or even to the breakdown of anaerobic digestion. Changes in the anaerobic population (e.g., proliferation of the genus Methanosarcina) resulting from the composition of influent were observed.

Accuracy of the FT-NIR Method in Evaluating the Fat Content of Milk Using Calibration Models Developed for the Reference Methods According to Röse-Gottlieb and Gerber.

The study examined the effect of the choice of reference method on the functionality and reliability of calibrations in near-IR (NIR) spectroscopy intended for measuring the fat content in raw cow's milk. The fat content in the milk samples was evaluated using methods according to either Röse-Gottlieb or Gerber. The same samples were then subjected to analysis on an Antaris FT-NIR spectrometer. Using a partial least-squares algorithm, calibration models were created for both methods from the values measured. The calibration models show very good values of standard error of calibration: 0.133 for the Gerber method and 0.095 for the Röse-Gottlieb method. These calibrations were subsequently used to analyze 30 new samples of cow's milk of undefined fat content, and the differences in the values were evaluated using statistical paired t-test to a median value at a probability level of α = 0.05. No statistically significant differences were found. It was revealed that the reference method used for calibrating the device evaluating the fat content in raw cow's milk has no effect on the functionality and reliability of the calibration model.

Dynamics of organohalide-respiring bacteria and their genes following in-situ chemical oxidation of chlorinated ethenes and biostimulation.

Application of Fenton's reagent and enhanced reductive dechlorination are currently the most common remediation strategies resulting in removal of chlorinated ethenes. In this study, the influence of such techniques on organohalide-respiring bacteria was assessed at a site contaminated by chlorinated ethenes using a wide spectrum of molecular genetic markers, including 16S rRNA gene of the organohalide-respiring bacteria Dehaloccocoides spp., Desulfitobacterium and Dehalobacter; reductive dehalogenase genes (vcrA, bvcA) responsible for dechlorination of vinyl chloride and sulphate-reducing and denitrifying bacteria. In-situ application of hydrogen peroxide to induce a Fenton-like reaction caused an instantaneous decline in all markers below detection limit. Two weeks after application, the bvcA gene and Desulfitobacterium relative abundance increased to levels significantly higher than those prior to application. No significant decrease in the concentration of a range of chlorinated ethenes was observed due to the low hydrogen peroxide dose used. A clear increase in marker levels was also observed following in-situ application of sodium lactate, which resulted in a seven-fold increase in Desulfitobacterium and a three-fold increase in Dehaloccocoides spp. after 70 days. An increase in the vcrA gene corresponded with increase in Dehaloccocoides spp. Analysis of selected markers clearly revealed a positive response of organohalide-respiring bacteria to biostimulation and unexpectedly fast recovery after the Fenton-like reaction.

Comparison of FT-NIR Spectroscopy and ELISA for Detection of Adulteration of Goat Cheeses with Cow's Milk.

This study investigated the ability of two methods to detect adulteration of goat cheeses via the addition of cow's milk, with a negligible effect on the raw materials. Cheeses were produced from a mixture of goat's and cow's milk and were then analyzed by Fourier transform near-IR (FT-NIR) spectroscopy and competitive ELISA. The cheese spectra were scanned in the spectroscope in reflectance mode on an integrating sphere at 80 scans and a resolution of 4 cm(-1). The spectra were evaluated via discriminant analysis, and a calibration was created via a partial least-squares algorithm to quantify the cow's milk admixture. A correlation coefficient of R = 0.999 was reached with a standard error of calibration of 0.0407. The results were statistically processed to a median value via a t-test. Adulteration detection by the ELISA method was performed using a commercial Milk Fraud/Bovine ELISA kit. It was found that the FT-NIR spectroscopy method is capable of detecting an admixture of cow's milk in goat cheese as small as 1%. The ELISA method did not return satisfactory results for the detection of adulteration with cow's milk.

Nitrification performance in a membrane bioreactor treating industrial wastewater.

The influence of industrial (pharmaceutical and chemical) wastewater composition on membrane bioreactor (MBR) performance was investigated in a pilot-scale installation. The study focussed on nitrification performance, which was evaluated based on influent and effluent parameters as well as batch nitrification rate tests. The industrial wastewater was pumped into the MBR in a mixture with municipal wastewater at constant flow rate. The loading of the MBR with industrial wastewater was increased stepwise from 0 to 75% share in the mixed influent to study the adaptation of nitrifying bacteria. Stable nitrification performance was observed until the content of industrial wastewater in the influent reached 40%, with effluent values of around 0.56 mg L(-1) NH4-N and 98.3% ammonia removal. Breakdown of nitratation was observed at a 40% industrial wastewater dose and breakdown of nitritation at a 50% dose, respectively. However, after several months of adaptation, both processes recovered. No nitrification was observed when the industrial wastewater share exceeded 50%. Adaptation of nitrifying bacteria in the MBR was also confirmed by results of kinetic tests. The inhibition effect of the concentrated industrial wastewater to the MBR sludge decreased substantially after several months of exposure, while the inhibition of referential activated sludge remained constant.

Influence of phosphorus precipitation on permeability and soluble microbial product concentration in a membrane bioreactor.

Many articles have been published on coagulant dosing in membrane bioreactors, though few have been long-term studies examining the treatment of real wastewater. This study summarises the results of a membrane bioreactor pilot-plant (flat sheet membrane, nominal pore size 0.03 µm) that treated real municipal wastewater for two-years. Both influence of phosphorus precipitation by ferric sulphate on membrane permeability (flux decrease) and soluble microbial product concentration (especially on carbohydrates and proteins) were monitored. Flux decrease over work cycles lasting several months without phosphorus precipitation were compared to two periods with precipitation. X-ray elemental diffractometry of the filtration cake showed differences in the main contributors to inorganic fouling, with decreases in Ca and Si during operation with coagulant addition, and an increase in Fe.

Operational experience with a seasonally operated full-scale membrane bioreactor plant.

A seasonally operated full-scale membrane bioreactor plant (flat sheet, 0.03 µm) treating municipal wastewater from a recreation facility was monitored for 2 years. In particular, membrane bioreactor operation characteristics and development and changes in extracellular polymeric substances and soluble microbial product concentrations were observed, which were both dependent on volume and quality of incoming wastewater. Microbiological effluent quality, nutrient removal efficiency and activated sludge characteristics were analysed on a regular basis. Correlations between activated sludge quality, extracellular polymeric substance and soluble microbial product concentrations were identified. Pathogen related changes in effluent quality during plant operation were also observed. Nutrient removal efficiency was very good, despite fluctuations in influent flow.

The impact of different operating conditions on membrane fouling and EPS production.

The main goal of this research was to investigate how different factors influence membrane fouling. The impact of the different concentrations of activated sludge and the amount of extracellular polymer substances (EPS) were monitored. Two pilot plants with submerged membrane modules (hollow fiber and flat sheet) were operated and the raw wastewater was used. Humic substances were identified as the major components of EPS in the activated sludge (more than 34%) in both pilot plants. As the basic constituent in permeate, humic substances were identified as the most dominant components in the effluent (61%) in both pilot plants. Conversely, proteins were mostly analyzed in permeate and supernatant below the detection limit. The total amount of EPS [mgg(-1) (VSS)] was similar for concentrations of activated sludge 6, 10 and 14 g L(-1). Carbohydrates were identified as the component of EPS which tends most to clog membranes.