Zero-Waste Approach for Heavy Metals' Removal from Water with an Enhanced Multi-Stage Hybrid Treatment System.

The aim of the work was to develop a zero-waste technological solution for hybrid removal of heavy metals from river sediments. The proposed technological process consists of sample preparation, sediment washing (a physicochemical process for sediment purification), and purification of the wastewater produced as a by-product. A suitable solvent for heavy metal washing and the effectiveness of heavy metal removal were determined by testing EDTA and citric acid. The process for removing heavy metals from the samples worked best with citric acid when the 2% sample suspension was washed over a 5-h period. The method was chosen of the adsorption of heavy metals from the exhausting washing solution on natural clay. Analyses were performed of the three main heavy metals, Cu(II), Cr(VI), and Ni(II), in the washing solution. Based on the laboratory experiments, a technological plan was prepared for the purification of 100,000 tons of material per year.

Probiotic Lactobacillus paragasseri K7 Nanofiber Encapsulation Using Nozzle-Free Electrospinning.

Probiotics are live microorganisms that can have beneficial effects on humans. Encapsulation offers them a better chance of survival. Therefore, nozzle-free electrospinning was introduced for their embedding in nanofibrous material. Probiotic Lactobacillus paragasseri K7 in lyophilized and fresh form, with and without inulin as prebiotic, was added to a polymer solution of sodium alginate (NaAlg) and polyethylene oxide (PEO). Conductivity, viscosity, pH, and surface tension were determined to define the optimal concentration and volume ratio for smooth electrospinning. The success of the formed nanoscale materials was examined by scanning electron microscope (SEM), while the entrapment of probiotics in the nanofibrous mats was detected by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Spontaneous diffusion of bacteria from electrospun samples in PBS buffer pH 7.4 was studied by plate counting on MRS agar. By exposing polymer solutions containing L. paragasseri K7 and inulin to a high electric field, the nanofilm was formed on a polypropylene substrate, used as collecting material. When polymer solutions without inulin were used, the bead-like nanofibers may have become visible. The SEM results suggest that inulin, in addition to K7 strain, additionally lowers the conductivity of spinning macromolecular solution and hinders the nanofiber formation. The results of ATR-FTIR confirmed the presence of L. paragasseri K7 embedded in nanocomposites by the appearance of characteristic peaks. The samples containing the probiotic regardless of its form with inulin had similar surface composition, except that the sodium content was higher in the samples with fresh probiotic, probably due to greater and thus less easy embedding of the bacteria in NaAlg. Within 2 h, the largest amount of probiotic strain K7 was spontaneously released from the electrospun sample containing the inulin and probiotic in freeze-dried form (44%), while the amount released from the nanofibrous sample, which also contained the inulin and probiotic in fresh form, was significantly lower (21%). These preliminary results demonstrate the potential of nozzle-free electrospinning technology for the development of probiotic delivery systems for short-term use, such as feminine hygiene materials (tampons, pads, napkins).

Potential of lignin multifunctionality for a sustainable skincare: Impact of emulsification process parameters and oil-phase on the characteristics of O/W Pickering emulsions.

Colloidal lignin particles (CLPs) from softwood kraft lignin were evaluated as a multifunctional ingredient to prepare bio-based oil-in-water (O/W) Pickering emulsions. After a preliminary screening, three Pickering emulsions systems were formulated using orange, coconut, and paraffin oils, at varying concentration of CLPs, oil/water ratio, and by applying two-step homogenisation processes (rotor-stator homogenisation followed by ultrasonication). Ultrasonication as a second homogenisation step considerably enhanced the emulsification efficiency, generating emulsions with smaller droplet size and less polydisperse distribution. Furthermore, the effect of ultrasonication on the characteristics of emulsions and the stability of the systems was evaluated over time. The oil content and type, the concentration of CLPs, and the homogenisation methods significantly influenced the characteristics of the emulsions and drop size. Higher concentrations of oil and CLPs favoured the formation of the emulsion and contributed to higher physical stability after 120 days of monitoring. The in vitro Sun Protection Factor (SPF) results demonstrated that the incorporation of natural oils containing phenolic compounds in Pickering formulations improves the SPF value of emulsions, showing an interesting synergic effect between lignin particles and vegetable oils, which was not observed in the case of paraffin oil. Furthermore, the broad-spectrum sun blocker of Pickering emulsions was confirmed by the values of UVA/UVB between 0.74 and 0.90 and Cλ > 380.

Nanofiltration of the Remaining Whey after Kefir Grains' Cultivation.

Acid whey is derived from fresh cheese. The proteins were isolated by a monolithic ion-exchange column. The remaining whey fraction was used as a starter culture substrate of kefir grains. The aim of this work was, firstly, to study the possibility of column replacement by a UF membrane. If we succeeded, the concentrate would be used as a starter culture substrate of kefir grains. The second part of the research was to purify the remaining solution. The idea was to separate this solution to the permeate and the concentrate by nanofiltration. Further application of both filtration streams was tested as aqueous solutions or dried matter. Chemical and microbiological analyses were performed of both the permeate and the concentrate. The permeate analyses showed that lactose had been fully removed. The aqueous permeate was not stable, mainly due to an increase of total bacteria from 103 to 106 CFU/mL. Therefore, the permeate was spray-dried. The dry permeate was added to the moisture solution in different concentrations. The results showed that up to 0.5% of the dry permeate could be added to the moisturizing solution, with negligible changes in properties having the ability to inhibit acne growth. Anaerobic digestion of industrial sludge was performed with the addition of an aqueous concentrate, which showed improvement in anaerobic fermentation.

The advantages of co-digestion of vegetable oil industry by-products and sewage sludge: Biogas production potential, kinetic analysis and digestate valorisation.

The production of edible vegetable oils generates considerable amounts of energy-rich waste, which is usually not utilised fully. Besides, inefficient management of such wastes can have a negative impact on the environment. On the other hand, this waste can also serve as a raw material for the production of high value-added products, such is biogas. The mono-digestion of seven different by-products and wastes from the vegetable oil industry was investigated in this study: Pumpkin seeds press cake (PSPC), grape seeds press cake (GSPC), olive mill pomace (OMP), coconut oil cake (CC), filtration additive (FA), spent bleaching earth (SBE) and sludge from a vegetable oil industry (SOI) wastewater treatment plant. In addition, co-digestion of these substrates was performed with municipal sewage sludge (SS). Besides inoculum, rumen fluid was added to the reactors to enhance biogas production. The biogas production potential of the tested substrates was monitored by measuring various parameters. A kinetic analysis was later carried out and a growth test was performed on the digestates to evaluate their potential for agricultural use. The highest biogas yields in the mono-digestion test were obtained with the substrates with the highest fat content: 1402, 1288, 830 and 750 mL of biogas/gVS for SOI, FA, PSPC and CC substrate, respectively. Co-digestion of SS with by-products of vegetable oil industry such as FA, SBE, CC, SOI and PSPC increased the biogas yields by 94.9%, 74.1%, 30.8%, 27.4% and 23.6% compared to SS mono-digestion. Furthermore, the data for mono-digestion of PSPC, GSPC, and FA, and co-digestion of SS with these substrates, CC and SBE, have not been found in the literature to date. The maximum methane content ranged from 61 to 74 vol%, while the chemical oxygen demand removal efficiency ranged from 42 to 78%. Relatively high fatty acids contents and ammonium concentrations were measured in the reactors. Kinetic analysis showed the best fit to the experimental data for the Cone kinetic model (R2 > 0.98). The First order kinetic model, Monod, and the modified Gompertz model also exhibited high R2 values. The digestates obtained from co-digestion proved to be excellent in the cress seeds growth test at digestate concentrations of 5-10 wt%, while higher concentrations had a toxic effect.

Reverse Osmosis Treatment of Wastewater for Reuse as Process Water-A Case Study.

The aim of this work was to purify mixed wastewater from three different production processes in such a manner that they could be reused as process water. The maximum allowed concentrations (MAC) from the Environmental Standards for emissions of substances released into surface water were set as target concentrations. Wastewaters contained solid particles, sodium, aluminium, chloride, and nitrogen in high amounts. Quantitatively, most wastewaters were generated in the production line of alumina washing. The second type of wastewater was generated from the production line of boehmite. The third type of wastewater was from regeneration of ion exchangers, which are applied for feed boiler water treatment. The initial treatment step of wastewater mixture was neutralisation, using 35% HCl. The precoat filtration followed, and the level of suspended solids was reduced from 320 mg/L to only 9 mg/L. The concentrations of ions, such as aluminium, sodium and chlorides remained above the MAC. Therefore, laboratory reverse osmosis was applied to remove the listed pollutants from the water. We succeeded in removal of all the pollutants. The concentration of aluminium decreased below 3 mg/L, the sodium to 145 mg/L and chlorides to 193 mg/L. The concentration of nitrate nitrogen decreased below 20 mg/L.

Study of Acid Whey Fouling after Protein Isolation Using Nanofiltration.

In this paper, nanofiltration (NF) of acid whey after isolation of proteins was studied. Two membranes were tested: NF-99 (Alfa Laval) and DL (Osmonic Desal). Based on previous measurements that determined the highest efficiency in separating lactic acid and lactose whey, the pH was adjusted to 3. First, the most appropriate transmembrane pressure (TMP) was determined based on the highest flux measured. The TMP range was 5-25 bar for the DL membrane and 10-30 bar for the NF-99 membrane. The temperature was kept at 4 °C using a thermostat. The mechanisms of membrane fouling were investigated. The Hermia models and the modified Tansel model were applied to study the fouling mechanism and to determine which membrane would foul earlier and more severely, respectively. The most suitable TMP was determined at 20 bar. Despite the 1.4 times higher flux of the sample at DL, the fouling rate was higher when NF-99 was used. The results showed that the Tansel model is suitable for predicting the fouling time of protein-isolated whey by nanofiltration.

Nutrient recovery from the digestate obtained by rumen fluid enhanced anaerobic co-digestion of sewage sludge and cattail: Precipitation by MgCl2 and ion exchange using zeolite.

The aim of this study was to recover nutrients (NPK and other) from the liquid fraction of digestate obtained by rumen fluid enhanced anaerobic co-digestion of sewage sludge and cattail (Typha latifolia grass). Firstly, anaerobic digestion (AD) studies were performed to examine the biogas potential of selected substrates. The liquid fraction of digestate was then used in nutrient recovery experiments. Four methods were applied to recover nutrients: i) conventional struvite precipitation by MgCl2, ii) simultaneous precipitation and ion exchange by Na-zeolite, and iii) two-step recovery using precipitation, followed by ion exchange with powdered or iv) granulated Na-zeolite. The products of nutrient recovery were characterised using different chemical methods and the cress seed germination test was performed to evaluate their fertility potential. The results show that co-digestion of sewage sludge with cattail enhanced biogas production by almost 50 vol%. The addition of rumen fluid positively contributed to the degradation of lignocellulosic materials and to biogas production. In all of the recovery methods tested, phosphorus was successfully recovered with efficiency of more than 99 wt%. Nitrogen recovery was less efficient than phosphorus recovery, 85-92 wt%. Simultaneous precipitation and ion exchange lowered nitrogen recovery efficiency compared to classical struvite precipitation, while sequential precipitation and ion exchange resulted in improvement. The most efficient method was two-step recovery using granulated zeolite. The precipitates consisted of different Mg and K-phosphates in quite irregular shapes. The struvite and K-struvite were detected in low quantities. The precipitates contained more than 25 wt% of macronutrients (NPK), exhibited effective utilization of nutrients by plants, and showed good fertility potential. Precipitate mixed with powdered Na-zeolite promises to be interesting for further agricultural use, as zeolite offers several potential improvements for soil. Both zeolites exhibited good performance in the recovery of K+ ions.

Magnetic nanostructures functionalized with a derived lysine coating applied to simultaneously remove heavy metal pollutants from environmental systems.

The pollution of environmental systems with heavy metals is becoming a serious problem worldwide. These contaminants are one of the main issues in sludge (which is considered waste) and can even have harmful effects if the sludge is not treated properly. Thus, the development of a novel functional magnetic nanoadsorbent based on a derived lysine is reported here, which can be efficiently applied for metal removal from sludge. Magnetic nanoparticles were coated with silica layer and further modified by covalent bonding of derived lysine. The morphology of the nanomaterial, its nano-size and the silica layer thickness were analyzed by transmission electron microscopy. The successful silanization of the lysine derivative to the silica-coated magnetic nanostructures was investigated by several physicochemical characterization techniques, while the magnetic properties were measured with a vibrating sample magnetometer. The synthesized nanostructures were used as adsorbents for simultaneous removal of most critical heavy metals (Cr, Zn, Cu) from real complex sludge suspensions. The main practical adsorption parameters, pH of the native stabilized sludge, adsorbent amount, time, and adsorbent regeneration were investigated. The results show promising adsorption properties among currently available adsorbents (the total equilibrium adsorption capacity was 24.5 mg/g) from the sludge with satisfactory nanoadsorbent reusability and its rapid removal. The stability of the nanoadsorbent in the sludge, an important but often neglected practical parameter for efficient removal, was verified. This work opens up new possibilities for the development of high-quality magnetic nanoadsorbents for metal pollutants applied in various complicated environmental fields and enables waste recovery.

Functionalized Wool as an Efficient and Sustainable Adsorbent for Removal of Zn(II) from an Aqueous Solution.

In this paper, the aim of the research was to obtain a highly efficient wool-based sorbent for the removal of zinc Zn(II) from wastewater. To increase the functional groups for metal binding, the wool was functionalized with chitosan. Chitosan has amino groups through which metals can be complexed easily to chelates. The physical and chemical modification of chitosan on wool was performed to analyze the influence of the coating bond on the final ability of the wool to remove metals. The presence of functional chitosan groups onto wool after adsorption was verified by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FT-IR) spectra. The effective binding of chitosan to wool was also determined by potentiometric and polyelectrolyte titration methods. The latter titration was used to analyze the chitosan desorption. The main part of the study was the sorption of Zn(II) on natural and functionalized wool. The influence was investigated as a function of contact time, pH, metal ion concentration and temperature on the sorption process. The absorbent with the highest concentration of protonated amino groups (607.7 mmol/kg) and responding sorption capacity of 1.52 mg/g was obtained with wool physically modified by a macromolecular chitosan solution (1%) at pH = 7. Adsorption of Zn(II) onto pristine and modified wool corresponded to pseudo-second order kinetics (R2 > 0.9884). The Langmuir model was found to be more suitable (R2 > 0.9866) in comparison to the Freundlich model. The Zn(II) sorption process was spontaneous (∆G < 0) and exothermic (∆H < 0). The results found in this study are significant for escalating the possible use of wool modified with polysaccharide coatings as a sustainable source to improve or increase the metal sorption activity of wool.

A pilot-scale microwave technology for sludge sanitization and drying.

Large volumes of sludge are produced from onsite sanitation systems in densely populated areas (e.g. slums and emergency settlements) and wastewater treatment facilities that contain high amounts of pathogens. There is a need for technological options which can effectively treat the rapidly accumulating sludge under these conditions. This study explored a pilot-scale microwave (MW) based reactor as a possible alternative for rapid sludge treatment. The reactor performance was examined by conducting a series of batch tests using centrifuged waste activated sludge (C-WAS), non-centrifuged waste activated sludge (WAS), faecal sludge (FS), and septic tank sludge (SS). Four kilograms of each sludge type were subjected to MW treatment at a power of 3.4kW for various time durations ranging from 30 to 240min. During the treatment the temperature change, bacteria inactivation (E. coli, coliforms, Staphylococcus aureus, and enterococcus faecalis) and sludge weight/volume reduction were measured. Calorific values (CV) of the dried sludge and the nutrient content (total nitrogen (TN) and total phosphorus (TP)) in both the dried sludge and the condensate were also determined. It was found that MW treatment was successful to achieve a complete bacterial inactivation and a sludge weight/volume reduction above 60%. Besides, the dried sludge and condensate had high energy (≥16MJ/kg) and nutrient contents (solids; TN≥28mg/g TS and TP≥15mg/g TS; condensate TN≥49mg/L TS and TP≥0.2mg/L), having the potential to be used as biofuel, soil conditioner, fertilizer, etc. The MW reactor can be applied for the rapid treatment of sludge in areas such as slums and emergency settlements.

Effect of Chlorella sorokiniana on the biological denitrification of drinking water.

The influence of Chlorella sorokiniana on drinking water's biological denitrification was studied at two different initial nitrate concentrations, 50 and 100 mg/L, respectively. Sucrose and grape juice were used as carbon sources. The experiments showed that the denitrification process in the presence of algae was, even at low concentrations, i.e. 50 mg/L of nitrate, slower than without them, but yet still more than 95% of nitrate was removed in 24 h. It was also discovered that, with the addition of ammonium and urea, the urea interfered much more with the denitrification process, as less than 50% of the initial nitrate was removed. However, algae did not contribute to the nitrate and ammonium removals, as the final concentrations of both in the presence of algae were higher by approx 5%. At 100 mg/L of initial nitrate, the denitrification kinetics in the presence of algae was apparently slower regarding those experiments at lower levels of nitrate and only 65-70% of nitrate was removed over 24 h. Using grape juice instead of sucrose improved the nitrate removal slightly.

Removal Efficiency of COD, Total P and Total N Components from Municipal Wastewater using Hollow-fibre MBR.

The membrane bioreactor (MBR) integrates well within the conventionally activated sludge system regarding advanced membrane separation for wastewater treatment. Over the last decade, a number of MBR systems have been constructed worldwide and this system is now accepted as a technology of choice for wastewater treatment especially for municipal wastewater. The aim of this work was to investigate and compare submerged MBR with conventionally-activated sludge system for the treatment of municipal wastewater in Maribor, Slovenia. It can be concluded from the results, that the efficiencies being determined by the parameters were satisfied, such as, chemical oxygen demand, total phosphorous, and total nitrogen, which were 97%, 75%, and 90%, respectively. The efficiencies of ultrafiltration membrane for the same parameters were also determined, and compared with biological treatment. The results of this analysis show an additional effect regarding an improvement in the quality of the permeate but primary treatment is also very important. For successfully application of MBR system smaller grid for primary treatment is needed.

Comparison between nitrate and pesticide removal from ground water using adsorbents and NF and RO membranes.

An investigation was carried out regarding the removal of pollutants such as nitrate and pesticides (atrazine, deethylatrazine and deisopropylatrazine) from actual ground water samples obtained in Slovenia, by the use of two new adsorption resins, one derived from styrenedivinylbenzene and one from polystyrene, and commercial nanofiltration and reverse osmosis membranes. Atrazine and deethylatrazine were also bound to the activated carbon. Despite the different technologies applied, the effort was directed towards simultaneous removal of the above-mentioned pollutants. According to the results, the first of the mentioned adsorption resins was successfully used for pesticides' removal among the tested adsorption media, whereas the removal of nitrates was unsuccessful. The reverse osmosis membrane displayed a high rejection of all compounds. All concentration values after treatment were below the maximum concentration allowed, while the nanofiltration membrane showed lower compound rejection, thus being suitable for atrazine removal.