Synthesis and characterization of TiO2-based supported materials for industrial application and recovery in a pilot photocatalytic plant using chemometric approach.

In this contribution, the performance of powdered titanium dioxide (TiO2)-based photocatalysts was evaluated in a pilot photocatalytic plant for the degradation of different dyes, with an investigated volume of 1 L and solar simulated light as irradiation source. Five different samples, synthesized in our laboratories, were tested in the pilot plant, each consisting of TiO2 nanoparticles (NPs) coupled with a different material (persistent luminescent material and semiconductor material) and treated in different thermal conditions. All synthesized samples have been subjected to X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller analysis (BET), and transmission electron microscopy (TEM) characterization, to shed light on the influence of introducing other materials on titania characteristics. To study and evaluate the significance of the parameters affecting the process in the pilot plant, a chemometric approach was applied, by selecting a mathematical model (D-Optimal) to simultaneously monitor a large number of variables (i.e., 7), both qualitative and quantitative, over a wide range of levels. At the same time, the recovery of the synthesized photocatalysts was studied following a novel promising recuperation method, i.e., annulling the surface charge of the suspended samples by reaching the isoelectric point (pHPZC) of each sample, for the quantitative precipitation of TiO2 nanoparticles.

Effects of the physical structure and surface charge of activated carbon on the reduction of biogenic amines in anchovy fish sauce.

This study aimed to efficiently reduce a large number of biogenic amines in salt-fermented fish sauce while minimizing sensory reduction using various activated carbons. Aromatic amines, such as tryptamine and phenethylamine, were reduced by 86.1-100 % after treating with activated carbon. Histamine with a heterocyclic structure decreased by 13-42 %. No significant effects were observed on the levels of aliphatic amines, putrescine, cadaverine, spermine, and spermidine. The major taste component, amino acid nitrogen, was reduced to within 3 %, and brown color removal was reduced depending on the type of activated carbon used. Acid-modified AC-A and AC-B had rough surfaces, high total acidity, low point of zero charge (pHpzc), and rich surface functional groups. Owing to its smooth surface, low total acidity, high pHpzc, and few surface functional groups, AC-C exhibited a higher histamine elimination and less color reduction despite its lower surface area compared to other activated carbons.

Effects of aging methods on the adsorption of antibiotics in wastewater by soybean straw biochar.

BACKGROUND: The environmental pollution and ecological risks caused by the widespread use of antibiotics have attracted attention in recent years. Biochar materials have a rich pore diameter and can effectively adsorb pollutants from wastewater. However, biochar will experience high temperatures, freezing and thawing in nature, affecting its physicochemical properties and adsorption capacity. Three types of aged biochar were prepared by artificial simulated aging using soybean straw as raw material. The aged biochar's elemental composition and functional group species were investigated by characterization analysis, and their adsorption kinetics and adsorption isotherms were studied. RESULTS: The specific surface area and pore size of the three aged biochars were lower than those of fresh biochars. The increased number of oxygen-containing functional groups of the aged biochars formed a water cluster interaction with norfloxacin (NOR), which was unfavorable to the adsorption of NOR. The adsorption mechanism of biochar on NOR comprises pore filling, electrostatic interaction, ion exchange and complexation. CONCLUSION: The adsorption of NOR on biochar before and after aging was spontaneous and was described by quasi-second kinetics and the Langmuir equation. Different aging methods influenced the physicochemical properties and adsorption performance of biochar, and the adsorption capacity of biochar was significantly reduced after aging. Therefore, the influence of climatic factors needs to be considered when using biochar to remove target pollutants. © 2023 Society of Chemical Industry.

The pH dependent surface charging and points of zero charge. X. Update.

Surfaces are often characterized by their points of zero charge (PZC) and isoelectric points (IEP). Different authors use these terms for different quantities, which may be equal to the actual PZC under certain conditions. Several popular methods lead to results which are inappropriately termed PZC. This present review is limited to zero-points obtained in the presence of inert electrolytes (halides, nitrates, and perchlorates of the 1st group metals). IEP are reported for all kinds of materials. PZC of metal oxides obtained as common intersection points of potentiometric curves for 3 or more ionic strengths (or by means of equivalent methods) are also reported, while the apparent PZC obtained by mass titration, pH-drift method, etc. are deliberately neglected. The results published in the recent publications and older results overlooked in the previous compilations by the same author are reported. The PZC/IEP are accompanied by information on the temperature and on the nature and concentration of supporting electrolyte (if available). The references to previous reviews by the same author allow to compare the newest results with the PZC/IEP of similar materials from the older literature.

Atomic force and infrared spectroscopic studies on the role of surface charge for the anti-biofouling properties of polydopamine films.

Antibacterial polymer materials have gained interest due to their capability to inhibit or eradicate biofilms with greater efficiency in comparison with their monomeric counterparts. Among the antimicrobial and anti-biofouling polymers, catecholamine-based polymers - and in particular polydopamine - have been studied due to their favorable adhesion properties, which can be tuned by controlling the pH value. In this study, we used atomic force microscopy (AFM)-based spectroscopy to investigate the relation between the adhesion properties and surface charge density and the pH of electrochemically deposited polydopamine films presenting a dissociation constant of polydopamine of 6.3 ± 0.2 and a point of zero charge of 5.37 ± 0.06. Furthermore, using AFM and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), the influence of the surface charge density of polydopamine on bacterial adhesion and biofilm formation was investigated. It was shown that the adhesion of Escherichia coli at positively charged polydopamine is three times higher compared to a negatively charged polymer, and that the formation of biofilms is favored at positively charged polymers.

Solid leather wastes as adsorbents for cationic and anionic dye removal.

The removal of anionic and cationic dyes from aqueous solutions was investigated by different leather shavings, which are solid wastes generated in the leather industry. Wet-blue leather shavings (WB), vegetable-tanned leather shavings (VT), pickled hide (not tanned) shavings (PIC) and wet-white leather (pre-tanned) shavings (WW) were used. The cationic dye was Basic Red 2 and the anionic dye was Acid Brown 414. Point of zero charge, functional groups, shrinkage temperature and adsorbent surface area were characterized. The point of zero charge was 4.0, 6.0, 3.9 and 4.1 for WB, VT, PIC and WW, respectively. The specific surface area showed low values which was expected for this type of material. Tanning agent influence was verified through shrinkage temperature analysis of leather shavings. Main functional groups of the acid dye and the collagen structure of the solid wastes were determined. The tests with Basic Red 2 solutions showed only VT had a considerable removal for this cationic dye (96.7%). The tests with Acid Brown 414 were carried out with different contact times and adsorbent mass. Results showed high efficiency of WW and PIC, whose percentages of dye removal were above 96% at contact time of 30 min and above 90% using 20 mg of adsorbent. In this way, the final dye removal was 98.1% and 98.3% for contact time tests and 97.7% and 98% for adsorbent mass tests for WW and PIC, respectively. These results highlight the promising use of leather shavings as alternative adsorbents for the treatment of wastewater containing dyes.

Post-fabrication structural changes and enhanced photodegradation activity of semiconductors@zeolite composites towards noxious contaminants.

This review article provides the recent progress in semiconductor-based zeolite photoactive materials for the application of noxious contaminants removal. The rapidly expanding industrialization and globalization cause serious threats to the environment or water bodies. The semiconductor@zeolite photocatalysts were implemented for water quality management/sustainment. The exclusive properties of zeolite material have been elaborated with their role in the photocatalysis process. The photoactive material's properties like single-atom catalysts (SACs), distribution of metal in the zeolite crystal were elaborated along with their role in catalytic reactions. Differently prepared semiconductor@zeolite composites such as TiO2@zeolite, binary and ternary composites, Fe/Ag/bismuth-modified/ZnO/ZnS/NiO/g-C3N4/core-shell/quantum dots modified zeolite composites, were systematically summarized. The research progress in morphologies, structural effect, degradation mechanism were recapitulated and tabulated form of % degradation with their optimal parameters such as catalyst dose, pollutant concentrations, pH, light source intensities were also provided. The significance of zeolite frameworks, the structural properties of semiconductor@zeolite photoactive materials to enhance the degradation efficiencies was explored. Analysis of the intermediate products of Norfloxacin, TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin), TCDF (2,3,7,8-tetrachlorodibenzofuran), diclofenac contaminants were systematically represented and structurally identified by GC-MS/HPLC-MS techniques.

The pH dependent surface charging and points of zero charge. IX. Update.

of the points of zero charge (PZC) and isoelectric points (IEP) of various materials published in the recent literature and of older results overlooked in the previous compilations. The roles of experimental conditions, especially of the temperature, of the nature and concentration of supporting electrolyte, and of the type of apparatus are emphasized. The newest results are compared with the zero points reported in previous reviews. Most recent studies were carried out with materials whose pH dependent surface charging is already well-documented, and the newest results are consistent with the older literature. Isoelectric points of Gd(OH)3, Sm(OH)3, and TeO2 have been reported for the first time in the recent literature.

Investigation of Adsorption Behavior of Anticancer Drug on Zinc Oxide Nanoparticles: A Solid State NMR and Cyclic Voltammetry (CV) Analysis.

The present study aims to comprehend the adsorption behavior of a set of anticancer drugs namely 5-fluorouracil (5-FU), doxorubicin and daunorubicin on ZnO nanoparticles (ZnO NPs) proposed as drug delivery systems employing solid state (ss) NMR, FTIR and Cyclic Voltammetry (CV) analysis. FTIR and 1H MAS ssNMR data recorded for bare ZnO nanoparticle confirmed the presence of adsorbed -OH groups on the surface. 13C CP-MAS NMR spectra recorded for free and ZnO surface adsorbed drug samples exhibited considerable line broadening and chemical shift changes that complemented our earlier report on UV-DRS and XRD data of surface adsorption in case of 5-FU. Moreover, a remarkable enhancement of 13C signal intensity in case of loaded 5-FU was observed. This clearly indicated rigid nature of the drug on the surface allowing efficient transfer of 1H polarization from the hetero nitrogen of 5-FU to ZnO to form surface hydroxyl (-OH) groups and the same has been observed in the quantum chemical calculations. To further analyze the motional dynamics of the surface adsorbed 5-FU, longitudinal relaxation times (T1) were quantified employing Torchia method that revealed significant enhancement of 13C relaxation rate of adsorbed 5-FU. The enhanced rate suggested an effective role of quadrupolar contribution from 67Zn to the 13C relaxation mechanism of ZnO_5-FU. The heterogeneous rate constant (khet), average free energy of activation (∆G≠) and point of zero charge (PZC) measured for free and drug loaded ZnO NPs samples using CV further support the SS-NMR results.

The Isoelectric Point of an Exotic Oxide: Tellurium (IV) Oxide.

The pH-dependent surface charging of tellurium (IV) oxide has been studied. The isoelectric point (IEP) of tellurium (IV) oxide was determined by microelectrophoresis in various 1-1 electrolytes over a concentration range of 0.001-0.1 M. In all electrolytes studied and irrespective of their concentration the zeta potential of TeO2 was negative over the pH range 3-12. In other words the IEP of TeO2 is at pH below 3 (if any). TeO2 specifically adsorbs ionic surfactants, and their presence strongly affects the zeta potential. In contrast the effect of multivalent inorganic ions on the zeta potential of TeO2 is rather insignificant (no shift in the IEP). In this respect TeO2 is very different from metal oxides.

Investigation of water treatment sludge from drinking water treated with Zetafloc 553I coagulant for phosphorus removal from wastewater.

Water treatment sludge have shown promising results as adsorbent for phosphorus and sulphate removal from real wastewater. The study was conducted through batch kinetics and equilibrium isotherm modes. The chemical composition reveal that aluminium compounds were dominant in the fresh sludge and aluminium phosphates were also observed in the used sludge. The results reveal that Manganese was leached from the material at all pH values investigated with the highest level observed at pH 2 and all concentrations higher than the national standard of discharge into the relevant environment. The point of zero charge of the adsorbent was pH 8.04 and high adsorption capacities for both sulphate and phosphate ions were observed at pH values lower than this point. Batch kinetic results revealed 96.0 ± 3.0% sulphates removal in the first 30 min whereas the highest phosphates removal was 88.0 ± 4.0% attained at 300 min of the experiment. Pseudo - second order reaction fitted the data better than Pseudo-first order reaction. The percentage removal of sulphates was observed decreasing with increasing adsorbent dose after 2.4 g dose but removal increased with increasing media dosage for phosphorus. The equilibrium data was better described by Freundlich isotherm with constants relating to adsorption capacities being 6.76 and 6.2 L g-1 respectively, for sulphates and phosphates adsorption. The adsorption capacity of phosphates was observed decreasing with increasing temperature, but the results were not conclusive in the case of sulphates. The results reveal that copper, nickel, and zinc have affinity for sulphates. The water treatment sludge can be used for phosphate and sulphate removal from wastewater though the leachability of manganese is a concern. Further investigations through fixed bed columns will need to be investigated before field trials. In conclusion, the sludge can be used as adsorbent for phosphorus and sulphates removal from wastewater through filtration and onsite treatment methods such as vertical or horizontal flow wetland systems. The success of the adsorbent will reduce the costs associated with its disposal which can also lead to leachability of metals into the environment with time.

Improved Virus Isoelectric Point Estimation by Exclusion of Known and Predicted Genome-Binding Regions.

Knowledge of the isoelectric points (pIs) of viruses is beneficial for predicting virus behavior in environmental transport and physical/chemical treatment applications. However, the empirically measured pIs of many viruses have thus far defied simple explanation, let alone prediction, based on the ionizable amino acid composition of the virus capsid. Here, we suggest an approach for predicting the pI of nonenveloped viruses by excluding capsid regions that stabilize the virus polynucleotide via electrostatic interactions. This method was applied first to viruses with known polynucleotide-binding regions (PBRs) and/or three-dimensional (3D) structures. Then, PBRs were predicted in a group of 32 unique viral capsid proteome sequences via conserved structures and sequence motifs. Removing predicted PBRs resulted in a significantly better fit to empirical pI values. After modification, mean differences between theoretical and empirical pI values were reduced from 2.1 ± 2.4 to 0.1 ± 1.7 pH units.IMPORTANCE This model fits predicted pIs to empirical values for a diverse set of viruses. The results suggest that many previously reported discrepancies between theoretical and empirical virus pIs can be explained by coulombic neutralization of PBRs of the inner capsid. Given the diversity of virus capsid structures, this nonarbitrary, heuristic approach to predicting virus pI offers an effective alternative to a simplistic, one-size-fits-all charge model of the virion. The accurate, structure-based prediction of PBRs of the virus capsid employed here may also be of general interest to structural virologists.

Comments on "Fast and efficient removal of Cr(VI) to ppb level together with Cr(III) sequestration in water using layered double hydroxide interclated with diethyldithiocarbamate".

This paper primarily aimed to provide some concerns and continue discussion about the previous published paper in this journal. First, when the mechanism of Cr(VI) removal from solution involved in adsorption-coupled reduction was proposed, the X-ray photoelectron spectroscopy (XPS) of Cr 2p spectrum of laden adsorbent (i.e., DDTC-LDH after adsorption) needs to demonstrate the co-existence of Cr(VI) and Cr(III). The detection of reduced Cr(III) in solution after the completed adsorption of Cr(VI) only provides information on the mechanism regarding reduction, not adsorption-coupled reduction. Second, adsorption mechanism (chemisorption or physisorption) cannot be drawn only based on the best statistical fit between the time-dependent data of adsorption experiment and the kinetic model (i.e., the pseudo-second-order, Elovich, or Avrami model). Third, the constant KRP (liters per grams of adsorbent not adsorbate; L/g) of the Redlich-Peterson isotherm model is not equal to or used as the thermodynamic equilibrium constant KEqo. The application of the constant KRP for calculating the thermodynamic parameters of adsorption process (∆G°, ∆H°, and ∆G°) using the van't Hoff equation leads to a certain error in the values (sign and magnitude) of those parameters. Fourth, the pHPZC of adsorbent is significant different to its pHIEP on both meanings and analysis methods. The use of those terminologies in the fields of material and sorption (adsorption and absorption) must be correct. Finally, some important information needs to provide in the studies of adsorption isotherm and mechanism (i.e., solution pH) and characteristics of diethyldithiocarbamate intercalated-LDH (i.e., arrangement and orientation of diethyldithiocarbamate in the interlayer region of DDTC-LDH).

Comments on "High-efficiency removal of dyes from wastewater by fully recycling litchi peel biochar".

This paper provided further discussion on some identified mistakes and inconsistencies. Such problems included (1) the determination and discussion on the pHPZC value of the biochar, (2) the excellent adsorption capacity of the biochar toward the dye contaminant, (3) the proposd adsorption mechanism (i.e., chemical adsorption) only based on the best fitting of the experimental data to the kinetic model (i.e., the pseudo-second-order or Elovich model), (4) the conception on the Freundlich model, and (5) the presentation of the adsorption mechanism involved in hydrogen bonding. Some other potential problems regarding the determination of adsorption capacity of an adsorbent towards an adsorbate (qe; mg/g) were additionally discussed herein. It gives readers a gentle reminder that the initial concentration of adsorbate (also known as the blank sample; Co) always plays a vital role in accurately calculating the qe value. The Co value from experiment (i.e., 254 mg/L or 245 mg/L) is often dissimilar to the Co value from theory (i.e., 250 mg/L). The difference becomes enormously significant when the Co value reaches very high concentration (i.e., 1000 mg/L) because an extremely high dilution factor is applied to determine the concentration of adsorbate in solution. The author hopes that the comments and contents in this paper will be particularly helpful for other researchers who are interested in the field of adsorption science and technology. Some highly-readable recent publications, which comprise the different types of paper as "comment", "discussion", "perspective", and "critical review", have also introduced in this paper. The expert reviewers and editors should give a great concern to such problems for further evaluations of submitted manuscripts in the field.

Some Properties of Electron Beam-Irradiated Sheep Wool Linked to Cr(III) Sorption.

We examined the characteristics of an electron beam irradiated wool with an absorbed dose of (21-410) kGy in comparison with natural wool with respect to the determination of the isoelectric point (IEP), zero charge point (ZCP), mechanism of Cr(III) sorption from higher concentrated solutions, and the modelling of the wool-Cr(III) interaction. The data of ZPC and IEP differed between natural and irradiated samples. Increasing the dose shifted the pH of ZPC from 6.85 for natural wool to 6.20 for the highest dosed wool, while the natural wool IEP moved very little, from pH = 3.35 to 3.40 for all of the irradiated samples. The sorption experiments were performed in a pH bath set at 3.40, and the determination of the residual Cr(III) in the bath was performed by VIS spectrometry under optimized conditions. The resulting sorptivity showed a monotonically rising trend with increasing Cr(III) concentration in the bath. Lower doses, unlike higher doses, showed better sorptivity than the natural wool. FTIR data indicated the formation of complex chromite salts of carboxylates and cysteinates. Crosslinks via ligands coming from different keratin chains were predicted, preferably on the surface of the fibers, but to a degree that did not yet inhibit the diffusion of Cr(III)-cations into the fiber volume. We also present a concept of a complex octahedral structure.

Electrokinetic mobility, pH and conductance/conductivity data for aqueous silica and PTFE suspension of controlled composition for selected temperature ranges.

The Data in Brief contains data on the electrokinetic mobility of PTFE and silica particles in aqueous suspensions as a function of pH and temperature. Furthermore, the concomitant conductivities and pH values are reported both for systems in the absence and presence of PTFE particles as a function of temperature and are compatible with the associated research paper "The influence of temperature on the charging of Polytetrafluoroethylene surfaces in electrolyte solutions" (Barisic et al.). The trend of the electrokinetic charging with temperature can be inferred from this for both kinds of particles. The data on the evolution of the pH and the measured conductivities are valuable input for future models that simulate the charge of inert surfaces at variable temperature.

Biofilm microbial composition changes due to different surface chemical modifications of activated carbon cloths in the biotransformation of 4-nitrophenol.

Activated carbon cloths (ACCs) were used as biofilms supports in the anaerobic biotransformation of 4-nitrophenol (4NP). As received ACC material (AW) was oxidized with HNO3 (OX) and then functionalized with anthraquinone-2,6-disulfonate (AQ). The three ACCs were packed in hybrid UASB reactors and seeded with anaerobic granular sludge for biotransformation experiments. The results indicated that ACC-packed bioreactors improved the biotransformation of 4NP by twofold as compared to the control reactor without support materials. However, the biotransformation effciency of AW, OX and AQ was very similar (59%), indicating the role of ACC as biofilm support and not as redox mediator. After 4NP biotransformation several physicochemical and biological changes were observed like (1) the point of zero charge (pHPZC) shift from acidic values (AW = 5.0, OX = 3.4, AQ = 3.1) to neutral values (pHPZC = 7.6 on average), (2) increase in the concentration of acidic and basic surface functional groups over ACC materials and the amount of supported biomass on ACCs due to biofilm formation, and (3) enrichment of exoelectrogenic microorganisms belonging to the genera Geobacter over carbonyl-rich ACC surface as revealed by 16S rRNA amplicon sequencing. Overall, the results suggest that chemical modifications of ACCs changed the microbial composition of the biofilm, but the higher concentration of carbonyl groups on ACC did not affect the biotransformation of 4NP.

Influence of electro-osmosis on physicochemical parameters and microstructure of clay soils.

The change in properties and structure of clay soils due to electro-osmosis was studied. These alterations were exemplified by mantle loam and kaolin. It is shown that electro-osmotic treatment of the soils on the open scheme resulted in the transformations in their moisture content, total and dry density, salinity, pH, and the parameters of their particles. The most notable changes occurred within the diffuse double layers (DDLs) of soil particles such as their recharge in the anodic zone. The transformations of the loam particles DDLs resulted in their aggregation in the cathodic and anodic zones. Also, electro-osmotic flow caused the redistribution of pore sizes within the soils between the electrodes. In the case of the kaolin, electro-osmosis resulted in the formation of the anisotropic, flow-oriented structure. The change in the types of soil particles contacts formed was observed during electro-osmosis as well. The obtained data can be used to study the behavior of soil during electro-osmosis as a function of the soil type.

Regulation of clay particles charge for design of protective electrokinetic barriers.

Coupled electrokinetic protective reactive barriers (PRB) are considered as a perspective technology for the treatment of contaminated groundwater. Design of PRB is directly connected with a problem of barrier material choice. Clays can be considered as an appropriate material due to high adsorptive properties and relative cheapness. The barrier internals are formed by clay surface charge properties. We revealed that acidic and alkaline treatment of clay is an effective way to affect its protective properties so that clay can be used to treat various pollutants. Surface charge and electrokinetic properties of clays were characterized by point of zero charge (p.z.c.), point of zero net proton charge (p.z.n.p.c.) and ζ-potential at different pH. Suspensions of 3 main clay types were studied by microelectrophoresis and potentiometric titration methods. At pH > p.z.n.p.c. clayey barrier adsorbs predominantly cationic toxicants and at pH < p.z.c. - anionic ones. The barrier is seemed to be the least effective in pH range between p.z.c. and p.z.n.p.c. Given the physicochemical and electrokinetic parameters, the most efficient clays for barrier design are Cambrian illite and all montmorillonite clays.

Effect of preconditioning on silver leaching and bromide removal properties of silver-impregnated activated carbon (SIAC).

Silver impregnated activated carbon (SIAC) has been found to be effective in mitigating the formation of brominated-disinfection by products during drinking water treatment. However, there are still uncertainties regarding its silver leaching properties, and strategies for the prevention of silver leaching have remained elusive. This study focused on the evaluation of one type of commercially available SIAC for its ability to remove bromide while minimising silver leaching from the material. Both synthetic and real water matrices were tested. Depending on solution pH, it was found that changing the surface charge properties of SIAC, as measured by the point of zero charge pH, can result in additional bromide removal while minimising the extent of silver leaching. To better understand the mechanism of silver leaching from the SIAC, eight preconditioning environments, i.e. variable pH and ionic strength were tested for a fixed amount of SIAC and two preconditioning environments were selected for a more detailed investigation. Experiments carried out in synthetic water showed that preconditioning at pH 10.4 did not deteriorate the capacity of SIAC to remove bromide, but significantly decreased the release of silver in the form of ionic silver (Ag+), silver bromide (AgBr) and silver chloride (AgCl) from 40% for the pristine to 3% for the treated SIAC. This was confirmed using a groundwater sample. These results suggest that preconditioned SIAC has the potential to be an effective method for bromide removal with minimised silver leaching in a long-term field application for drinking water production.