Optimization of Cyanocobalamin (Vitamin B12) Sorption onto Mesoporous Superparamagnetic Iron Oxide Nanoparticles.

The techniques used to detect and quantify cyanocobalamin (vitamin B12) vary considerably in terms of detection sensitivity, from the most sensitive, based on radioisotopes and mass spectrometry (MS) with limits of detection (LOD) in fg mL-1, to fluorescence (FL) and surface plasmon resonance (SPR) biosensors with LOD values in the range of a few µg mL-1. For accurate quantification of an analyte present at trace levels in complex biological matrices, a selective separation and enrichment step is required to overcome matrix interferences and ensure sufficient detection sensitivity. In this study, iron oxide magnetic nanoparticles (IONPs) were used for the extraction and initial preconcentration of cyanocobalamin (vitamin B12). In the dependence of the magnetization on the H-field (hysteresis loop), no coercivity and remanence values were found at 300 K, indicating the superparamagnetic properties of the tested IONPs. Perfluorinated acids were used as amphiphilic agents to allow the sorption of cyanocobalamin onto the IONPs. FT-IR/ATR spectroscopy was used to confirm the sorption of cyanocobalamin on the IONPs. The influence of the addition of a homologous series of perfluorinated acids such as trifluoroacetic acid (TFAA), heptafluorobutyric acid (HFBA), and trichloroacetic acid (TCAA) to the extraction mixture was tested considering their type, mass, and time required for effective sorption. The adsorption kinetics and isotherm, described by the Freundlich and Langmuir equations, were analyzed. The maximum adsorption capacity (qm) exceeded 6 mg g-1 and was 8.9 mg g-1 and 7.7 mg g-1 for HFBA and TCAA, respectively, as the most efficient additives. After the desorption process using aqueous KH2PO4 solution, the sample was finally analyzed spectrophotometrically and chromatographically. The IONP-based method was successfully applied for the isolation of cyanocobalamin from human urine samples. The results showed that the developed approach is simple, cheap, accurate, and efficient for the determination of traces of cyanocobalamin in biological matrices.

Mesoporous Silica MCM-41 from Fly Ash as a Support of Bimetallic Cu/Mn Catalysts for Toluene Combustion.

The main outcome of this research was to demonstrate the opportunity to obtain a stable and well-ordered structure of MCM-41 synthesized from fly ash. A series of bimetallic (Cu/Mn) catalysts supported at MCM-41 were prepared via grinding method and investigated in catalytic toluene combustion reaction to show the material's potential application. It was proved, that the Cu/Mn ratio had a crucial effect on the catalytic activity of prepared materials. The best catalytic performance was achieved with sample Cu/Mn(2.5/2.5), for which the temperature of 50% toluene conversion was found to be 300 °C. This value remains in line with the literature reports, for which comparable catalytic activity was attained for 3-fold higher metal loadings. Time-on-stream experiment proved the thermal stability of the investigated catalyst Cu/Mn(2.5/2.5). The obtained results bring a valuable background in the field of fly ash utilization, where fly ash-derived MCM-41 can be considered as efficient and stable support for dispersion of active phase for catalyst preparation.

Selective Removal of Chlorophyll and Isolation of Lutein from Plant Extracts Using Magnetic Solid Phase Extraction with Iron Oxide Nanoparticles.

In recent years, there has been a growing interest in plant pigments as readily available nutraceuticals. Photosynthetic pigments, specifically chlorophylls and carotenoids, renowned for their non-toxic antioxidant properties, are increasingly finding applications beyond their health-promoting attributes. Consequently, there is an ongoing need for cost-effective methods of isolation. This study employs a co-precipitation method to synthesize magnetic iron oxide nanoparticles. Scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) confirms that an aqueous environment and oxidizing conditions yield nanosized iron oxide with particle sizes ranging from 80 to 140 nm. X-ray photoelectron spectroscopy (XPS) spectra indicate the presence of hydrous iron oxide FeO(OH) on the surface of the nanosized iron oxide. The Brunauer-Emmett-Teller (BET) surface area of obtained nanomaterial was 151.4 m2 g-1, with total pore volumes of pores 0.25 cm3 g-1 STP. The material, designated as iron oxide nanoparticles (IONPs), serves as an adsorbent for magnetic solid phase extraction (MSPE) and isolation of photosynthetic pigments (chlorophyll a, lutein) from extracts of higher green plants (Mentha piperita L., Urtica dioica L.). Sorption of chlorophyll a onto the nanoparticles is confirmed using UV-vis spectroscopy, Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS), and high-performance liquid chromatography (HPLC). Selective sorption of chlorophyll a requires a minimum of 3 g of IONPs per 12 mg of chlorophyll a, with acetone as the solvent, and is dependent on a storage time of 48 h. Extended contact time of IONPs with the acetone extract, i.e., 72 h, ensures the elimination of remaining components except lutein, with a spectral purity of 98%, recovered with over 90% efficiency. The mechanism of chlorophyll removal using IONPs relies on the interaction of the pigment's carbonyl (C=O) groups with the adsorbent surface hydroxyl (-OH) groups. Based on molecular dynamics (MD) simulations, it has been proven that the selective adsorption of pigments is also influenced by more favorable dispersion interactions between acetone and chlorophyll in comparison with other solutes. An aqueous environment significantly promotes the removal of pigments; however, it results in a complete loss of selectivity.

Characteristics and Antimicrobial Activities of Iron Oxide Nanoparticles Obtained via Mixed-Mode Chemical/Biogenic Synthesis Using Spent Hop (Humulus lupulus L.) Extracts.

Iron oxide nanoparticles (IONPs) have many practical applications, ranging from environmental protection to biomedicine. IONPs are being investigated due to their high potential for antimicrobial activity and lack of toxicity to humans. However, the biological activity of IONPs is not uniform and depends on the synthesis conditions, which affect the shape, size and surface modification. The aim of this work is to synthesise IONPs using a mixed method, i.e., chemical co-precipitation combined with biogenic surface modification, using extracts from spent hops (Humulus lupulus L.) obtained as waste product from supercritical carbon dioxide hop extraction. Different extracts (water, dimethyl sulfoxide (DMSO), 80% ethanol, acetone, water) were further evaluated for antioxidant activity based on the silver nanoparticle antioxidant capacity (SNPAC), total phenolic content (TPC) and total flavonoid content (TFC). The IONPs were characterised via UV-vis spectroscopy, scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and Fourier-transform infrared (FT-IR) spectroscopy. Spent hop extracts showed a high number of flavonoid compounds. The efficiency of the solvents used for the extraction can be classified as follows: DMSO > 80% ethanol > acetone > water. FT-IR/ATR spectra revealed the involvement of flavonoids such as xanthohumol and/or isoxanthohumol, bitter acids (i.e., humulones, lupulones) and proteins in the surface modification of the IONPs. SEM images showed a granular, spherical structure of the IONPs with diameters ranging from 81.16 to 142.5 nm. Surface modification with extracts generally weakened the activity of the IONPs against the tested Gram-positive and Gram-negative bacteria and yeasts by half. Only the modification of IONPs with DMSO extract improved their antibacterial properties against Gram-positive bacteria (Staphylococcus epidermidis, Staphylococcus aureus, Micrococcus luteus, Enterococcus faecalis, Bacillus cereus) from a MIC value of 2.5-10 mg/mL to 0.313-1.25 mg/mL.

Antimicrobial and Apoptotic Efficacy of Plant-Mediated Silver Nanoparticles.

Phytogenically synthesised nanoparticle (NP)-based drug delivery systems have promising potential in the field of biopharmaceuticals. From the point of view of biomedical applications, such systems offer the small size, high surface area, and possible synergistic effects of NPs with embedded biomolecules. This article describes the synthesis of silver nanoparticles (Ag-NPs) using extracts from the flowers and leaves of tansy (Tanacetum vulgare L.), which is known as a remedy for many health problems, including cancer. The reducing power of the extracts was confirmed by total phenolic and flavonoid content and antioxidant tests. The Ag-NPs were characterised by various analytical techniques including UV-vis spectroscopy, scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), Fourier transform infrared (FT-IR) spectroscopy, and a dynamic light scattering (DLS) system. The obtained Ag-NPs showed higher cytotoxic activity than the initial extracts against both human cervical cancer cell lines HeLa (ATCC CCL-2) and human melanoma cell lines A375 and SK-MEL-3 by MTT assay. However, the high toxicity to Vero cell culture (ATCC CCL-81) and human fibroblast cell line WS-1 rules out the possibility of their use as anticancer agents. The plant-mediated Ag-NPs were mostly bactericidal against tested strains with MBC/MIC index ≤4. Antifungal bioactivity (C. albicans, C. glabrata, and C. parapsilosis) was not observed for aqueous extracts (MIC > 8000 mg L-1), but Ag-NPs synthesised using both the flowers and leaves of tansy were very potent against Candida spp., with MIC 15.6 and 7.8 µg mL-1, respectively.

Optimization of the Composition of Mesoporous Polymer-Ceramic Nanocomposite Granules for Bone Regeneration.

Difficult-to-treat bone damage resulting from metabolic bone diseases, mechanical injuries, or tumor resection requires support in the form of biomaterials. The aim of this research was to optimize the concentration of individual components of polymer-ceramic nanocomposite granules (nanofilled polymer composites) for application in orthopedics and maxillofacial surgery to fill small bone defects and stimulate the regeneration process. Two types of granules were made using nanohydroxyapatite (nanoHA) and chitosan-based matrix (agarose/chitosan or curdlan/chitosan), which served as binder for ceramic nanopowder. Different concentrations of the components (nanoHA and curdlan), foaming agent (sodium bicarbonate-NaHCO3), and chitosan solvent (acetic acid-CH3COOH) were tested during the production process. Agarose and chitosan concentrations were fixed to be 5% w/v and 2% w/v, respectively, based on our previous research. Subsequently, the produced granules were subjected to cytotoxicity testing (indirect and direct contact methods), microhardness testing (Young's modulus evaluation), and microstructure analysis (porosity, specific surface area, and surface roughness) in order to identify the biomaterial with the most favorable properties. The results demonstrated only slight differences among the resultant granules with respect to their microstructural, mechanical, and biological properties. All variants of the biomaterials were non-toxic to a mouse preosteoblast cell line (MC3T3-E1), supported cell growth on their surface, had high porosity (46-51%), and showed relatively high specific surface area (25-33 m2/g) and Young's modulus values (2-10 GPa). Apart from biomaterials containing 8% w/v curdlan, all samples were predominantly characterized by mesoporosity. Nevertheless, materials with the greatest biomedical potential were obtained using 5% w/v agarose, 2% w/v chitosan, and 50% or 70% w/v nanoHA when the chitosan solvent/foaming agent ratio was equal to 2:2. In the case of the granules containing curdlan/chitosan matrix, the most optimal composition was as follows: 2% w/v chitosan, 4% w/v curdlan, and 30% w/v nanoHA. The obtained test results indicate that both manufactured types of granules are promising implantable biomaterials for filling small bone defects that can be used in maxillofacial surgery.

Preparation and Thermo-Mechanical Characteristics of Composites Based on Epoxy Resin with Kaolinite and Clinoptilolite.

Herein the synthesis, characterization, and study of spectroscopic, thermal, and thermo-mechanical properties of polymeric composites are presented. The composites were obtained in special molds (8 × 10 cm) based on the commercially available epoxy resin Epidian® 601 cross-linked by 10% w/w triethylenetetramine (TETA). To improve the thermal and mechanical properties of the synthetic epoxy resins, natural fillers in the form of minerals from the silicate cluster kaolinite (KA) or clinoptilolite (CL) were added to the composites. The structures of the materials obtained were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR/FTIR). The thermal properties of the resins were investigated by differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA) in an inert atmosphere. The hardness of the crosslinked products was determined using the Shore D method. Moreover, strength tests were performed on the 3PB (three-point bending) specimen, with the analysis of tensile strains conducted using the Digital Image Correlation (DIC) technique.

Zeolite Composite Materials from Fly Ash: An Assessment of Physicochemical and Adsorption Properties.

Waste fly ash, with both low (with the addition of vermiculite) and high contents of unburned coal, were subjected to hydrothermal syntheses aiming to obtain zeolite composite materials-zeolite + vermiculite (NaX-Ver) and zeolite + unburned carbon (NaX-C). The composites were compared with parent zeolite obtained from waste fly ash with a low content of unburned carbon (NaX-FA). In this study, the physicochemical characteristics of the obtained materials were evaluated. The potential application of the investigated zeolites for the adsorption of ammonium ions from aqueous solutions was determined. Composite NaX-Ver and parent zeolite NaX-FA were characterized by comparable adsorption capacities toward ammonium ions of 38.46 and 40.00 mg (NH4+) g-1, respectively. The nearly 2-fold lower adsorption capacity of composite NaX-C (21.05 mg (NH4+) g-1) was probably a result of the lower availability of ion exchange sites within the material. Adsorbents were also regenerated using 1 M NaCl solution at a pH of 10 and subjected to 3 cycles of adsorption-desorption experiments, which proved only a small reduction in adsorption properties. This study follows the current trend of waste utilization (fly ash) and the removal of pollutants from aqueous solutions with respect to their reuse, which remains in line with the goals of the circular economy.

Erythromycin Scavenging from Aqueous Solutions by Zeolitic Materials Derived from Fly Ash.

Erythromycin (EA) is an antibiotic whose concentration in water and wastewater has been reported to be above the standard levels. Since the methods used so far to remove EA from aquatic environments have not been effective, the development of effective methods for EA removal is necessary. In the present study, fly ash (FA)-based zeolite materials, which have not been investigated as EA sorbents before, were used. The possibilities of managing waste FA and using its transformation products for EA sorption were presented. The efficiency of EA removal from experimental solutions and real wastewater was evaluated. In addition, the sorbents' mineral composition, chemical composition, and physicochemical properties and the effects of adsorbent mass, contact time, initial EA concentration, and pH on EA removal were analyzed. The EA was removed within the first 2 min of the reaction with an efficiency of 99% from experimental solutions and 94% from real wastewater. The maximum adsorption capacities were 314.7 mg g-1 for the fly ash-based synthetic zeolite (NaP1_FA) and 363.0 mg g-1 for the carbon-zeolite composite (NaP1_C). A fivefold regeneration of the NaP1_FA and NaP1_C showed no significant loss of adsorption efficiency. These findings indicate that zeolitic materials effectively remove EA and can be further investigated for removing other pharmaceuticals from water and wastewater.

A critical review on mechanochemical processing of fly ash and fly ash-derived materials.

Fly ash (FA) is a solid, fine powder that constitutes a by-product obtained when coal, biomass, municipal solid waste or a mixture of these are combusted. This review article focuses on the mechanochemistry of coal fly ash (CFA), as well as highlights the issue of fly ash from municipal solid waste (MSW). In general, FA is regarded as a waste of public concern (since it contains hazardous components), which is primarily consumed in the construction industry, as well as in chemical synthesis and environmental engineering. However, the actual amount of FA recycled is still less than the amount produced, with the reuse rate of only up to 30 %. Due to its relatively low reactivity and heterogeneity, FA is commonly landfilled in huge quantities. Nevertheless, the physical and chemical properties of FA can be tailored, for example, by mechanical forces, ultimately leading to a higher value-added product. Currently, mechanochemistry (MC) is drawing attention in chemical synthesis, pollution remediation and waste management, especially as a possible solution for various drawbacks of conventional syntheses and processes. Mechanochemical processing of FA can be considered eco-friendly, inexpensive and efficient, in particular for processing tons of readily available fly ash already stored in ponds or landfills. With the aim of highlighting the hidden potential and facilitating the favorable use of FA, this article deals with FA as an environmentally challenging material, FA reactivity and recycling through mechanochemical processing, mechanochemical stabilization of heavy metals in FA, as well as up-to-date challenges for life cycle assessment (LCA) in evaluating FA-derived materials. Furthermore, all these full-potential aspects of FA mechanochemistry have not been addressed before, which is a valuable contribution to the existing literature.

Low-cost zeolitic carriers for delivery of hydroxychloroquine immunomodulatory agent with antiviral activity.

The coronavirus pandemic prompted scientists to look for active pharmaceutical ingredients that could be effective in treating COVID-19. One of them was hydroxychloroquine, an antimalarial and immunomodulatory agent exhibiting antiviral activity. The anchoring of this drug on porous carriers enables control of its delivery to a specific place in the body, and thus increases bioavailability. In this work, we developed low-cost zeolitic platforms for hydroxychloroquine. The waste solution generated during zeolite production from fly ashes was used in the synthesis of Na-A and Na-X carriers at laboratory and technical scale. The materials were characterized by high purity and single mineral phase composition. The surface charge of zeolites varied from negative at pH 5.8, and 7.2, to positive at pH 1.2. All samples indicated good sorption ability towards hydroxychloroquine. The mechanism of drug adsorption was based on electrostatic interactions and followed the Freundlich model. Zeolitic carriers modified the hydroxychloroquine release profiles at conditions mimicking the pH of body fluids. The mode of drug liberation was affected by particle size distributions, morphological forms, and chemical compositions of zeolites. The most hydroxychloroquine controlled release at pH 5.8 for the Na-X material was noted, which indicates that it can enhance the drug therapeutic efficacy.

Mechanochemically Assisted Coal Fly Ash Conversion into Zeolite.

Mechanically treated fly ash (FA) was utilised to provide Al and Si atoms for zeolite synthesis. A combination of mechanical fly ash activation and classical hydrothermal synthesis led to favourable dissolution of activated fly ash and improved crystallization of zeolites. The milling activation step induced structural changes in FA to promote its reactivity in alkaline solution. The conversion of milled FA into zeolite materials was finally completed in the second step, during hydrothermal synthesis. The effect of such factors as crystallization temperature, milling time, and solution conditioning were systematically studied. The physicochemical properties characterising the obtained zeolite materials were determined via particle size distribution (PSD), nitrogen adsorption-desorption, X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), and powder X-ray diffraction (XRD). As a result, the best samples achieved a high degree of crystallinity and an extensive specific surface area of 292 m2/g, 87.4 m2/g, 41.9 m2/g for Na-X, Na-P1, and Na-A, respectively. The obtained results provide new and useful data for utilising fly ash resources and synthesising other practical zeolites through an innovative, mechanochemically assisted, and template-free approach.

Use of New Green Bitumen Modifier for Asphalt Mixtures Recycling.

Nowadays, an increasing amount of reclaimed asphalt pavement (RAP) is being produced from the reconstruction and/or modernisation of asphalt pavements. It is necessary to recycle the obtained RAP according to principles of sustainable development. Therefore, this work includes the design of asphalt mixtures containing RAP with bio-derived modifier and evaluates their performance properties. Crosslinked sodium alginate was applied for bitumen modification. The studies were carried out for four different modifier contents, i.e., 1.0%, 2.5%, 4.0% and 5.5%, with and without crosslinking agent. On the basis of the binder test results, the optimal amount of the additive was found to be 2.5%. The nanostructure analysis for the base and modified binders indicated a dual crosslinked biopolymer effect. As a result of the bee structure size decrease, the binder softening effect was observed. The asphalt mix properties showed that application of biopolymer-modified binder is fully justified due to the functional parameters of the mixture, especially the increased resistance to water and frost by about 9%.

Transition Zone Enhancement with Waste Limestone Powder as a Reason for Concrete Compressive Strength Increase.

Modification of concrete with waste materials is an increasingly common process, and they are primarily used as a partial substitution for cement. In the case of inert or nearly inert additions according to EN 206, the effectiveness of such a modification mainly concerns ecological aspects and, only to a small extent, mechanical properties. This article analyses the effect of modifying cement concrete with waste limestone powder as a partial substitution for fine aggregate. The analysed waste arises as a result of the accumulation of dust produced during the initial preparation of aggregate for the production of hot mix asphalt (HMA). In order to analyse the effect of waste on compressive strength, an experimental design was prepared with variable substitution levels and variable water/cement ratios. Compressive strength tests were performed after 28 to 90 days. Statistical analysis of the results was performed. Microscopic evaluation of the fractures of the samples was carried out to clarify the mechanism of transition zone enhancement, which resulted in an increase of compressive strength of the composite.

Functionalization of Zeolite NaP1 for Simultaneous Acid Red 18 and Cu(II) Removal.

The efficiency of azo dye Acid Red 18 (AR18) and Cu(II) ions simultaneous removal from an aqueous solution on NaP1CS and NaP1H was investigated, taking into account the effect of the phase contact time, pH, initial concentration, temperature, and interfering ions presence. Zeolite denoted as NaP1CS was modified by chitosan (CS) and zeolite denoted as NaP1H was modified by hexadecyltrimethylammonium bromide (HDTMA). In order to characterize sorption properties of NaP1CS, the obtained sorbent was characterized using Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption/desorption (ASAP). The kinetic parameters were determined by means of the pseudo first order (PFO), pseudo second order (PSO), and intraparticle diffusion (IPD) kinetic models. To present the adsorption data, three different isotherm models (Langmuir, Freundlich and Dubinin-Radushkevich) were used. The desorption process was also examined. It was found that for sorbent NaP1CS the pseudo second order (PSO) kinetic model and the Langmuir isotherm fitted best the experimental data. Moreover, it was noted that the acidic pH is appropriate to achieve the best sorption properties of NaP1CS for Cu(II) and NaP1H for AR18 and Cu(II). The thermodynamic parameters indicate an endothermic process. The most effective solution for the desorption process was found to be 1 M HCl. The results indicate that simultaneous removal of dye AR18 and Cu(II) on modified zeolite NaP1CS or NaP1H is possible and proceeds with a very good efficiency. The obtained zeolites could effectively adsorb AR18 an Cu(II) simultaneously, but their adsorption abilities were rather different.

Green Synthesis of Silver Nanoparticles Using Natural Extracts with Proven Antioxidant Activity.

Natural extracts are a rich source of biomolecules that are useful not only as antioxidant drugs or diet supplements but also as complex reagents for the biogenic synthesis of metallic nanoparticles. The natural product components can act as strong reducing and capping substrates guaranteeing the stability of formed NPs. The current work demonstrates the suitability of extracts of Camellia sinensis, Ilex paraguariensis, Salvia officinalis, Tilia cordata, Levisticum officinale, Aegopodium podagraria, Urtica dioica, Capsicum baccatum, Viscum album, and marine algae Porphyra Yezoensis for green synthesis of AgNPs. The antioxidant power of methanolic extracts was estimated at the beginning according to their free radical scavenging activity by the DPPH method and reducing power activity by CUPRAC and SNPAC (silver nanoparticle antioxidant capacity) assays. The results obtained by the CUPRAC and SNAPC methods exhibited excellent agreement (R2~0.9). The synthesized AgNPs were characterized by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), dynamic light scattering (DLS) particle size, and zeta potential. The UV-vis absorption spectra showed a peak at 423 nm confirming the presence of AgNPs. The shapes of extract-mediated AgNPs were mainly spherical, spheroid, rod-shaped, agglomerated crystalline structures. The NPs exhibited a high negative zeta potential value in the range from -49.8 mV to -56.1 mV, proving the existence of electrostatic stabilization. FTIR measurements indicated peaks corresponding to different functional groups such as carboxylic acids, alcohol, phenol, esters, ethers, aldehydes, alkanes, and proteins, which were involved in the synthesis and stabilization of AgNPs. Among the examined extracts, green tea showed the highest activity in all antioxidant tests and enabled the synthesis of the smallest nanoparticles, namely 62.51, 61.19, and 53.55 nm, depending on storage times of 30 min, 24 h, and 72 h, respectively. In turn, the Capsicum baccatum extract was distinguished by the lowest zeta potential, decreasing with storage time from -66.0 up to -88.6 mM.

Zeolite NaP1 Functionalization for the Sorption of Metal Complexes with Biodegradable N-(1,2-dicarboxyethyl)-D,L-aspartic Acid.

The possibility of application of chitosan-modified zeolite as sorbent for Cu(II), Zn(II), Mn(II), and Fe(III) ions and their mixtures in the presence of N-(1,2-dicarboxyethyl)-D,L-aspartic acid, IDHA) under different experimental conditions were investigated. Chitosan-modified zeolite belongs to the group of biodegradable complexing agents used in fertilizer production. NaP1CS as a carrier forms a barrier to the spontaneous release of the fertilizer into soil. The obtained materials were characterized by Fourier transform infrared spectroscopy (FTIR); surface area determination (ASAP); scanning electron microscopy (SEM-EDS); X-ray fluorescence (XRF); X-ray diffraction (XRD); and carbon, hydrogen, and nitrogen (CHN), as well as thermogravimetric (TGA) methods. The concentrations of Cu(II), Zn(II), Mn(II), and Fe(III) complexes with IDHA varied from 5-20 mg/dm3 for Cu(II), 10-40 mg/dm3 for Fe(III), 20-80 mg/dm3 for Mn(II), and 10-40 mg/dm3 for Zn(II), respectively; pH value (3-6), time (1-120 min), and temperature (293-333 K) on the sorption efficiency were tested. The Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin adsorption models were applied to describe experimental data. The pH 5 proved to be appropriate for adsorption. The pseudo-second order and Langmuir models were consistent with the experimental data. The thermodynamic parameters indicate that adsorption is spontaneous and endothermic. The highest desorption percentage was achieved using the HCl solution, therefore, proving that method can be used to design slow-release fertilizers.

Brick Debris Dust as an Ecological Filler and Its Effect on the Durability of Asphalt Mix.

Brick debris is one of the main construction wastes obtained from demolition of buildings. However, this material can be successfully used in the recycling process. The purpose of the study was to determine the brick dust addition effect on asphalt surface service life. An asphalt concrete reference mix was designed for bonding layer and prepared using a Marshall compacting device. In addition, three mixes with combined lime-brick filler were prepared as well as one mix containing only brick filler. The samples were tested for their volumetric properties-density, bulk density, air void content, resistance to water and frost and stiffness modulus with varying test temperatures. It was found that 25% of brick dust addition to the filler did not considerably change the properties of the tested samples, while in the case of 50% filler the replacement stiffness and frost resistance decrease; however, the minimum required value is maintained. It can be concluded that the lime filler can be replaced with up to 50% of brick dust without a negative impact on the properties of asphalt mix. The proposed solution fits into the idea of sustainable development indicating a way of brick debris management.

Laboratory Methods for Assessing the Influence of Improper Asphalt Mix Compaction on Its Performance.

Compaction index is one of the most important technological parameters during asphalt pavement construction which may be negatively affected by wrong asphalt paving machine set, weather conditions, or the mix temperature. Presented laboratory study analyzes the asphalt mix properties in case of inappropriate compaction. The reference mix was designed for AC 11 S wearing layer (asphalt concrete for wearing layer with maximum grading of 11 mm). Asphalt mix samples used in the tests were prepared using Marshall device with the compaction energy of 2 × 20, 2 × 35, 2 × 50, and 2 × 75 blows as well as in a roller compactor where the slabs were compacted to various heights: 69.3 mm (+10% of nominal height), 66.2 mm (+5%), 63 mm (nominal), and 59.9 mm (-5%) which resulted in different compaction indexes. Afterwards the samples were cored from the slabs. Both Marshall samples and cores were tested for air void content, stiffness modulus in three temperatures, indirect tensile strength, and resistance to water and frost indicated by ITSR value. It was found that either insufficient or excessive level of compaction can cause negative effect on the road surface performance.

Behavior of Ag species in presence of aquatic sediment minerals - In context of aquatic environmental safety.

In recent years, there has been a growth in the number of products containing Ag nanoparticles (AgNPs) in many areas and their use suggests that the water-soil environment may be exposed to the contaminant with different Ag species. Therefore, the sorption of two Ag forms (i.e. Ag(I) ions and nanoparticles - AgNPs) on clay minerals (montmorillonite and kaolinite) and iron (oxyhydr)oxides (ferrihydrite) as a function of solution:mineral ratio (100:1, 250:1, 500:1), solution pH (3.0, 5.5 and 7.0) and initial Ag concentration (0.1-100 mg/dm3) was studied using batch method. In addition the binding strength/mobility of the bonded Ag species was researched. The results show a great sorption potential of clay minerals for both Ag forms and lower sorption capacity of ferrihydrite, in particular for Ag(I) ions. The maximum sorption capacities of montmorillonite, kaolinite and ferrihydrite estimated from three-parameter isotherm model of Sips were 94.39 mg/g, 117.8 mg/g and 26.48 mg/g for AgNPs and 17.92 mg/g, 21.14 mg/g and 3.072 mg/g for Ag(I) ions, respectively. Aggregation process plays an important role in sorption and mobility of AgNPs. The sequential extraction study indicated different binding mechanisms of the Ag forms onto the clay minerals and ferrihydrite, which depended on the active sites of minerals as well as the Ag species nature in the solution. Ag(I) was weakly bound by clay minerals but presence of iron (oxyhydr)oxides decreased the Ag(I) mobility and bioavailability. On the other hand, AgNPs bound with the active centers of minerals in a very strong way and were not able to release into water. The study of the binding of Ag forms by clay minerals and (oxyhydr)oxides allows to determine the influence of their physicochemical and structural properties, including e.g. pore size on Ag sorption. These results allow these properties to be taken into account in the study of environmental samples, including waters and soils. Moreover, the results showed that in the study of behavior of Ag forms in contact with the minerals, in addition to the sorption capacity, the susceptibility to their release is very important. Studies on sorption/desorption of AgNPs and Ag(I) ions as a form of oxidation of AgNPs is important for understanding the transport and fate of the Ag species in soil, sediments and surface water because of different their behavior in contact with the minerals.