Municipal Sewage Sludge as a Source for Obtaining Efficient Biosorbents: Analysis of Pyrolysis Products and Adsorption Tests.

In the 21st century, the development of industry and population growth have significantly increased the amount of sewage sludge produced. It is a by-product of wastewater treatment, which requires appropriate management due to biological and chemical hazards, as well as several legal regulations. The pyrolysis of sewage sludge to biochar can become an effective way to neutralise and use waste. Tests were carried out to determine the effect of pyrolysis conditions, such as time and temperature, on the properties and composition of the products obtained and the sorption capacity of the generated biochar. Fourier transform infrared analysis (FTIR) showed that the main components of the produced gas phase were CO2, CO, CH4 and to a lesser extent volatile organic compounds. In tar, compounds of mainly anthropogenic origin were identified using gas chromatography mass spectrometry (GC-MS). The efficiency of obtaining biochars ranged from 44% to 50%. An increase in the pyrolysis temperature resulted in a decreased amount of biochar produced while improving its physicochemical properties. The biochar obtained at high temperatures showed the good adsorption capacity of Cu2+ (26 mg·g-1) and Zn2+ (21 mg·g-1) cations, which indicates that it can compete with similar sorbents. Adsorption of Cu2+ and Zn2+ proceeded according to the pseudo-second-order kinetic model and the Langmuir isotherm model. The biosorbent obtained from sewage sludge can be successfully used for the separation of metal cations from water and technological wastewater or be the basis for producing modified and mixed carbon sorbents.

Sustainable Management of Calcite Contaminated with Waste Toner Powder in the Construction Industry.

Due to the highly explosive nature of toners, absorbers are used in toner processing plants to prevent the explosion of toner dust suspension in the air. Usually, finely divided calcite (in the form of a dust) is used. The mixture of toner-calcite is treated as waste and landfilled. The main aim of this study was to investigate the possibility of using toner-contaminated calcite as an additive to concrete. Materials originating from the toner processing plant were analyzed by using TGA, AAS, XRD, FTIR and SEM techniques. Calcite-waste toner powder mixture in amounts 0%, 1%, 5%, 10%, 15% and 20% were used to produce concrete. The results of the study showed that an increase in the amount of calcite contaminated with toner to 20% causes a decrease in compressive strength of concrete by 24-51% depending on material sample. The addition of calcite in amounts up to 5% can be a suitable method of its management.

A New Approach to the Determination of Silicon in Zinc, Lead-Bearing Materials and in Waste Using the ICP-OES Method.

This work describes the implementation of the ICP-OES silicon determination method for zinc and lead-bearing materials and waste at the Mining and Metallurgical Works ZGH "Boleslaw". The proposed method was validated. On the basis of linearity tests, it was found that the course of the calibration curve is linear up to a silicon concentration of 100 mg/L, with the determined working range being 0.10-50%. Precision tests, on the basis of which the repeatability was checked, were carried out for nine types of real samples: zinc sulfides, zinc oxides, zinc-lead ore, lead sulfide and zinc-bearing waste. Real samples and six certified reference materials were tested using the ICP-OES radial position. The identified interferences of molybdenum, chromium and vanadium did not statistically significantly affect the measurement results.

Effect of sewage sludge-based fertilizers on biomass growth and heavy metal accumulation in plants.

This study was focused on an assessment of the agronomic efficiency of organo-mineral fertilizers based on sewage sludge and possible accumulation of heavy metals in plant biomass. Fertilizers optimized for industrial crops (rape, maize, sunflower) were used in the study. The impact of fertilizers based on sewage sludge on early stage plant growth was assessed using germination tests, and the impact on further growth and development was assessed using pot trials. The germination index of cress, sorghum and mustard was in the range of 50-92% depending on the type and dose of fertilizer and on the plant tested, which corresponded to moderate to zero toxicity. The results of pot trials showed a significant impact of fertilizers based on sewage sludge on the biomass growth of selected plants. The use of fertilizers caused an increase in fresh mass of 75-138% for rape, 96-138% for maize and 23-54% for sunflower with respect to the control sample. An increase in the dose of fertilizers for rape did not significantly affect the heavy metal content in plants, except for the content of Ni. In the case of fertilizers optimized for maize and sunflower, an increase in the dose caused an accumulation of Cd, Ni, Pb and Cr in the biomass of the tested plants. However, it should be noted that the pollution level of plant biomass for all treatments was zero to medium (1.00-1.66).

Tannery waste-derived biochar as a carrier of micronutrients essential to plants.

The leather tannery industry generates about 33 Mt/year of solid waste with different properties, turning its management into a challenge. One of the valorization methods of tannery wastes is the production of biochar by pyrolysis of leather scratches. Biochar's sorption properties and its high nitrogen content (10%) make it suitable for its application as a soil conditioner or carrier of microelements for fertilizers. The paper presents an innovative spray method to enrich biochar with cationic micronutrients: Cu, Mn, Zn. Enriched biochar contained 1095 mg/kg Cu(II), 1334 mg/kg Mn(II) and 1205 mg/kg Zn(II). The high bioavailability of nutrients and the effectiveness of the new fertilizer were demonstrated in extraction in vitro tests - the analysis of leachability of elements to water and bioavailability of micro-nutrients. The functional properties of enriched biochar were examined in vivo (germination, pot) tests. A high biomass increase (approximately 10%) was observed compared to the group fertilized with a commercial product. The proposed solution benefits the environment in that it is made from alternative resources from which innovative fertilizers are produced according to the circular economy concept.

Formulation and evaluation of organo-mineral fertilizers based on sewage sludge optimized for maize and sunflower crops.

The depletion of natural resources, energy consumption and environmental issues relating to fertilizer production processes are driving a move towards a more sustainable use of resources and the recycling of nutrients. With regard to the fertilizer industry, this gives the opportunity to use the fertilizing potential of alternative raw materials. This paper evaluates the possibility of using dried sewage sludge in the manufacture of organo-mineral fertilizers. Fertilizers based on sewage sludge with an addition of poultry litter ash and mineral fertilizers were developed and characterized in the study. It was possible to produce multicomponent organo-mineral fertilizers with optimized compositions for maize and sunflower crops, characterized by total nutrient content over 20%. Moreover, they contained beneficial secondary nutrients and micronutrients originated from waste materials. The fertilizers were free of pathogens and fulfilled the requirements related to heavy metal content according to Polish legislation. The method of manufacturing organo-mineral fertilizers based on waste materials is a simple waste management solution offering organic matter and nutrient recycling in line with the circular economy and reducing reliance on imported raw materials.

Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline.

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.

Potentiality of sewage sludge-based organo-mineral fertilizer production in Poland considering nutrient value, heavy metal content and phytotoxicity for rapeseed crops.

Sewage sludge is a valuable source of nutrients and organic matter, which are beneficial for plant growth. The use of sewage sludge for agricultural purposes can be limited by the potential content of heavy metals and toxic organic compounds that pose a threat to the environment. The characterisation of sewage sludges from 11 Polish wastewater treatment plants (WWTPs) in terms of their fertilizing properties and heavy metal contents are presented in the study. Based on the chemical composition of sewage sludge from the WWTP in Zywiec, the compositions of organo-mineral fertilizers dedicated for rapeseed crop was developed. Alternative raw materials such as poultry litter ash and biomass ash were considered as components for fertilizer production. The production process of organo-mineral fertilizers included mixing sewage sludge with poultry litter ash/biomass ash and mineral fertilizers and granulation with mineral acids. The final products contained 24-34% of total NPK and fulfilled the requirements regarding heavy metal content according to Polish legislation. Using sewage sludge for fertilizer production is a promising solution for sewage sludge management, allowing the recycling of 82-140 tonnes of phosphorus (as P2O5) and 42-73 tonnes of nitrogen (N) annually in the WWTP in Zywiec.

Fertilisers production from ashes after sewage sludge combustion - A strategy towards sustainable development.

Sustainable development and circular economy rules force the global fertilizer industry to develop new phosphorous recovery methods from alternative sources. In this paper a phosphorus recovery technology from Polish industrial Sewage Sludge Ashes was investigated (PolFerAsh - Polish Fertilizers form Ash). A wet method with the use of mineral acid and neutralization was proposed. Detailed characteristic of SSA from largest mono-combustion plans were given and compared to raw materials used on the market. The technological factors associated with such materials were discussed. The composition of the extracts was compared to typical industrial phosphoric acid and standard values characterizing suspension fertilizers. The most favorable conditions for selective precipitation of phosphorus compounds were revealed. The fertilizers obtained also meet EU regulations in the case of the newly discussed Cd content. The process was scaled up and a flow mass diagram was defined.

One-step synthesis of highly-biocompatible spherical gold nanoparticles using Artocarpus heterophyllus Lam. (jackfruit) fruit extract and its effect on pathogens.

INTRODUCTION: Novel approaches for the synthesis of gold nanoparticles (AuNPs) are of great importance due to its vast spectrum of applications in diverse fields, including medical diagnostics and therapeutics. Te presented study reports the successful AuNPs' synthesis using Artocarpus heterophyllus Lam. extract, and provides detailed characterization and evaluation of its antibacterial potential. OBJECTIVE: The aim was to develop a cost-effective and environmentally friendly synthesis method of gold nanoparticles using aqueous fruit extract of Artocarpus heterophyllus Lam. as a reducing and capping agent, which has proven activity against human pathogens, such as microbial species E.coli and Streptobacillus sps. MATERIALS AND METHOD: Characterizations were carried out using ultraviolet-visible (UV-Vis) spectrophotometry, scanning electron microscopy (SEM), energy dispersive X-ray and Fourier-Transform infra-red spectroscopy (FT-IR). RESULTS: SEM images showed the formation of gold nanoparticles with an average size of 20-25 nm. Spectra collected while infra-red analysis contained broad peaks in ranges from 4000-400 cm -1 . CONCLUSIONS: It can be concluded that the fruit of Artocarpus heterophyllus Lam. can be good source for synthesis of gold nanoparticles which showed antimicrobial activity against investigated microbes, in particul E. coli, and Streptobacillus. An important outcome of this study will be the development of value-added products from the medicinal plant Artocarpus heterophyllus Lam. for the biomedical and nanotechnology-based industries.

Biogenic catalysis in sulphide minerals' weathering processes and acid mine drainage genesis.

Bioleaching and biogenesis are the main outputs from a large group of environmental processes participating in the natural material cycle, used in raw materials processing. Bio-oxidation reactions are the main basis for bioleaching procedures, often participating in parallel leaching processes. During the leaching processes of polycomponent sulphide substrates, the factor of process selection also plays an important role, being in direct relation to the electric properties and galvanic effect occurring between the individual components of the leaching substrate. This work gives a summary of the results of a research focused on the possibilities of using biotechnological procedures for treatment of Slovak sulphide ores. The object of the research is extraction of valuable metals, undesirable admixtures and degradation of crystal lattice of sulphides for subsequent chemical leaching processing of precious metals. The results of experiments on the existence of biogenic processes in situ on waste dumps from exploitation containing residual sulphides are also presented. The processes result in acid mine drainage water generation. These waters are strongly mineralised (over 48 g/L) and of low pH; that is why they are very caustic. The arsenic content (2.558 mg/L) in outflowing waters from old mines is high and over the limits set by the law.

Phosphorus cycle - possibilities for its rebuilding.

The rebuilding of the phosphorus cycle can be performed with the use of both biotechnology and chemical technology. This paper presents a review of the phosphorus cycle and the different approaches that can be taken to the recovery of phosphorus from phosphate-rich waste. Critical issues in the phosphorus cycle are also discussed. Methods for the recovery of phosphorus form sewage sludge ash are widely explored and divided into two groups: wet extraction methods and thermochemical methods. Laboratory-scale methods are described, as well as proposed industrial technologies, with particular regard to the possibilities for their implementation in Poland. Phosphorus recovery methods from SSA (sewage sludge ash) in our country seems to be promising due to the increasing number of sewage sludge incineration plants, which could easily supply ash to future recovery installations. For the effective recovery of P from sewage sludge ash, it is essential to make the right choice in determining the appropriate method to use with respect to the particular properties of the ash composition available. A patented method of phosphorus recovery by acid extraction methods, developed by Cracow University of Technology, results in an efficiency of 80-96% for phosphorus recovery. 3000 to 4000 tons of phosphorus per year can be recycled and introduced back into the environment, that covers around 7% of the total amount of phosphorus ore imported into Poland between 2008 and 2009.

Surface of root cementum following air-polishing with bioactive hydroxyapatite (Ca and P mapping). A pilot study.

Air-polishing is a well-known and common technique to remove plaque, tartar and different kind of stains from teeth, using abrasive materials. Commonly used cleaning powders contain Al (aluminium) which is still controversial in terms of its inertness and harmfulness for human body. Nowadays, new air-polishing materials, including biomaterials, are being introduced. In particular, biomaterials the structure of which imitates that of natural tissue are very promising materials of reparative and reconstructive features. The purpose of the study was to assess in vitro the influence of natural hydroxyapatite on cementum surface and to assess superficial qualitative distribution of such elements as calcium and phosphorus before and after air-polishing. Four teeth extracted for periodontal reasons were airpolished. Bioactive hydroxyapatite (prepared in the Cracow Institute of Technology) was a cleaning powder with particle size of up to 10 µm. Bioactive natural hydroxyapatite is a very effective cleaning powder, which removes efficiently tartar from cementum surface and does not cause any damage. The qualitative analysis of cementum images after air-polishing with natural hydroxyapatite showed that the cementum surface was fully saturated with such elements as calcium and phosphorus, which was not observed on control cementum images.

Physicochemical and biological properties of hydrogel/gelatin/hydroxyapatite PAA/G/HAp/AgNPs composites modified with silver nanoparticles.

Composites comprising biodegradable polymer matrix, bioactive ceramic fillers and metallic nanoparticles can be applied in the substitution of bone tissue and many others medical and dental applications. Recently, fully resorbable composite materials applicable as bone substitutes are the subject of intensive studies in surgical reconstruction and bone tissue engineering. Biological composites, such as bone and teeth, contain hydroxyapatite (HAp), a mineral component with composition Ca10(PO4)6(OH)2. Silver nanoparticles or silver ions have long been known to have strong inhibitory and bactericidal effects as well as a broad spectrum of antimicrobial activities. In this study we applied natural origin hydroxyapatite obtained from pork bone sludge. As polymer matrix gelatin and poly(acrylic acid) were used. Composite materials were obtained with the use of microwave irradiation. The influence of metallic nanoparticles presence on the degradation process of composite materials was investigated by pH and conductivity analyses of water filtrates. In vitro tests in simulated body fluid (SBF) and artificial saliva confirmed that it is possible to produce hydroxyapatite/polymer composites doped with silver nanoparticles for medical applications. Tests proved that content of silver nanoparticles in composites had influence on degradation behaviour of HA/Polymer/AgNPs in artificial media such as simulated body fluid and saliva.

Preparation of hydroxyapatite from animal bones.

This paper presents the method of obtaining hydroxyapatite from animal bones. Bone sludge and calcined products were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Calcium concentration was determined with titration, and phosphorus--spectrophotometrically. Making use of the AAS and ICP methods the content of microelements was determined. In all the products, hydroxyapatite was the only crystalline phase indicated. The FT-IR spectra confirmed that calcination removed the total of organic substances. Calcium and phosphorus contents were 38% and 18%, respectively, which corresponded to the Ca/P molar ratio of nonstoichiometric hydroxyapatite. The specific surfaces of products were measured by BET method. The volume of micro- and mesopores was determined.