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The overall effect of reactants in the form of sulfates of ammonium, calcium, copper(II), iron(III), manganese(II) and zinc on the thermal behavior of ammonium nitrate has been reported. Thermal stability assessment was performed with the use of thermogravimetric analysis and differential thermal analysis coupled with mass spectroscopy. Interestingly, sulfate anions present in the system were often not sufficient to properly inhibit the decomposition of ammonium nitrate. Sulfate ion and cation supplied with the selected compound significantly influence the studied process. Studied mixtures with ammonium sulfate and calcium sulfate were concluded to show the highest stability. Manganese and iron sulfate salts caused a significant acceleration of the initial thermal decomposition. The addition of these compounds led to visible changes in the process mechanism, which allowed them to be classified as catalysts of the decomposition of ammonium nitrate. Furthermore, small amounts of substances in the system, even those that are generally considered to be inhibitors, worsened the thermal stability of AN. Zinc and copper sulfates, under studied conditions, created double salts that were characterized by a higher thermal stability than pure ammonium nitrate. This property indicates the possibility of obtaining systems containing ammonium nitrate with significantly higher thermal stability, what could potentially have multiple useful applications.

The influence of cobalt, copper, iron(III), manganese and zinc nitrate salts on phase transitions and thermal stability of ammonium nitrate (AN) has been studied and discussed. Differential thermal analysis/differential scanning calorimetry coupled with thermogravimetry and mass spectrometry were used to evaluate the stability of analyzed systems. Each nitrate salt was appropriately mixed with ammonium nitrate to create samples with AN:salt mass ratios of 4:1, 9:1 and 49:1. It was concluded that the addition of every studied nitrate influenced phase transitions of AN. Most analyzed salts decreased the stability of AN by accelerating its exothermic decomposition process. Iron and cobalt nitrates were defined as the most hazardous additives, resulting in a creation of a highly destabilized mixture. Copper and manganese nitrates were also defined as catalysts of the AN decomposition process, lowering the initial decomposition temperature and increasing the rate of the observed process. Zinc nitrate hexahydrate was the only salt considered to be relatively neutral in such systems, especially in small amounts. The study allowed to define the influence of selected metal nitrate salts on the thermal stability of AN under conditions that are considered as potentially unsafe for such systems.

PurposeTechnological progress and high market demand contributed to a significant interest in the production of fertilizers based on humic acids. The aim of this study was to evaluate the possibilities of using humic acids obtained from lignite in the production of new commercial products. For this purpose, it is necessary to determine the quality standard requirements for such material. Properties of humic acids depend on source of origin as well as method of its extraction.Materials and methodsThe humic acids were extracted from polish deposit of lignite–Sieniawa Lubuska by alkaline extraction using for this purpose six kinds of extractants: 0.1 M NaOH and 0.25 M NaOH, 0.1 M KOH and 0.25 M KOH, and 0.1 M Na4P2O7 and 0.25 M Na4P2O7. The humic samples were used in solid powder form and characterized by UV-Vis spectroscopy, 13C NMR spectroscopy, fluorescence spectroscopy, and thermal analysis.Results and discussionThe determining factor influencing a degree of humic acids extraction from lignite and their structure is type of extractant. The largest efficiency of extraction (about 50%) was obtained with the use of NaOH solutions. All examined humic acids were generally characterized by simple and heterogeneous molecularly structure with low molecular weight and low aromatic polycondensation. Therefore, it can be concluded that humic acids extracted with NaOH and KOH solutions are less condensed than those extracted with Na4P2O7 solutions. It can suggest that humic acids obtained from lignite using solutions of Na4P2O7 are characterized by a low transformation degree and greater amount of carboxyl groups.ConclusionsLow rank coal can be successfully used in agriculture as a rich source of humic acids. Reagent used in their extraction, apart from high efficiency should have a neutral impact on their structure. Studies on the physicochemical properties of humic acids can be helpful in predicting behaviors of such fertilizer components in the environment and in inventing new products taking the principles of sustainable development into consideration.

Results of efficiency of obtaining humic substances (HSs) from peat in traditional alkaline extraction (TAE) and ultrasound-assisted alkaline extraction (UAAE) are presented. The influence of the duration of the process and ultrasound intensity on the efficiency of extraction of humic acids (HAs) and fulvic acids (FAs) extraction was determined. The composition of the fulvic acid fraction was examined depending on the type of eluent used. Fulvic acids were divided into fractions using columns packed with DAX-8 resin. For this process, 0.1 M NaOH and 0.5 M NH3∙H2O were used as eluents. For the quality assessment of specific fulvic acids fractions, spectroscopic methods (UV-Vis and FTIR) were used. Ultrasound had a positive effect on HS extraction efficiency, especially in increasing the amount of a desired hydrophobic fraction of fulvic acids (HPO). However, a negative effect of the excessive prolongation and ultrasound intensity (approximately 400 mW∙cm−2) on the extraction efficiency of HPO eluted with 0.1 M NaOH solution was observed. Using peat as a raw carbon material for the HS extraction process can be used as an alternative industrial application of peat. UAAE may be considered as an alternative method to TAE, which provides a higher efficiency in HS isolation from peat.

In application conditions, the influence of environmental parameters on used fertilizer chelates and their distribution over time is important. For this purpose, the changes in the content of micronutrient ions and Fe-EDDHA and Fe-EDDHSA chelates in an aqueous medium at different pH values were studied. In the assumed time, changes in the ions content were analyzed using the voltammetry method at pH 3, 5 and 7. The content of isomers and chelate forms was analyzed by ion pair chromatography at pH 3, 5 and 7. These studies allowed us to determine the effect of pH on the stability of iron chelates over time.

Due to the positive effect on soil structure and the influence on improving the efficiency of plant roots nutrient uptake, humic acids (HA) are widely considered for fertilizer production. Especially, it seems to be particularly promising to use them as additives in technologies of mineral fertilizer production. One of the common mineral fertilizer components, due to its good water solubility and the presence of nitrogen in two forms, is ammonium nitrate (AN). The aim of this study was to determine the influence of the humic acids extracted from peat and lignite on the thermal decomposition of HA and the thermal decomposition of ammonium nitrate and humic acids mixtures. For the quality assessment of HA, spectroscopic methods (FTIR/ATR and CP/MAS 13 C NMR) and analysis of elemental composition were used. The analysis of the spectra showed differences in the degree of humification of humic acids extracted from various raw materials. HA isolated from peat were distinguished by the presence of peptides, polysaccharides, and lignin residues. Elemental analysis showed the higher carbon and sulfur content in the extracted HA compared to the reference samples. The results of the TG-DTA-MS analysis confirmed the influence of differences in the molecular structure of humic acids, especially in the aliphatic and aromatic carbon content, on the thermal decomposition process. Total content of carboxylic and/or hydroxylic functional groups had a significant impact on the start of the decomposition temperature. Their increase visibly influenced the acceleration of the exothermic decomposition of AN.

The aim of the presented study was to evaluate an integrated, direct procedure for the synthesis of humic‐silica composites (HSiC) by the isolation of humic substances (HS) from peat and lignite by the use of sodium silicate solution as an extractant. The obtained materials, because of the presence of humic functional groups, may potentially be used for removing contaminants from aqueous solutions. The quantitative assessment was based on experiments designed according to the Box‐Behnken plan. The statistical analysis of the results allowed to determine the optimal conditions of the process tested, for which the isolation efficiency of humic substances (HS) was greater than 50 % for both raw materials. This made it possible to synthesize humic silica composites with a high content of HS, which have been qualitatively evaluated. This step was focused on the analysis of the humic structure using elemental analysis, spectroscopic methods, and differential thermal analysis coupled with thermogravimetry. On the basis of them, the presence of structures characteristic for HS in the HSiC tested was observed. Moreover, the results of the thermal analysis pointed to the higher thermal stability of the synthesized compounds, compared to the HS isolated with the use of a traditional extractant. The presented research focused on the new direct procedure for the synthesis of humic silica composites by the isolation of humic substances from peat and lignite. Process optimization was carried out based on the design of the experiment and statistical assessment. For the qualitative assessment of synthetized materials, spectroscopic methods (ATR‐FTIR and CP/MAS 13C NMR) methods as well as thermal analysis (TG‐DTA‐DTG and EGA) were applied.

Granular fertilizers (especially those based on ammonium nitrate (AN)) tend to agglomerate during storage. The aims of this research were to develop effective anti-caking coatings for ammonium nitrate fertilizers while improving the quality of fertilizers and to optimize the composition of effective anti-caking coatings. The influence of the composition of the prepared organic coatings on the effectiveness of preventing the caking of fertilizers was studied by response surface methodology (RSM) using Box–Behnken design (BBD). Additionally, the effect of the developed anti-caking agents on the quality of fertilizers was determined by measuring the crushing strength of the granules. The prepared coatings included fatty amine, stearic acid, surfactant, and paraffin wax. Gas chromatography–mass spectrometry (GC–MS) was used to analyze these coatings. The morphology of the fertilizers were examined by scanning electron microscopy (SEM). Composition studies, based on statistical assessment, showed the coating components had a varying influence on preventing the caking of fertilizers after granulation and after 30 days of storage. The results demonstrated that increasing the content of fatty amines and reducing surfactant in the composition of coating had positive effects on caking prevention. In this study, more effective and economically viable anti-caking coatings were developed. In addition, the present work could serve as a basis to further improve anti-caking coatings.

Samples of pure ammonium nitrate (AN) and its mixtures with calcium carbonate, potassium hydrogen carbonate and potassium carbonate were investigated with the use of differential thermal analysis with mass spectrometry, powder X-ray diffraction and scanning electron microscopy. The main objective of the study was to determine the influence of selected carbonate materials on phase transitions of ammonium nitrate and to consider a possibility to use such potassium salts as fillers in fertilizer production. It was proven that all carbonate salts caused the absence of a phase transition that normally would occur at around 84–86 °C. Potassium carbonates were too reactive in systems containing AN. Based on the performed study, it was concluded that even though potassium carbonates are not fit to replace mineral fillers in the production process of fertilizers containing ammonium nitrate, they could be used in lesser amounts to remove the presence of low-temperature phase transitions of AN.

The degree of complexation of microelement ions by the biodegradable chelating agent - IDHA was examined in the work. The tests were carried out in water and in a simulated fertilizer environment. In order to compare the obtained results, tests were also carried out for the commonly used EDTA. The performed analyzes allow to determine the influence of the presence of compounds containing macroelements on the degree of binding of microelement ions by the biodegradable IDHA and EDTA chelators. The obtained results make it possible to determine the optimal conditions for the chelation of cations by IDHA, which in the future may be used in the production of micronutrient fertilizers on a large scale.