Thermogravimetry–coupled with differential scanning calorimetry, quadrupole mass spectrometry, and Fourier-transform infrared spectroscopy (TG-DSC-QMS-FTIR)–was applied to monitor the thermal stability (in an N2 pyrolytic atmosphere) and chemical properties of natural polymers, fulvic (FA) and humic acids (HA), isolated from chemically different soils. Three temperature ranges, R1, 40–220°C; R2, 220–430°C; and R3, 430–650°C, were distinguished from the DSC data, related to the main thermal processes of different structures (including transformations without weight loss). Weight loss (ΔM) estimated from TG curves at the above temperature intervals revealed distinct differences within the samples in the content of physically adsorbed water (at R1), volatile and labile functional groups (at R2) as well as recalcitrant and refractory structures (at R3). QMS and FTIR modules enabled the chemical identification (by masses and by functional groups, respectively) of gaseous species evolved during thermal decomposition at R1, R2 and R3. Variability in shape, area and temperature of TG, DSC, QMS and FTIR peaks revealed differences in thermal stability and chemical structure of the samples between the FAs and HAs fractions of different origin. The statistical analysis showed that the parameters calculated from QMS (areas of m/z = 16, 17, 18, 44), DSC (MaxDSC) and TG (ΔM) at R1, R2 and R3 correlated with selected chemical properties of the samples, such as N, O and COOH content as well as E2/E6 and E2/E4 indexes. This indicated a high potential for the coupled method to monitor the chemical changes of humic substances. A new humification parameter, HTD, based on simple calculations of weight loss at specific temperature intervals proved to be a good alternative to indexes obtained from other methods. The above findings showed that the TG-DSC-QMS-FTIR coupled technique can represent a useful tool for the comprehensive assessment of FAs and HAs properties related to their various origin.
Porosity is an important parameter for characterizing the microstructure of solids that corresponds to the volume of the void space, which may contain fluid or air, over the total volume of the material. Many materials of natural and technically manufactured origin have a large number of voids in their internal structure, relatively small in size, compared to the characteristic dimensions of the body itself. Thus, porosity is an important feature of industrial materials, but also of biological ones. The porous structure affects a number of material properties, such as sorption capacity, as well as mechanical, thermal, and electrical properties. Porosity of materials is an important factor in research on biomaterials. The most popular materials used to rebuild damaged tooth tissues are composites and ceramics, whilst titanium alloys are used in the production of implants that replace the tooth root. Research indicates that the most comprehensive approach to examining such materials should involve an analysis using several complementary methods covering the widest possible range of pore sizes. In addition to the constantly observed increase in the resolution capabilities of devices, the development of computational models and algorithms improving the quality of the measurement signal remains a big challenge.
Soil enhancements such as biochar (BC) are gaining attention as tools to mitigate climate change and also to promote crop growth. However, biochar use can disrupt soil ecosystems by changing the soil’s physical, chemical, and biological properties. The study aimed to determine how biochar influences soil physical changes such as specific surface area (SSA) and water vapor sorption, and how these conditions affect arbuscular mycorrhizal fungal (AMF) hyphae growth and glomalin production. The study analyzed these factors at different plant phenological phases (i.e., flowering, development of fruit, and ripening of fruit and seed) to better understand the changes within the system while varying biochar amounts. The study also investigated the effect of different soil physical and chemical parameters on mycorrhizal hyphae growth and glomalin production. Four treatments were investigated: 0, 0.5%, 2.5%, and 5.0% (w/w) biochar amended silt loam soil planted with pepper. Soil samples were taken at the beginning and weeks 6, 10, and 12 of the study. The amount of adsorbed water vapor increased with an increasing amount of biochar added to the soils. Compared to control, SSA was significantly higher in all biochar amended treatments based on adsorption data, and only in the highest biochar amended soils for the desorption data at the end of the experiment. The presence of AMF in the roots appeared at week 6 of the experiment and the intensity of AMF root colonization increased with the age of plants. The AMF colonization parameters were significantly lower in BC2.5 compared to all other biochar amended soils. The abundance of intraradical AMF structures was highly correlated with several physicochemical soil parameters, such as SSA, the geometric mean diameter of soil aggregate, soil aggregate sizes, or pH. Glomalin production was negatively correlated with SSA, water vapor adsorption, aggregate stability, aggregate size, total nitrogen, potassium, and organic carbon content of the soil, while positive correlation was observed with bulk density. Increased biochar amount resulted in a significant decrease in glomalin production, concurrent with the age of the plants. Our results highlight the great complexity of interactions between soil physicochemical and biological parameters, and the importance of the time of sampling when biochar is used in soil, as the effects of biochar additions on the plant, soil physical characteristics, and soil microsymbionts vary over time.
The main goal of this work was to study the structural transformation of humic acids (HAs) under the influence of selected strains of fungi (Aspergillus niger and Paecilomyces lilacinus) and bacteria (Bacillus sp., Paenibacillus polymyxa and Bacillus amyloliquefaciens) with/without the presence of NPK fertilizers. Two-year experiments were conducted on two different soils and HAs isolated from these soils were examined for structure, humification degree, and quantity using fluorescence and UV-Vis spectroscopy, elemental analysis, and extraction methods. Results showed that the applied additives contributed to the beneficial transformation of HAs, but effects differed for various soils. HAs from silty soil with higher organic carbon content showed simplification of their structure, and decreases in humification, molecular weight, and aromaticity under the influence of fungi and bacteria without NPK, and with NPK alone. With both fungi and NPK, increases in O/H and O/C atomic ratios indicated an increase in the number of O-containing functional groups. HAs from sandy soil did not show as many significant changes as did those from silty soil. Sandy soil exhibited a strong decline in HA content in the second year that was reduced/neutralized by the presence of fungi, bacteria, and NPK. Periodically observed fluorescence at ~300 nm/450 nm reflected formation of low-molecular HAs originating from the activity of microorganisms.
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