Comparison of Sample Preparation Techniques for the (-)ESI-FT-ICR-MS Analysis of Humic and Fulvic Acids.

Soil organic matter (SOM) plays a key role in the global carbon and nitrogen cycles. Soil biogeochemistry is regularly studied by extracting the base-soluble fractions of SOM: acid-insoluble humic acid (HA) and acid-soluble fulvic acid (FA). Electrospray ionization-Fourier transform-ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) is commonly utilized for molecularly characterizing these fractions. Different sample preparation techniques exist for the analysis of HA and FA though questions remain regarding data comparability following different preparations. Comparisons of different sample preparation techniques here revealed that the negative-mode ESI-FT-ICR-MS analytical window can be skewed to detect different groups of molecules, with primary differences in oxygenation, aromaticity, and molecular weight. It was also observed that HA and FA from soils versus an aquatic matrix behaved very differently. Thus, we conclude that sample preparation techniques determined to be "most optimal" in our study are in no way universal. We recommend that future studies of HA and FA involve similar comparative studies for determining the most suitable sample preparation technique for their particular type of HA or FA matrices. This will enhance data comparability among different studies and environmental systems and ultimately allow us to better understand the complex composition of environmental matrices.

Structural characterization using 2D NMR spectroscopy and TMAH-GC × GC-MS: Application to humic acids from soils of an integrated agricultural system and an Atlantic native forest.

Understanding the chemical make-up of soils and their structure is critical for constraining the role of soil organic matter (SOM) into the global biogeochemical cycles, as well as to understand the capability of SOM to sequester carbon and mitigate greenhouse gas emissions. Here, we use two-dimensional 1H-13C heteronuclear single quantum coherence nuclear magnetic resonance (2D 1H-13C HSQC NMR) spectroscopy to structurally characterize the most refractory component of SOM, the humic acid (HA). The observations from 2D 1H-13C HSQC NMR were coupled with lignin phenol and fatty acid measurements using tetramethylammonium hydroxide (TMAH) thermochemolysis - two-dimensional gas chromatography - mass spectrometry (TMAH-GC × GC-MS). We studied humic acids extracted from an integrated Crop - Livestock - Forest System (CLFS) agricultural area and an undisturbed Atlantic Native Forest (NF) area. We evaluated soils from two different depths: the topsoil (0-20 cm) and subsoil (60-100 cm) layers, and reveal the presence of oxidized ligninaceous phenols as we had previously hypothesized. Collectively, our results indicate that there are significant oxidative processes with increasing soil depth which are more pronounced in the CLFS relative to the NF area. Degradation of stearic acid with increasing depth in the CLFS soils indicated that the CLFS is more microbiologically active than NF. Therefore, CLFS is less biochemically stable than we originally perceived. The enhanced bio-reactivity of CLFS is likely driving the enhanced carbon sequestration in the CLFS soils. This is perhaps due to the diversity of biomass remnants available at the CLFS soil rhizosphere which allows for more different types of biomass to be sequestered as oxidized ligninaceous phenols. Our results employing structural characterization with 2D 1H-13C HSQC NMR and TMAH-GC × GC-MS provide a new layer of knowledge about the practice of integrated agricultural systems and allow us to understand the structure and fate of sequestered carbon in soils from different soil environments.

Synergy of Aspergillus niger and Components in Biofertilizer Composites Increases the Availability of Nutrients to Plants.

Intensive fertilization has been required to provide nutrients for plant growth under the current agricultural practices being applied to meet the global food demands. Micronutrients such as zinc, manganese, and copper are required in small quantities when compared to macronutrients (such as nitrogen, phosphorus and potassium), but they are essential for the plant growth cycle and consequently for increasing productivity. Mineral oxides such as ZnO, MnO, and CuO are used in agriculture as micronutrient sources, but their low solubility limits practical applications in plant nutrition. Similarly, elemental sulfur (S0) can provide a high-concentration source of sulfate, but its availability is limited by the ability of the soil to promote S0 oxidation. We propose here the integration of these nutrients in a composite based on a biodegradable starch matrix containing mineral oxides and S0 in a dispersion that allowed encapsulation of the acidifying agent Aspergillus niger, a native soil fungus. This strategy effectively improved the final nutrient solubility, with the composite starch/S0/oxidemixture multi-nutrient fertilizer showing remarkable results for solubilization of the oxides, hence confirming a synergic effect of S0 oxidation and microbial solubilization. This composite exhibited an extended shelf life and soil-plant experiments with Italian ryegrass (Lolium multiflorum Lam.) confirmed high efficiencies for dry matter production, nutrient uptake, and recovery. These findings can contribute to the development of environmentally friendly fertilizers towards a more sustainable agriculture and could open up new applications for formulations containing poorly soluble oxide sources.

Urea-montmorillonite-extruded nanocomposites: a novel slow-release material.

The present study describes the preparation and characterization of a novel urea slow-release nanocomposite, based on urea intercalation into montmorillonite clay by an extrusion process at room temperature. Nanocomposites with urea contents ranging from 50 to 80 wt % were successfully produced and characterized. Analyses by XRD, DTA, and SEM-EDX confirmed the effectiveness of this simple process to exfoliate the clay lamellae into the urea matrix, forming a product that can be classified as a nanocomposite, due to the exfoliation degree attained. Diametral compression tests showed that the samples were very deformable, and the release rate of active components in water showed that the nanocomposite showed a slow release behavior for urea dissolution, even in low montmorillonite amounts (20% in weight).

Nutrient release by a Brazilian sedimentary zeolite

This report describes the characterization of a sedimentary occurrence from the Parnaíba Basin, Brazil, containing the zeolite stilbite intertwined with smectitic clay mineral. The head samples from different sites present a wide content range of the zeolitic phase - 15 percent to 50 percent. The use of simple separation techniques - conventional gravitic treatments - yields concentrates containing about 67 percent of the zeolitic component. Assays with the amendments of these concentrates with plant nutrients yield release rates matching those reported for similar commercial products.

São apresentadas as propriedades físico-químicas de uma ocorrência sedimentar da Bacia do Parnaíba, Brasil, da zeólita estilbita, agregada a uma argila esmectítica. As amostras de diferentes sítios apresentam uma ampla variação do mineral zeolítico: entre 15 por cento a 50 por cento. A utilização de espirais concentradoras foi suficiente para obtenção de concentrados contendo até 67 por cento do mineral. Ensaios laboratoriais do concentrado dopado com fertilizantes revelam taxas de liberação de nutrientes comparáveis aos obtidos com produtos comerciais similares.