All soils harbor microaggregates, i.e., compound soil structures smaller than 250 μm. These microaggregates are composed of diverse mineral, organic and biotic materials that are bound together during pedogenesis by various physical, chemical and biological processes. Consequently, microaggregates can withstand strong mechanical and physicochemical stresses and survive slaking in water, allowing them to persist in soils for several decades. Together with the physiochemical heterogeneity of their surfaces, the three-dimensional structure of microaggregates provides a large variety of ecological niches that contribute to the vast biological diversity found in soils. As reported for larger aggregate units, microaggregates are composed of smaller building units that become more complex with increasing size. In this context, organo-mineral associations can be considered structural units of soil aggregates and as nanoparticulate fractions of the microaggregates themselves. The mineral phases considered to be the most important as microaggregate forming materials are the clay minerals and Fe-and Al-(hydr)oxides. Within microaggregates, minerals are bound together primarily by physicochemical and chemical interactions involving cementing and gluing agents. The former comprise, among others, carbonates and the short-range ordered phases of Fe, Mn, and Al. The latter comprise organic materials of diverse origin and probably involve macromolecules and macromolecular mixtures. Work on microaggregate structure and development has largely focused on organic matter stability and turnover. However, little is known concerning the role microaggregates play in the fate of elements like Si, Fe, Al, P, and S. More recently, the role of microaggregates in the formation of microhabitats and the biogeography and diversity of microbial communities has been investigated. Little is known regarding how microaggregates and their properties change in time, which strongly limits our understanding of micro-scale soil structure dynamics. Similarly, only limited information is available on the mechanical stability of microaggregates, while essentially nothing is known about the flow and transport of fluids and solutes within the micro-and nanoporous microaggregate systems. Any quantitative approaches being developed for the modeling of formation, structure and properties of microaggregates are, therefore, in their infancy. We respond to the growing awareness of the importance of microaggregates for the structure, properties and functions of soils by reviewing what is currently known about the formation, composition and turnover of microaggregates. We aim to provide a better understanding of their role in soil function, and to present the major unknowns in current microaggregate research. We propose a harmonized concept for aggregates in soils that explicitly considers the structure and build-up of microaggregates and the role of organo-mineral associations. We call for experiments, studies and modeling endeavors that will link informatio...

Biochars are increasingly used as soil amendment and for C sequestration in soils. The influence of feedstock differences and pyrolysis temperature on biochar characteristics has been widely studied. However, there is a lack of knowledge about the formation of potentially toxic compounds that remain in the biochars after pyrolysis. We investigated biochars from three feedstocks (wheat straw, poplar wood, and spruce wood) that were slowly pyrolyzed at 400, 460, and 525°C for 5 h (straw) and 10 h (woodchips), respectively. We characterized the biochars' pH, electrical conductivity, elemental composition (by dry combustion and X-ray fluorescence), surface area (by N adsorption), water-extractable major elements, and cation exchange capacity (CEC). We further conducted differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffractometry to obtain information on the biochars' molecular characteristics and mineralogical composition. We investigated trace metal content, total polycyclic aromatic hydrocarbon (PAH) content, and PAH composition in the biochars. The highest salt (4.92 mS cm) and ash (12.7%) contents were found in straw-derived biochars. The H/C ratios of biochars with highest treatment temperature (HTT) 525°C were 0.46 to 0.40. Surface areas were low but increased (1.8-56 m g) with increasing HTT, whereas CEC decreased (162-52 mmol kg) with increasing HTT. The results of DSC and FTIR suggested a loss of labile, aliphatic compounds during pyrolysis and the formation of more recalcitrant, aromatic constituents. X-ray diffractometry patterns indicated a mineralogical restructuring of biochars with increasing HTT. Water-extractable major and trace elements varied considerably with feedstock composition, with trace elements also affected by HTT. Total PAH contents (sum of EPA 16 PAHs) were highly variable with values up to 33.7 mg kg; irrespective of feedstock type, the composition of PAHs showed increasing dominance of naphthalene with increasing HTT. The results demonstrate that biochars are highly heterogeneous materials that, depending on feedstock and HTT, may be suitable for soil application by contributing to the nutrient status and adding recalcitrant C to the soil but also potentially pose ecotoxicological challenges.

Soil structure depends on the association between mineral soil particles (sand, silt, and clay) and organic matter, in which aggregates of different size and stability are formed. Although the chemistry of organic materials, total microbial biomass, and different enzyme activities in different soil particle size fractions have been well studied, little information is available on the structure of microbial populations in microhabitats. In this study, topsoil samples of different fertilizer treatments of a long-term field experiment were analyzed. Size fractions of 200 to 63 m (fine sand fraction), 63 to 2 m (silt fraction), and 2 to 0.1 m (clay fraction) were obtained by a combination of low-energy sonication, wet sieving, and repeated centrifugation. Terminal restriction fragment length polymorphism analysis and cloning and sequencing of 16S rRNA genes were used to compare bacterial community structures in different particle size fractions. The microbial community structure was significantly affected by particle size, yielding higher diversity of microbes in small size fractions than in coarse size fractions. The higher biomass previously found in silt and clay fractions could be attributed to higher diversity rather than to better colonization of particular species. Low nutrient availability, protozoan grazing, and competition with fungal organisms may have been responsible for reduced diversities in larger size fractions. Furthermore, larger particle sizes were dominated by ␣-Proteobacteria, whereas high abundance and diversity of bacteria belonging to the Holophaga/Acidobacterium division were found in smaller size fractions. Although very contrasting organic amendments (green manure, animal manure, sewage sludge, and peat) were examined, our results demonstrated that the bacterial community structure was affected to a greater extent by the particle size fraction than by the kind of fertilizer applied. Therefore, our results demonstrate specific microbe-particle associations that are affected to only a small extent by external factors.

When is an acene stable? The pronounced multiradical character of graphene nanoribbons of different size and shape was investigated with high‐level multireference methods. Quantitative information based on the number of effectively unpaired electrons leads to specific estimates of the chemical stability of graphene nanostructures.

Hydrogen-bonded interactions in the acetic acid dimer and in complexes formed by acetic acid with acetaldehyde, acetamide, ammonia, methanol, and phenol and in corresponding complexes between the acetate anion and the same ligands as before were studied in the gas phase and in solution by means of quantum chemical DFT/BLYP calculations. Three solvents (heptane, DMSO, and water) of largely varying polarity were chosen. The polarized continuum model was used for the description of the solvent. Optimized geometries, reaction energies, and Gibbs free energies of complex formation were computed. In the neutral complexes an opening of the weaker of the two hydrogen bonds formed in the complex is observed with increasing polarity of the solvent. This opening is interpreted by the creation of optimal conditions for separate solvation of the subsystems of the hydrogen bond in competition with the geometrical requirements for the formation of this bond. Even though almost all reaction energies are found to be negative, only the strongly bound complexes, acetic acid dimer, and acetic acid-acetamide are stable according to Gibbs free energy results. The main factors for this finding are the entropy loss on the formation of the bimolecular complex and the changes of the free energy of solvation. Solvation effects are interpreted in terms of dipole moments, solvent-accessible surfaces, and cavity volumes of the separate molecules and of the complexes.

The structure and dynamics of a monomolecular water layer on the octahedral and tetrahedral surfaces of the kaolinite layer have been investigated using short-time ab initio molecular dynamics. The arrangement and the structure of the water layer differ significantly on both surfaces. On the octahedral side the water layer forms relatively strong hydrogen bonds with the surface hydroxyl groups. This interaction significantly influences the layout of the water molecules in this case. On the other hand, the water molecules on the tetrahedral surface have the tendency to aggregate, forming hydrogen bonds among themselves. Only weak hydrogen bonds with the basal oxygen atoms of the tetrahedral surface are formed. Thus, the octahedral and tetrahedral surfaces of the kaolinite layer are of different chemical nature and can be considered as hydrophilic and hydrophobic, respectively.

No abstract

No abstract