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...
Steroids are used as faecal markers in environmental and in archaeological studies, because they provide insights into ancient agricultural practices and the former presence of animals. Up to now, steroid analyses could only identify and distinguish between herbivore, pig, and human faecal matter and their residues in soils and sediments. We hypothesized that a finer differentiation between faeces of different livestock animals could be achieved when the analyses of several steroids is combined (Δ5-sterols, 5α-stanols, 5β-stanols, epi-5β-stanols, stanones, and bile acids). We therefore reviewed the existing literature on various faecal steroids from livestock and humans and analysed faeces from old livestock breed (cattle, horse, donkey, sheep, goat, goose, and pig) and humans. Additionally, we performed steroid analyses on soil material of four different archaeological periods (sites located in the Lower Rhine Basin, Western Germany, dating to the Linearbandkeramik, Urnfield Period / Bronze Age, Iron Age, Roman Age) with known or supposed faecal inputs. By means of already established and newly applied steroid ratios of the analysed faeces together with results from the literature, all considered livestock faeces, except sheep and cattle, could be distinguished on the basis of their steroid signatures. Most remarkably was the identification of horse faeces (via the ratio: epi-5β-stigmastanol: 5β-stigmastanol + epicoprostanol: coprostanol; together with the presence of chenodeoxycholic acid) and a successful differentiation between goat (with chenodeoxycholic acid) and sheep/cattle faeces (without chenodeoxycholic acid). The steroid analysis of archaeological soil material confirmed the supposed faecal inputs, even if these inputs had occurred several thousand years ago.
Production of charcoal has accompanied human life from the beginning. We aimed at evaluating the degree to which the chemical signatures of charcoal may serve as a fingerprint for burning conditions. After a compilation of fire literature we differentiated three typical fire regimes [grass and forest ground (285 ± 143°C), shrub (503 ± 211°C) and domestic fires (797 ± 165°C)] and three main factors impacting on charcoal formation: charring duration, temperature and fuel. For fingerprint calibration and validation, typical fuels of prehistoric burning events (wood and grass) were charred under laboratory conditions (300-700°C; varying duration) and compared with residues from natural fires in SE Europe. Analysis comprised assessment of benzene polycarboxylic acids (BPCAs), organic carbon (Corg) content, nitrogen content, oxygen index (OI: CO2/Corg) and hydrogen index (HI: HC/Corg), temperature of maximum heating (Tmax) and mid-infrared spectroscopy (MIRS). All parameters including mass loss increased with increasing combustion temperature, but were unaffected by charring duration. Grass charcoal had consistently lower Corg content and HI than wood, but values showed a bias towards the natural charcoals, probably because the latter contained higher amounts of mineral matter or were combusted under greater O2 supply. Nevertheless, natural charcoals could be differentiated into forest ground fires (B5CA/B6CA 1.3-1.9; OI >20; intense CH2 stretching, Tmax <488°C) and grass fires (B5CA/B6CA 0.8-1.4; OI >20; weak CH2 stretching, Tmax <425°C), whereas domestic fires revealed B5CA/B6CA values <0.8, OI values <20 and little MIRS absorbance. In summary, it appears possible to reconstruct fire regimes from the temperature sensitivity of BPCA patterns, Tmax, OI and aromatic and aliphatic MIRS signals, whereas assignment of fuel source was less reliable. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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