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.
Biochar applications to soils can improve soil fertility by increasing the soil's cation exchange capacity (CEC) and nutrient retention. Because biochar amendment may occur with the applications of organic fertilizers, we tested to which extent composting with farmyard manure increases CEC and nutrient content of charcoal and gasification coke. Both types of biochar absorbed leachate generated during the composting process. As a result, the moisture content of gasification coke increased from 0.02 to 0.94 g g, and that of charcoal increased from 0.03 to 0.52 g g. With the leachate, the chars absorbed organic matter and nutrients, increasing contents of water-extractable organic carbon (gasification coke: from 0.09 to 7.00 g kg; charcoal: from 0.03 to 3.52 g kg), total soluble nitrogen (gasification coke: from not detected to 705.5 mg kg; charcoal: from 3.2 to 377.2 mg kg), plant-available phosphorus (gasification coke: from 351 to 635 mg kg; charcoal: from 44 to 190 mg kg), and plant-available potassium (gasification coke: from 6.0 to 15.3 g kg; charcoal: from 0.6 to 8.5 g kg). The potential CEC increased from 22.4 to 88.6 mmol kg for the gasification coke and from 20.8 to 39.0 mmol kg for the charcoal. There were little if any changes in the contents and patterns of benzene polycarboxylic acids of the biochars, suggesting that degradation of black carbon during the composting process was negligible. The surface area of the biochars declined during the composting process due to the clogging of micropores by sorbed compost-derived materials. Interactions with composting substrate thus enhance the nutrient loads but alter the surface properties of biochars.
Biochar application has been suggested for reducing toxic levels of metals in contaminated soils and enhancing nutrient retention in agro‐ecosystems. We studied sorption of copper (Cu(II)) and sulphate‐sulphur (SO4‐S) to charcoal, gasification coke and flash‐pyrolysis biochar in order to relate sorption to char properties. Furthermore, we investigated the effect of composting of charcoal and gasification coke on sorptive properties. Langmuir sorption affinity coefficients for Cu(II) for non‐composted biochars increased in the order flash‐pyrolysis char < charcoal < gasification coke. The sorption capacity for Cu(II) of the chars decreased in the order gasification coke (629 mg kg−1) > flash‐pyrolysis char (196 mg kg−1) > charcoal (56 mg kg−1). Composting significantly increased the sorption affinity coefficient approximately by a factor of 5 for charcoal (up to 1.1 l mg−1) and by a factor of 3–4 for gasification coke (up to 3.2 l mg−1). Whereas Cu(II) sorption to gasification coke (composted or not) was largely irreversible, sorption to flash‐pyrolysis char and charcoal showed higher reversibility. Relationships between Cu(II) sorption and biochar properties such as cation exchange capacity, specific surface area or aromaticity suggest that sorption was largely determined by complexation with organic matter. Sorption of SO4‐S was negligible by non‐composted and composted biochars. Composted gasification coke might be suited to reducing toxic Cu(II) concentrations in contaminated soils. Composted charcoal can potentially improve Cu(II) retention in a plant available form in acidic, sandy soils with small organic matter contents. Transient effects of biochars on soil pH can over‐ride the influence of sorption to biochars on concentrations of trace elements in soil solution and their availability to plants.
Ecological sanitation via thermophilic composting could be a promising solution to the lack of sanitation and limited access to fertilizers, particularly in developing countries. Here, we conducted a 185‐d thermophilic composting experiment with human excreta, and separately with cattle manure, mixed with kitchen scraps, teff [Eragrostis tef (Zuccagni) Trotter] straw, sawdust, and biochar (BC) by using an appropriate‐technology approach. We followed the dynamics of the most important macronutrients (N, P, K), temperature, moisture, pH, electrical conductivity, cation exchange capacity, as well as content of organic matter, organic C, Ca, Mg, and micronutrients throughout the process. Low N (<47%), P (<9%), K (<11%), Ca (<18%), and Mg (<21%) losses and the temperature profile indicated a well‐functioning thermophilic composting process. Compost temperature was >60 °C for 7, 6, 5, and 8 consecutive days for treatments containing human excreta, human excreta amended with BC, cattle manure, and cattle manure amended with BC, respectively, suggesting a final compost product free of pathogens. The compost mixture with cattle manure and BC reached a significantly higher temperature than the same variant without BC, with a maximum value of 65.9 °C on Day 6. For all treatments, final germination index values >100% indicated compost maturity and the absence of phytotoxic substances. Biochar addition reduced losses of organic matter (18−23%), C (33−42%), and N (49−100%) and decreased the amount of extractable NO3− (32−36%) in the final compost. The tested ecological sanitation concept via thermophilic composting is thus a promising strategy to improve access to cheap fertilizer by safe and sustainable sanitation and waste management.
Neolithic and Bronze Age topsoil relicts revealed enhanced extractable phosphorus (P) and plant available inorganic P fractions, thus raising the question whether there was targeted soil amelioration in prehistoric times. This study aimed (i) at assessing the overall nutrient status and the soil organic matter content of these arable topsoil relicts, and (ii) at tracing ancient soil fertilizing practices by respective stable isotope and biomarker analyses. Prehistoric arable topsoils were preserved in archaeological pit fillings, whereas adjacent subsoils served as controls. One Early Weichselian humic zone represented the soil status before the introduction of agriculture. Recent topsoils served as an additional reference. The applied multi-proxy approach comprised total P and micronutrient contents, stable N isotope ratios, amino acid, steroid, and black carbon analyses as well as soil color measurements. Total contents of P and selected micronutrients (I, Cu, Mn, Mo, Se, Zn) of the arable soil relicts were above the limits for which nutrient deficiencies could be assumed. All pit fillings exhibited elevated δ15N values close to those of recent topsoils (δ15N>6 to 7‰), giving first hints for prehistoric organic N-input. Ancient legume cultivation as a potential source for N input could not be verified by means of amino acid analysis. In contrast, bile acids as markers for faecal input exhibited larger concentrations in the pit fillings compared with the reference and control soils indicating faeces (i.e. manure) input to Neolithic arable topsoils. Also black carbon contents were elevated, amounting up to 38% of soil organic carbon, therewith explaining the dark soil color in the pit fillings and pointing to inputs of burned biomass. The combination of different geochemical analyses revealed a sufficient nutrient status of prehistoric arable soils, as well as signs of amelioration (inputs of organic material like charcoal and faeces-containing manure).
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