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Charcoal-rich Technosols on century-old relict charcoal hearths (RCHs) are the subject of ongoing research regarding potential legacy effects that result from historic charcoal production and subsequent charcoal amendments on forest soil properties and forest ecosystems today. RCHs consist mostly of Auh horizons that are substantially enriched in soil organic carbon (SOC), of which the largest part seems to be of pyrogenic origin (PyC). However, the reported range of SOC and PyC contents in RCH soil also suggests that they are enriched in nonpyrogenic SOC. RCH soils are discussed as potential benchmarks for the long-term influence of biochar amendment and the post-wildfire influences on soil properties. In this study, we utilised a large soil sample dataset (n = 1245) from 52 RCH sites in north-western Connecticut, USA, to quantify SOC contents by total element analysis. The contents of condensed highly aromatic carbon as a proxy for black carbon (BC) were predicted by using a modified benzene polycarboxylated acid (BPCA) marker method in combination with diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy-based partial least square regression (r2 = 0.89). A high vertical spatial sampling resolution allowed the identification of soil organic matter (SOM) enrichment and translocation processes. The results show an average 75% and 1862% increase in TOC and BPCA-derived carbon, respectively, for technogenic Auh horizons compared to reference soils. In addition to an increase in aromatic properties, increased carboxylic properties of the RCH SOC suggest self-humification effects of degrading charcoal and thereby the continuing formation of leachable aromatic carbon compounds, which could have effects on pedogenic processes in buried soils. Indeed, we show BPCA-derived carbon concentrations in intermediate technogenic Cu horizons and buried top/subsoils that suggest vertical translocation of highly aromatic carbon originating in RCH Auh horizons. Topmost Auh horizons showed a gradual decrease in total organic carbon (TOC) contents with increasing depth, suggesting accumulation of recent, non-pyrogenic SOM. Lower aliphatic absorptions in RCH soil spectra suggest different SOM turnover dynamics compared to reference soils. Furthermore, studied RCH soils featured additional TOC enrichment, which cannot be fully explained now.
In Germany, at more than 1000 sites, soil is polluted with an anthropogenic contaminant in form of iron-cyanide complexes. These contaminations are caused by former Manufactured Gas Plants (MGPs), where electricity for lighting was produced in the process of coal gasification. The production of manufactured gas was restrained in 1950, which caused cessation of MGPs. Our study describes the application of Polychromix Handheld Field Portable Near-Infrared (NIR) Analyzer to predict the cyanide concentrations in soil. In recent times, when the soil remediation is of major importance, there is a need to develop rapid and non-destructive methods for contaminant determination in the field. In situ analysis enables determination of ‘hot spots’, is cheap and time saving in comparison to laboratory methods. This paper presents a novel usage of NIR spectroscopy, where a calibration model was developed, using multivariate calibration algorithms, in order to determine NIR spectral response to the cyanide concentration in soil samples. As a control, the contaminant concentration was determined using conventional Flow Injection Analysis (FIA). The experiments revealed that portable near-infrared spectrometers could be a reliable device for identification of contamination ‘hot spots’, where cyanide concentration are higher than 2400
mg kg-1 in the field and >1750 mg kg-1 after sample preparation in the laboratory, but cannot replace traditional laboratory analyses due to high limits of detection.
Vicinities of manufactured gas plants were often contaminated with solid iron–cyanide complexes
as a result of the coal gasification process. During the remediation of affected soils, knowledge about contaminant concentrations is crucial, but laboratory methods are often expensive and time consuming. Rapid and non-destructive field methods for contaminant determination permit an analysis of large sample numbers and hence, facilitate identification of ‘hot spots’ of contamination. Diffuse near infrared reflectance spectroscopy has proven to be a reliable analytical tool in soil investigation. In order to determine the feasibility of a Polychromix Handheld Field Portable Near-Infrared Analyzer (FP NIR), various sample preparation methods were examined, including homogenizing, sieving, drying, and grinding. Partial least squares calibration models were developed to determine near infrared (NIR) spectral responses to the cyanide concentration in the soil samples. As a control, the contaminant concentration
was determined using conventional flow injection analysis. The experiments revealed that portable
near-infrared spectrometers could be a reliable device for detecting cyanide concentrations >2,400 mgkg−1 in the field and >1,750 mgkg−1 after sample preparation in the laboratory.We found that portable NIR spectrometry cannot replace traditional laboratory analyses due to high limits of detection, but that it could be used for identification of contamination ‘hot spots’.
The influence of biological soil crusts in natural ecosystems on structures and processes is well investigated. However, in South-Brandenburg (Germany), it is possible to study the development of biological soil crusts (BSC) during initial ecosystem genesis on two artificial water catchments with well-known ages and under differing starting conditions. The two experimental sites are located in the recultivation area of the lignite open-cast mining district of southern Brandenburg with a distance of approximately 1 km between them. Two different topographies were constructed at the experimental sites: the experimental plot at the catchment Neuer Lugteich was shaped like a dune, whereas the artificial water catchment Hühnerwasser was modelled as an inclined slope. The catchment Neuer Lugteich is four years older than Hühnerwasser. The original substrate at Neuer Lugteich is more sandy and carbonate-free compared to the original substrate dumped at Hühnerwasser. At both sites geomorphological differentiation and crust development were compared and the importance of substrate-dependent water availability and crust type clarified. Once settled, the crusts influenced the water regime of the soils by delaying infiltration through enhanced water repellency, and by limiting water infiltration. Chlorophyll analysis revealed that all crusts were at early stages of development. At Neuer Lugteich, the establishment of the biological soil crusts was closely associated with the vegetation succession, whereas no clear succession of the crusts could be observed at Hühnerwasser. The mosaic-like pattern of the biological soils crusts is associated with the distribution of fine-grained material here.zeige weniger
Iron-cyanide (Fe-CN) complexes have been detected at Manufactured Gas Plant sites (MGP) worldwide. The risk of groundwater contamination depends mainly on the dissolution of ferric ferrocyanide. In order to design effective reme- diation strategies, it is relevant to understand the contaminant’s fate and transport in soil, and to quantify and mathe- matically model a release rate. The release of iron-cyanide complexes from four contaminated soils, originating from the former MGP in Cottbus, has been studied by using a column experiment. Results indicated that long-term cyanide (CN) release is governed by two phases: one readily dissolved and one strongly fixed. Different isotherm and kinetic equations were used to investigate the driving mechanisms for the ferric ferrocyanide release. Applying the isotherm equations assumed an approach by which two phases were separate in time, whereas the multiple first order equation considered simultaneous occurrence of both cyanide pools. Results indicated varying CN release rates according to the phase and soil. According to isotherm and kinetic models, the long-term iron cyanide release from the MGP soils is a complex phenomenon driven by various mechanisms parallely involving desorption, diffusion and transport processes. Phase I (rapid release) is presumably mainly constrained by the transport process of readily dissolved iron-cyanide complexes combined with desorption of CN bound to reactive heterogeneous surfaces that are in direct contact with the aqueous phase (outer-sphere complexation). Phase II (limited rate) is presumably driven by the diffusion controlled processes involving dissolution of precipitated ferric ferrocyanide from the mineral or inner-sphere complexation of fer- ricyanides. CN release rates in phase I and II were mainly influenced by the pH, organic matter (OM) and the total CN content. The cyanide release rates increased with increasing pH, decreased with low initial CN concentration and were retarded by the increase in OM content.
Cross-linked polyacrylates in post-mining substrates: persistence and effects on plant growth
(2014)
Application of hydrophilic polymers composed of cross-linked polyacrylate can improve soil water-holding capacity and accelerate the restoration of post-mining substrates. In this work, we studied the persistence of a polyacrylate polymer incorporated into a soil and its impact on plant nutrients at a reclamation site of former lignite mining in Lusatia (Germany). In contrast to autumn application, the incorporation of the polymer enhanced the sequestration of plant-derived carbon in the soil, which was reflected by a significant increase in the concentration of a lignin marker. Attenuated total reflexion–Fourier transform infrared spectra (ATR-FTIR) and total elemental contents in the applied polymer suggested an intensive cation exchange between the polymer framework and the soil-forming substrate. In addition, there was an enrichment of carbonaceous material, which seems to reduce the swelling and thus the water-holding capacity of the cross-linked polyacrylate. Conversely, this process protected the polymer structure from rapid decomposition.