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Clay-sized soil minerals are known to protect organic carbon (OC) from mineralisation by formation of organo-mineral associations limiting its availability to microorganisms. The impact of soil fauna on these processes is poorly known. The aim of this study was to investigate the effect of earthworms on organic matter (OM) decomposition and association with minerals during a laboratory experiment. We used a model system consisting of fresh OM incubated with and without epigeic earthworms (Eisenia andrei and foetida) in presence of different types and amounts of phyllosilicates (kaolinite, montmorillonite) and an iron oxide (goethite) and combinations of these minerals. Our experimental setup included a high OM:mineral ratio to represent the soil-litter interphase. We monitored OC mineralisation during 196 days. Additionally, we investigated physicochemical parameters and chemical OM characteristics of decomposition products by determination of water-soluble OC (WSOC) and acquisition of solid-state 13C NMR spectra. We also analysed microscale organisation of the organo-mineral associations produced with and without earthworms by transmission electron microscopy (TEM). Earthworms enhanced OC mineralisation in all treatments. They also led to greater reductions of OC emissions in the presence of minerals as compared to the mineral-free control, depending on the type and amount of minerals added. The presence of earthworms affected microbial biomass, the concentration of WSOC and increased the contribution of aromatic compounds to OM decomposition products. Microscale analyses by TEM showed that earthworms favoured association of minerals with partly degraded OM along with completely degraded material, while in absence of earthworms only completely degraded OM was associated with minerals. We conclude that earthworms impact OM decomposition through (1) their effect on microbial biomass and the physicochemical parameters of microbial habitat and (2) the formation of OM associations by changing the OM types associated to minerals and possibly by creating closer association of partly degraded OM and iron oxides. The stability of these associations remains to be investigated. • Earthworms increase organic carbon mineralisation in presence of minerals. • Earthworms strengthen stabilising effect of minerals. • Earthworm impact on physicochemical soil parameters depends on mineral type. • Earthworms influence organic matter types associated to soil minerals. [ABSTRACT FROM AUTHOR]

The structure of soil aggregates plays an important role for the turnover of particulate organic matter (POM) and vice versa. Analytical approaches usually do not disentangle the continuous re-organization of soil aggregates, caught between disintegration and assemblage. This led to a lack of understanding of the mechanistic relationship between aggregation and organic matter dynamics in soils. In this study, we took advantage of a process-based mechanistic model that describes the interaction between the dynamic (re-)arrangement of soil aggregates, based on dynamic image analysis data of wet-sieved aggregates, to analyze the turnover of POM, and simultaneous soil surface interactions in a spatially and temporally explicit way. Our novel modeling approach enabled us to unravel the temporal development of aggregate sizes, organic carbon (OC) turnover of POM, and surface coverage as affected by soil texture, POM input, and POM decomposition rate comparing a low and high clay soil (18% and 33% clay content). Our results reveal the importance of the dynamic re-arrangement of soil structure on POM-related turnover of OC in soils. Firstly, aggregation was largely determined by the POM input fostering aggregates through additional gluing joints outweighing soil texture at lower decomposition rate, whereas at higher decomposition rate, soil texture had a higher influence leading to larger aggregates in the high clay soil. Secondly, the POM storage increased with clay content, showing that surface interactions may delay the turnover of OC into CO 2 . Thirdly, we observed a structural priming effect in which the increased input of POM induced increased structural re-arrangement stimulating the mineralization of old POM. This work highlights that the dynamic re-arrangement of soil aggregates has important implications for OC turnover and is driven by underlying surface interactions where temporary gluing spots stabilize larger aggregates., (© 2022 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Microbial necromass is a central component of soil organic matter (SOM), whose management may be essential in mitigating atmospheric CO 2 concentrations and climate change. Current consensus regards the magnitude of microbial necromass production to be heavily dependent on the carbon use efficiency of microorganisms, which is strongly influenced by the quality of the organic matter inputs these organisms feed on. However, recent concepts neglect agents relevant in many soils: earthworms. We argue that the activity of earthworms accelerates the formation of microbial necromass stabilized in aggregates and organo-mineral associations and reduces the relevance of the quality of pre-existing organic matter in this process. Earthworms achieve this through the creation of transient hotspots (casts) characterized by elevated contents of bioavailable substrate and the efficient build-up and quick turnover of microbial biomass, thus converting SOM not mineralized in this process into a state more resistant against external disturbances, such as climate change. Promoting the abundance of earthworms may, therefore, be considered a central component of management strategies that aim to accelerate the formation of stabilized microbial necromass in wide locations of the soil commonly not considered hotspots of microbial SOM formation., (© 2022 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

The charge- and concentration-dependent sorption behavior of a range of per- and polyfluoroalkyl substances (PFASs) was studied for three organic soil samples with different organic matter quality, one Spodosol Oe horizon (Mor Oe) and two Sphagnum peats with different degrees of decomposition (Peat Oi and Peat Oe). Sorption to the two peat materials was, on average, four times stronger compared to that onto the Mor Oe material. In particular, longer-chained PFASs were more strongly bound by the two peats as compared to the Mor Oe sample. The combined results of batch sorption experiments and 13 C NMR spectroscopy suggested sorption to be positively related to the content of carbohydrates (i.e., O-alkyl carbon). Sorption of all PFAS subclasses was inversely related to the pH value in all soils, with the largest pH effects being observed for perfluoroalkyl carboxylates (PFCAs) with C 10 and C 11 perfluorocarbon chain lengths. Experimentally determined sorption isotherms onto the poorly humified Peat Oi did not deviate significantly from linearity for most substances, while for the Mor Oe horizon, sorption nonlinearity was generally more pronounced. This work should prove useful in assessing PFAS sorption and leaching in organic soil horizons within environmental risk assessment., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Nutrient turnover in soils is strongly driven by soil properties, including clay mineral composition. One main nutrient is phosphorus (P), which is known to be easily immobilized in soil. Therefore, the specific surface characteristics of clay minerals might substantially influence P availability in soil and thus the microbial strategies for accessing P pools. We used a metagenomic approach to analyze the microbial potential to access P after 842 days of incubation in artificial soils with a clay mineral composition of either non-expandable illite (IL) or expandable montmorillonite (MT), which differ in their surface characteristics like soil surface area and surface charge. Our data indicate that microorganisms of the two soils developed different strategies to overcome P depletion, resulting in similar total P concentrations. Genes predicted to encode inorganic pyrophosphatase (ppa), exopolyphosphatase (ppx), and the pstSCAB transport system were higher in MT, suggesting effective P uptake and the use of internal poly-P stores. Genes predicted to encode enzymes involved in organic P turnover like alkaline phosphatases (phoA, phoD) and glycerophosphoryl diester phosphodiesterase were detected in both soils in comparable numbers. In addition, P o concentrations did not differ significantly. Most identified genes were assigned to microbial lineages generally abundant in agricultural fields, but some were assigned to lineages known to include oligotrophic specialists, such as Bacillaceae and Microchaetaceae.

Sustainable soil carbon sequestration practices need to be rapidly scaled up and implemented to contribute to climate change mitigation. We highlight that the major potential for carbon sequestration is in cropland soils, especially those with large yield gaps and/or large historic soil organic carbon losses. The implementation of soil carbon sequestration measures requires a diverse set of options, each adapted to local soil conditions and management opportunities, and accounting for site-specific trade-offs. We propose the establishment of a soil information system containing localised information on soil group, degradation status, crop yield gap, and the associated carbon-sequestration potentials, as well as the provision of incentives and policies to translate management options into region- and soil-specific practices.

Soil health is the continued capacity of soil to function as a vital living ecosystem that sustains plants, animals and humans, and connects agricultural and soil science to policy, stakeholder needs and sustainable supply chain management. Historically, soil assessments focused on crop production, but today soil health also includes the role of soil in water quality, climate change and human health. However, quantifying soil health is still dominated by chemical indicators, despite growing appreciation of the importance of soil biodiversity, due to limited functional knowledge and lack of effective methods. In this Perspective, the definition and history of soil health are described and compared to other soil concepts. We outline ecosystem services provided by soils, the indicators used to measure soil functionality, and their integration into informative soil health indices. Scientists should embrace soil health as an overarching principle that contributes to sustainability goals, rather than only a property to measure., Toc Blurb: Soil health is essential to crop production, but is also key to many ecosystem services. In this Perspective, the definition, impact and quantification of soil health are examined, and the needs in soil health research are outlined., Competing Interests: Competing interests The authors declare no competing interests.

Subsoil organic carbon (OC) is generally lower in content and more heterogeneous than topsoil OC, rendering it difficult to detect significant differences in subsoil OC storage. We tested the application of laboratory hyperspectral imaging with a variety of machine learning approaches to predict OC distribution in undisturbed soil cores. Using a bias-corrected random forest we were able to reproduce the OC distribution in the soil cores with very good to excellent model goodness-of-fit, enabling us to map the spatial distribution of OC in the soil cores at very high resolution (~53 × 53 µm). Despite a large increase in variance and reduction in OC content with increasing depth, the high resolution of the images enabled statistically powerful analysis in spatial distribution of OC in the soil cores. In contrast to the relatively homogeneous distribution of OC in the plough horizon, the subsoil was characterized by distinct regions of OC enrichment and depletion, including biopores which contained ~2-10 times higher SOC contents than the soil matrix in close proximity. Laboratory hyperspectral imaging enables powerful, fine-scale investigations of the vertical distribution of soil OC as well as hotspots of OC storage in undisturbed samples, overcoming limitations of traditional soil sampling campaigns.

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 )., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Biochar (BC) amendments may be suitable to increase the ecosystems resistance to drought due to their positive effects on soil water retention and availability. We investigated the effect of BC in situ ageing on water availability and microbial parameters of a grassland soil. We used soil containing 13 C labeled BC and determined its water holding capacity, microbial biomass and activity during a 3 months incubation under optimum and drought conditions. Our incubation experiment comprised three treatments: soil without BC (Control), soil containing aged BC (BC aged ) and soil containing fresh BC (BC fresh ), under optimum soil water (pF 1.8) and drought conditions (pF 3.5). Under optimum water as well as drought conditions, soils containing BC showed higher soil organic carbon (SOC) mineralization as compared to control soil. Moreover, BC effects on the soil water regime increase upon in situ aging. Native SOC mineralization increased most for soils containing BC aged . The BC aged led to improved C use under drought as compared to the other treatments. We conclude that BC addition to soils can ameliorate their water regime, especially under drought conditions. This beneficial effect of BC increases upon its aging, which also improved native substrate availability.

Rationale: Aluminium (Al)-substituted goethite is ubiquitous in soils and sediments. The extent of Al-substitution affects the physicochemical properties of the mineral and influences its macroscale properties. Bulk analysis only provides total Al/Fe ratios without providing information with respect to the Al-substitution of single minerals. Here, we demonstrate that nanoscale secondary ion mass spectrometry (NanoSIMS) enables the precise determination of Al-content in single minerals, while simultaneously visualising the variation of the Al/Fe ratio., Methods: Al-substituted goethite samples were synthesized with increasing Al concentrations of 0.1, 3, and 7 % and analysed by NanoSIMS in combination with established bulk spectroscopic methods (XRD, FTIR, Mössbauer spectroscopy). The high spatial resolution (50-150 nm) of NanoSIMS is accompanied by a high number of single-point measurements. We statistically evaluated the Al/Fe ratios derived from NanoSIMS, while maintaining the spatial information and reassigning it to its original localization., Results: XRD analyses confirmed increasing concentration of incorporated Al within the goethite structure. Mössbauer spectroscopy revealed 11 % of the goethite samples generated at high Al concentrations consisted of hematite. The NanoSIMS data show that the Al/Fe ratios are in agreement with bulk data derived from total digestion and demonstrated small spatial variability between single-point measurements. More advantageously, statistical analysis and reassignment of single-point measurements allowed us to identify distinct spots with significantly higher or lower Al/Fe ratios., Conclusions: NanoSIMS measurements confirmed the capacity to produce images, which indicated the uniform increase in Al-concentrations in goethite. Using a combination of statistical analysis with information from complementary spectroscopic techniques (XRD, FTIR and Mössbauer spectroscopy) we were further able to reveal spots with lower Al/Fe ratios as hematite., (Copyright © 2018 John Wiley & Sons, Ltd.)

The enrichment culture KS is one of the few existing autotrophic, nitrate-reducing, Fe(II)-oxidizing cultures that can be continuously transferred without an organic carbon source. We used a combination of catalyzed amplification reporter deposition fluorescence in situ hybridization (CARD-FISH) and nanoscale secondary ion mass spectrometry (NanoSIMS) to analyze community dynamics, single-cell activities, and interactions among the two most abundant microbial community members (i.e., Gallionellaceae sp. and Bradyrhizobium spp.) under autotrophic and heterotrophic growth conditions. CARD-FISH cell counts showed the dominance of the Fe(II) oxidizer Gallionellaceae sp. under autotrophic conditions as well as of Bradyrhizobium spp. under heterotrophic conditions. We used NanoSIMS to monitor the fate of 13 C-labeled bicarbonate and acetate as well as 15 N-labeled ammonium at the single-cell level for both taxa. Under autotrophic conditions, only the Gallionellaceae sp. was actively incorporating 13 C-labeled bicarbonate and 15 N-labeled ammonium. Interestingly, both Bradyrhizobium spp. and Gallionellaceae sp. became enriched in [ 13 C]acetate and [ 15 N]ammonium under heterotrophic conditions. Our experiments demonstrated that Gallionellaceae sp. was capable of assimilating [ 13 C]acetate while Bradyrhizobium spp. were not able to fix CO 2 , although a metagenomics survey of culture KS recently revealed that Gallionellaceae sp. lacks genes for acetate uptake and that the Bradyrhizobium sp. carries the genetic potential to fix CO 2 The study furthermore extends our understanding of the microbial reactions that interlink the nitrogen and Fe cycles in the environment. IMPORTANCE Microbial mechanisms by which Fe(II) is oxidized with nitrate as the terminal electron acceptor are generally referred to as "nitrate-dependent Fe(II) oxidation" (NDFO). NDFO has been demonstrated in laboratory cultures (such as the one studied in this work) and in a variety of marine and freshwater sediments. Recently, the importance of NDFO for the transport of sediment-derived Fe in aquatic ecosystems has been emphasized in a series of studies discussing the impact of NDFO for sedimentary nutrient cycling and redox dynamics in marine and freshwater environments. In this article, we report results from an isotope labeling study performed with the autotrophic, nitrate-reducing, Fe(II)-oxidizing enrichment culture KS, which was first described by Straub et al. (1) about 20 years ago. Our current study builds on the recently published metagenome of culture KS (2)., (Copyright © 2018 American Society for Microbiology.)

Global change contributes to the retreat of glaciers at unprecedented rates. The deglaciation facilitates biogeochemical processes on glacial deposits with initiating soil formation as an important driver of evolving ecosystems. The underlying mechanisms of soil formation and the association of soil organic matter (SOM) with mineral particles remain unclear, although further insights are critical to understand carbon sequestration in soils. We investigated the microspatial arrangement of SOM coatings at intact soil microaggregate structures during various stages of ecosystem development from 15 to >700 years after deglaciation in the proglacial environment of the Damma glacier (Switzerland). The functionally important clay-sized fraction (<2 μm) was separated into two density fractions with different amounts of organo-mineral associations: light (1.6-2.2 g/cm 3 ) and heavy (>2.2 g/cm 3 ). To quantify how SOM extends across the surface of mineral particles (coverage) and whether SOM coatings are distributed in fragmented or connected patterns (connectivity), we developed an image analysis protocol based on nanoscale secondary ion mass spectrometry (NanoSIMS). We classified SOM and mineral areas depending on the 16 O - , 12 C - , and 12 C 14 N - distributions. With increasing time after glacial retreat, the microspatial coverage and connectivity of SOM increased rapidly. The rapid soil formation led to a succession of patchy distributed to more connected SOM coatings on soil microaggregates. The maximum coverage of 55% at >700 years suggests direct evidence for SOM sequestration being decoupled from the mineral surface, as it was not completely masked by SOM and retained its functionality as an ion exchange site. The chemical composition of SOM coatings showed a rapid change toward a higher CN:C ratio already at 75 years after glacial retreat, which was associated with microbial succession patterns reflecting high N assimilation. Our results demonstrate that rapid SOM sequestration drives the microspatial succession of SOM coatings in soils, a process that can stabilize SOM for the long term., (© 2017 John Wiley & Sons Ltd.)

Agricultural soils are widely recognized to be capable of carbon sequestration that contributes to mitigating CO 2 emissions. To better understand soil organic carbon (SOC) stock dynamics and its driving and controlling factors corresponding with a period of rapid agronomic evolution from the 1980s to the 2010s in the North China Plain (NCP), we collected data from two region-wide soil sampling campaigns (in the 1980s and 2010s) and conducted an analysis of the controlling factors using the random forest model. Between the 1980s and 2010s, environmental (i.e. soil salinity/fertility) and societal (i.e. policy/techniques) factors both contributed to adoption of new management practices (i.e. chemical fertilizer application/mechanization). Results of our work indicate that SOC stocks in the NCP croplands increased significantly, which also closely related to soil total nitrogen changes. Samples collected near the surface (0-20 cm) and deeper (20-40 cm) both increased by an average of 9.4 and 5.1 Mg C ha -1 , respectively, which are equivalent to increases of 73% and 56% compared with initial SOC stocks in the 1980s. The annual carbon sequestration amount in surface soils reached 10.9 Tg C year -1 , which contributed an estimated 43% of total carbon sequestration in all of China's cropland on just 27% of its area. Successful desalinization and the subsequent increases in carbon (C) inputs, induced by agricultural projects and policies intended to support crop production (i.e. reconstruction of low yield farmland, and agricultural subsidies), combined with improved cultivation practices (i.e. fertilization and straw return) since the early 1980s were the main drivers for the SOC stock increase. This study suggests that rehabilitation of NCP soils to reduce salinity and increase crop yields have also served as a pathway for substantial soil C sequestration., (© 2017 John Wiley & Sons Ltd.)

Phosphorus (P) constitutes one of five macronutrients essential for plant growth and development due to the central function of phosphate in energy metabolism, inheritance and metabolic control. In many ecosystems, plant available soil-P gets limited by soil aging. Hence, plants have developed adaptation strategies to cope with such limitation by an efficient plant and ecosystem internal P-cycling during annual growth. The natural floodplain habitat of fast-growing Populus × canescens is characterized by high soil-P availability. It was thus expected that the P-nutrition of P. × canescens had adapted to this conditions. Therefore, different P-fractions in different twig tissues were investigated during two annual growth cycles. The P-nutrition of P. × canescens markedly differs from that of European beech grown at low soil-P availability (Netzer F, Schmid C, Herschbach C, Rennenberg H (2017) Phosphorus-nutrition of European beech (Fagus sylvatica L.) during annual growth depends on tree age and P-availability in the soil. Environ Exp Bot 137:194-207). This was mainly due to a lack of tree internal P-cycling during annual growth indicated by the absence of P-storage and remobilization in twig bark and wood. Hence, strategies to economize P-nutrition and to prevent P-losses had not developed. This fits with the fast-growth strategy of P. × canescens at unrestricted P-availability. Hence, the P-nutrition strategy of P. × canescens can be seen as an evolutionary adaptation to its natural growth habitat., (© The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

We examined the potential of stable-isotope Raman microspectroscopy (SIRM) for the evaluation of differently enriched 13 C-labeled humic acids as model substances for soil organic matter (SOM). The SOM itself can be linked to the soil water holding capacity. Therefore, artificial humic acids (HA) with known isotopic compositions were synthesized and analyzed by means of SIRM. By performing a pregraphitization, a suitable analysis method was developed to cope with the high fluorescence background. Results were verified against isotope ratio mass spectrometry (IRMS). The limit of quantification was 2.1 × 10 -1 13 C/C tot for the total region and 3.2 × 10 -2 13 C/C tot for a linear correlation up to 0.25 13 C/C tot . Complementary nanoscale secondary ion mass spectrometry (NanoSIMS) analysis indicated small-scale heterogeneity within the dry sample material, even though-owing to sample topography and occurring matrix effects-obtained values deviated in magnitude from those of IRMS and SIRM. Our study shows that SIRM is well-suited for the analysis of stable isotope-labeled HA. This method requires no specific sample preparation and can provide information with a spatial resolution in the micrometer range. Graphical abstract Analysis of the isotopic composition of humic acids by Raman microspectroscopy in combination with isotope ratio mass spectrometry and nanoscale secondary ion mass spectrometry.

The physical, chemical, and biological processes forming the backbone of important soil functions (e.g., carbon sequestration, nutrient and contaminant storage, and water transport) take place at reactive interfaces of soil particles and pores. The accessibility of these interfaces is determined by the spatial arrangement of the solid mineral and organic soil components, and the resulting pore system. Despite the development and application of novel imaging techniques operating at the micrometer and even nanometer scale, the microstructure of soils is still considered as a random arrangement of mineral and organic components. Using nanoscale secondary ion mass spectroscopy (NanoSIMS) and a novel digital image processing routine adapted from remote sensing (consisting of image preprocessing, endmember extraction, and a supervised classification), we extensively analyzed the spatial distribution of secondary ions that are characteristic of mineral and organic soil components on the submicrometer scale in an intact soil aggregate (40 measurements, each covering an area of 30 μm × 30 μm with a lateral resolution of 100 nm × 100 nm). We were surprised that the 40 spatially independent measurements clustered in just two complementary types of micrometer-sized domains. Each domain is characterized by a microarchitecture built of a definite mineral assemblage with various organic matter forms and a specific pore system, each fulfilling different functions in soil. Our results demonstrate that these microarchitectures form due to self-organization of the manifold mineral and organic soil components to distinct mineral assemblages, which are in turn stabilized by biophysical feedback mechanisms acting through pore characteristics and microbial accessibility. These microdomains are the smallest units in soil that fulfill specific functionalities.

Accumulating evidence indicates that future rates of atmospheric N deposition have the potential to increase soil C storage by reducing the decay of plant litter and soil organic matter (SOM). Although the microbial mechanism underlying this response is not well understood, a decline in decay could alter the amount, as well as biochemical composition of SOM. Here, we used size-density fractionation and solid-state 13 C-NMR spectroscopy to explore the extent to which declines in microbial decay in a long-term (ca. 20 yrs.) N deposition experiment have altered the biochemical composition of forest floor, bulk mineral soil, as well as free and occluded particulate organic matter. Significant amounts of organic matter have accumulated in occluded particulate organic matter (~20%; oPOM); however, experimental N deposition had not altered the abundance of carboxyl, aryl, alkyl, or O/N-alkyl C in forest floor, bulk mineral soil, or any soil fraction. These observations suggest that biochemically equivalent organic matter has accumulated in oPOM at a greater rate under experimental N deposition, relative to the ambient treatment. Although we do not understand the process by which experimental N deposition has fostered the occlusion of organic matter by mineral soil particles, our results highlight the importance of interactions among the products of microbial decay and the chemical and physical properties of silt and clay particles that occlude organic matter from microbial attack. Because oPOM can reside in soils for decades to centuries, organic matter accumulating under future rates of anthropogenic N deposition could remain in soil for long periods of time. If temperate forest soils in the Northern Hemisphere respond like those in our experiment, then unabated deposition of anthropogenic N from the atmosphere has the potential to foster greater soil C storage, especially in fine-texture forest soils., (© 2016 John Wiley & Sons Ltd.)

Climate change and stagnating crop yields may cause a decline of SOC stocks in agricultural soils leading to considerable CO2 emissions and reduced agricultural productivity. Regional model-based SOC projections are needed to evaluate these potential risks. In this study, we simulated the future SOC development in cropland and grassland soils of Bavaria in the 21(st) century. Soils from 51 study sites representing the most important soil classes of Central Europe were fractionated and derived SOC pools were used to initialize the RothC soil carbon model. For each site, long-term C inputs were determined using the C allocation method. Model runs were performed for three different C input scenarios as a realistic range of projected yield development. Our modelling approach revealed substantial SOC decreases of 11-16% under an expected mean temperature increase of 3.3 °C assuming unchanged C inputs. For the scenario of 20% reduced C inputs, agricultural SOC stocks are projected to decline by 19-24%. Remarkably, even the optimistic scenario of 20% increased C inputs led to SOC decreases of 3-8%. Projected SOC changes largely differed among investigated soil classes. Our results indicated that C inputs have to increase by 29% to maintain present SOC stocks in agricultural soils.

European beech forests growing on marginal calcareous soils have been proposed to be vulnerable to decreased soil water availability. This could result in a large-scale loss of ecological services and economical value in a changing climate. In order to evaluate the potential consequences of this drought-sensitivity, we investigated potential species range shifts for European beech forests on calcareous soil in the 21st century by statistical species range distribution modelling for present day and projected future climate conditions. We found a dramatic decline by 78% until 2080. Still the physiological or biogeochemical mechanisms underlying the drought sensitivity of European beech are largely unknown. Drought sensitivity of beech is commonly attributed to plant physiological constraints. Furthermore, it has also been proposed that reduced soil water availability could promote nitrogen (N) limitation of European beech due to impaired microbial N cycling in soil, but this hypothesis has not yet been tested. Hence we investigated the influence of simulated climate change (increased temperatures, reduced soil water availability) on soil gross microbial N turnover and plant N uptake in the beech-soil interface of a typical mountainous beech forest stocking on calcareous soil in SW Germany. For this purpose, triple 15N isotope labelling of intact beech seedling-soil-microbe systems was combined with a space-for-time climate change experiment. We found that nitrate was the dominant N source for beech natural regeneration. Reduced soil water content caused a persistent decline of ammonia oxidizing bacteria and therefore, a massive attenuation of gross nitrification rates and nitrate availability in the soil. Consequently, nitrate and total N uptake of beech seedlings were strongly reduced so that impaired growth of beech seedlings was observed already after one year of exposure to simulated climatic change. We conclude that the N cycle in this ecosystem and here specifically nitrification is vulnerable to reduced water availability, which can directly lead to nutritional limitations of beech seedlings. This tight link between reduced water availability, drought stress for nitrifiers, decreased gross nitrification rates and nitrate availability and finally nitrate uptake by beech seedlings could represent the Achilles' heel for beech under climate change stresses.

Soil organic carbon (SOC) from aboveground and belowground sources has rarely been differentiated although it may drive SOC turnover and stabilization due to a presumed differing source dependent degradability. It is thus crucial to better identify the location of SOC from different sources for the parameterization of SOC models, especially in the less investigated subsoils. The aim of this study was to spatially assess contributions of organic carbon from aboveground and belowground parts of beech trees to subsoil organic carbon in a Dystric Cambisol. Different sources of SOC were distinguished by solvent-extractable and hydrolysable lipid biomarkers aided by (14)C analyses of soil compartments <63 μm. We found no effect of the distance to the trees on the investigated parameters. Instead, a vertical zonation of the subsoil was detected. A high contribution of fresh leaf- and root-derived organic carbon to the upper subsoil (leaf- and root-affected zone) indicate that supposedly fast-cycling, leaf-derived SOC may still be of considerable importance below the A-horizon. In the deeper subsoil (root-affected zone), roots were an important source of fresh SOC. Simultaneously, strongly increasing apparent (14)C ages (3860 yrs BP) indicate considerable contribution of SOC that may be inherited from the Pleistocene parent material.

The carbon (C) balance of agricultural soils may be largely affected by climate change. Increasing temperatures are discussed to cause a loss of soil organic carbon (SOC) due to enhanced decomposition of soil organic matter, which has a high intrinsic temperature sensitivity. On the other hand, several modeling studies assumed that potential SOC losses would be compensated or even outperformed by an increased C input by crop residues into agricultural soils. This assumption was based on a predicted general increase of net primary productivity (NPP) as a result of the CO2 fertilization effect and prolonged growing seasons. However, it is questionable if the crop C input into agricultural soils can be derived from NPP predictions of vegetation models. The C input in European croplands is largely controlled by the agricultural management and was strongly related to the development of crop yields in the last decades. Thus, a glance at past yield development will probably be more instructive for future estimations of the C input than previous modeling approaches based on NPP predictions. An analysis of European yield statistics indicated that yields of wheat, barley and maize are stagnating in Central and Northern Europe since the 1990s. The stagnation of crop yields can probably be related to a fundamental change of the agricultural management and to climate change effects. It is assumed that the soil C input is concurrently stagnating which would necessarily lead to a decrease of agricultural SOC stocks in the long-term given a constant temperature increase. Remarkably, for almost all European countries that are faced with yield stagnation indications for agricultural SOC decreases were already found. Potentially adverse effects of yield stagnation on the C balance of croplands call for an interdisciplinary investigation of its causes and a comprehensive monitoring of SOC stocks in agricultural soils of Europe., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Organic carbon (OC) sequestration in degraded semi-arid environments by improved soil management is assumed to contribute substantially to climate change mitigation. However, information about the soil organic carbon (SOC) sequestration potential in steppe soils and their current saturation status remains unknown. In this study, we estimated the OC storage capacity of semi-arid grassland soils on the basis of remote, natural steppe fragments in northern China. Based on the maximum OC saturation of silt and clay particles <20 μm, OC sequestration potentials of degraded steppe soils (grazing land, arable land, eroded areas) were estimated. The analysis of natural grassland soils revealed a strong linear regression between the proportion of the fine fraction and its OC content, confirming the importance of silt and clay particles for OC stabilization in steppe soils. This relationship was similar to derived regressions in temperate and tropical soils but on a lower level, probably due to a lower C input and different clay mineralogy. In relation to the estimated OC storage capacity, degraded steppe soils showed a high OC saturation of 78-85% despite massive SOC losses due to unsustainable land use. As a result, the potential of degraded grassland soils to sequester additional OC was generally low. This can be related to a relatively high contribution of labile SOC, which is preferentially lost in the course of soil degradation. Moreover, wind erosion leads to substantial loss of silt and clay particles and consequently results in a direct loss of the ability to stabilize additional OC. Our findings indicate that the SOC loss in semi-arid environments induced by intensive land use is largely irreversible. Observed SOC increases after improved land management mainly result in an accumulation of labile SOC prone to land use/climate changes and therefore cannot be regarded as contribution to long-term OC sequestration., (© 2015 John Wiley & Sons Ltd.)

Microscale processes occurring at biogeochemical interfaces in soils and sediments have fundamental impacts on phenomena at larger scales. To obtain the organo-mineral associations necessary for the study of biogeochemical interfaces, bulk samples are usually fractionated into microaggregates or micrometer-sized single particles. Such fine-grained mineral particles are often prepared for nanoscale secondary ion mass spectroscopy (NanoSIMS) investigations by depositing them on a carrier. This introduces topographic differences, which can strongly affect local sputtering efficiencies. Embedding in resin causes undesired C impurities. We present a novel method for preparing polished cross-sections of micrometer-sized primary soil particles that overcomes the problems of topography and C contamination. The particles are coated with a marker layer, embedded, and well-polished. The interpretation of NanoSIMS data is assisted by energy-dispersive X-ray spectroscopy on cross-sections prepared by a focused ion beam. In the cross-sections, organic assemblages on the primary soil particles become visible. This novel method significantly improves the quality of NanoSIMS measurements on grainy mineral samples, enabling better characterization of soil biogeochemical interfaces. In addition, this sample preparation technique may also improve results from other (spectro-) microscopic techniques.

Clay minerals, charcoal and metal oxides are essential parts of the soil matrix and strongly influence the formation of biogeochemical interfaces in soil. We investigated the role of these parental materials for the development of functional microbial guilds using the example of alkane-degrading bacteria harbouring the alkane monooxygenase gene (alkB) in artificial mixtures composed of different minerals and charcoal, sterile manure and a microbial inoculum extracted from an agricultural soil. We followed changes in abundance and community structure of alkane-degrading microbial communities after 3 and 12 months of soil maturation and in response to a subsequent 2-week plant litter addition. During maturation we observed an overall increasing divergence in community composition. The impact of metal oxides on alkane-degrading community structure increased during soil maturation, whereas the charcoal impact decreased from 3 to 12 months. Among the clay minerals illite influenced the community structure of alkB-harbouring bacteria significantly, but not montmorillonite. The litter application induced strong community shifts in soils, maturated for 12 months, towards functional guilds typical for younger maturation stages pointing to a resilience of the alkane-degradation function potentially fostered by an extant 'seed bank'.

Ongoing climate change will lead to more extreme weather events, including severe drought periods and intense drying rewetting cycles. This will directly influence microbial nitrogen (N) turnover rates in soil by changing the water content and the oxygen partial pressure. Therefore, a space for time climate change experiment was conducted by transferring intact beech seedling-soil mesocosms from a northwest (NW) exposed site, representing today's climatic conditions, to a southwest (SW) exposed site, providing a model climate for future conditions with naturally occurring increased soil temperature (+0.8°C in average). In addition, severe drought and intense rainfall was simulated by a rainout shelter at SW and manual rewetting after 39 days drought, respectively. Soil samples were taken in June, at the end of the drought period (August), 24 and 72 hours after rewetting (August) and after a regeneration period of four weeks (September). To follow dynamics of bacterial and archaeal communities involved in N turnover, abundance and activity of nitrifiers, denitrifiers, N2-fixing microbes and N-mineralizers was analyzed based on marker genes and the related transcripts by qPCR from DNA and RNA directly extracted from soil. Abundance of the transcripts was reduced under climate change with most pronounced effects for denitrification. Our results revealed that already a transfer from NW to SW without further treatment resulted in decreased cnor and nosZ transcripts, encoding for nitric oxide reductase and nitrous oxide reductase, respectively, while nirK transcripts, encoding for nitrite reductase, remained unaffected. Severe drought additionally led to reduced nirK and cnor transcripts at SW. After rewetting, nirK transcripts increased rapidly at both sites, while cnor and nosZ transcripts increased only at NW. Our data indicate that the climate change influences activity pattern of microbial communities involved in denitrification processes to a different extend, which may impact emission rates of the greenhouse gas N2O.

Artificial soils were used in this study to analyse the importance of different mineral compositions for the diversity of soil microorganisms. Variants containing montmorillonite (MT), illite (IL) and illite + ferrihydrite (IL+FH) were compared to each other. Bulk material and their particle size fractions, as obtained by ultracentrifugation and wet-sieving, were characterised for abundance and diversity of Bacteria, Archaea and Fungi. Samples were analysed 6 and 18 months after inoculation with sterilised manure and a soil-extracted microbial community. Generally, IL, and even more pronouncedly IL+FH, supported the growth of more Bacteria, Archaea and Fungi, than MT. This trend was most pronounced in the finest fraction (< 20 μm). The structural diversity of Fungi responded more strongly to the different mineral compositions than the Bacteria, for which particle size fractions were more important. Archaea established a specific community in the finest fraction and showed no response to the different mineral compositions. Overall, this study demonstrates that the mineral composition and the particle size fractions have specific and different selective effects on the three domains and, thus, suggests that these factors strongly contribute to niche separation and the high diversity of microbial communities in natural soils with complex mineral compositions., (© 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.)

The fate of polycyclic aromatic hydrocarbons (PAHs) in soil is determined by a suite of biotic and abiotic factors, and disentangling their role in the complex soil interaction network remains challenging. Here, we investigate the influence of soil composition on the microbial community structure and its response to the spiked model PAH compound phenanthrene and plant litter. We used long-term matured artificial soils differing in type of clay mineral (illite, montmorillonite) and presence of charcoal or ferrihydrite. The soils received an identical soil microbial fraction and were incubated for more than two years with two sterile manure additions. The matured artificial soils and a natural soil were subjected to the following spiking treatments: (I) phenanthrene, (II) litter, (III) litter + phenanthrene, (IV) unspiked control. Total community DNA was extracted from soil sampled on the day of spiking, 7, 21, and 63 days after spiking. Bacterial 16S rRNA gene and fungal internal transcribed spacer amplicons were quantified by qPCR and subjected to denaturing gradient gel electrophoresis (DGGE). DGGE analysis revealed that the bacterial community composition, which was strongly shaped by clay minerals after more than two years of incubation, changed in response to spiked phenanthrene and added litter. DGGE and qPCR showed that soil composition significantly influenced the microbial response to spiking. While fungal communities responded only in presence of litter to phenanthrene spiking, the response of the bacterial communities to phenanthrene was less pronounced when litter was present. Interestingly, microbial communities in all artificial soils were more strongly affected by spiking than in the natural soil, which might indicate the importance of higher microbial diversity to compensate perturbations. This study showed the influence of soil composition on the microbiota and their response to phenanthrene and litter, which may increase our understanding of complex interactions in soils for bioremediation applications.

Sequestration of atmospheric carbon (C) in soils through improved management of forest and agricultural land is considered to have high potential for global CO2 mitigation. However, the potential of soils to sequester soil organic carbon (SOC) in a stable form, which is limited by the stabilization of SOC against microbial mineralization, is largely unknown. In this study, we estimated the C sequestration potential of soils in southeast Germany by calculating the potential SOC saturation of silt and clay particles according to Hassink [Plant and Soil 191 (1997) 77] on the basis of 516 soil profiles. The determination of the current SOC content of silt and clay fractions for major soil units and land uses allowed an estimation of the C saturation deficit corresponding to the long-term C sequestration potential. The results showed that cropland soils have a low level of C saturation of around 50% and could store considerable amounts of additional SOC. A relatively high C sequestration potential was also determined for grassland soils. In contrast, forest soils had a low C sequestration potential as they were almost C saturated. A high proportion of sites with a high degree of apparent oversaturation revealed that in acidic, coarse-textured soils the relation to silt and clay is not suitable to estimate the stable C saturation. A strong correlation of the C saturation deficit with temperature and precipitation allowed a spatial estimation of the C sequestration potential for Bavaria. In total, about 395 Mt CO2 -equivalents could theoretically be stored in A horizons of cultivated soils - four times the annual emission of greenhouse gases in Bavaria. Although achieving the entire estimated C storage capacity is unrealistic, improved management of cultivated land could contribute significantly to CO2 mitigation. Moreover, increasing SOC stocks have additional benefits with respect to enhanced soil fertility and agricultural productivity., (© 2013 John Wiley & Sons Ltd.)

The sequestration of carbon and nitrogen by clay-sized particles in soils is well established, and clay content or mineral surface area has been used to estimate the sequestration potential of soils. Here, via incubation of a sieved (<2 mm) topsoil with labelled litter, we find that only some of the clay-sized surfaces bind organic matter (OM). Surprisingly, <19% of the visible mineral areas show an OM attachment. OM is preferentially associated with organo-mineral clusters with rough surfaces. By combining nano-scale secondary ion mass spectrometry and isotopic tracing, we distinguish between new labelled and pre-existing OM and show that new OM is preferentially attached to already present organo-mineral clusters. These results, which provide evidence that only a limited proportion of the clay-sized surfaces contribute to OM sequestration, revolutionize our view of carbon sequestration in soils and the widely used carbon saturation estimates.

To study the influence of the clay minerals montmorillonite (M) and illite (I), the metal oxides ferrihydrite (F) and aluminum hydroxide (A), and charcoal (C) on soil bacterial communities, seven artificial soils with identical texture provided by quartz (Q) were mixed with sterilized manure as organic carbon source before adding a microbial inoculant derived from a Cambisol. Bacterial communities established in artificial soils after 90 days of incubation were compared by DGGE analysis of bacterial and taxon-specific 16S rRNA gene amplicons. The bacterial community structure of charcoal-containing soils highly differed from the other soils at all taxonomic levels studied. Effects of montmorillonite and illite were observed for Bacteria and Betaproteobacteria, but not for Actinobacteria or Alphaproteobacteria. A weak influence of metal oxides on Betaproteobacteria was found. Barcoded pyrosequencing of 16S rRNA gene amplicons done for QM, QI, QIF, and QMC revealed a high bacterial diversity in the artificial soils. The composition of the artificial soils was different from the inoculant, and the structure of the bacterial communities established in QMC soil was most different from the other soils, suggesting that charcoal provided distinct microenvironments and biogeochemical interfaces formed. Several populations with discriminative relative abundance between artificial soils were identified., (© 2013 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.)

Microbial communities in soil reside in a highly heterogeneous habitat where diverse mineral surfaces, complex organic matter and microorganisms interact with each other. This study aimed to elucidate the long-term effect of the soil mineral composition and charcoal on the microbial community composition established in matured artificial soils and their response to phenanthrene. One year after adding sterile manure to different artificial soils and inoculating microorganisms from a Cambisol, the matured soils were spiked with phenanthrene or not and incubated for another 70 days. 16S rRNA gene and internal transcribed spacer fragments amplified from total community DNA were analyzed by denaturing gradient gel electrophoresis. Metal oxides and clay minerals and to a lesser extent charcoal influenced the microbial community composition. Changes in the bacterial community composition in response to phenanthrene differed depending on the mineral composition and presence of charcoal, while no shifts in the fungal community composition were observed. The abundance of ring-hydroxylating dioxygenase genes was increased in phenanthrene-spiked soils except for charcoal-containing soils. Here we show that the formation of biogeochemical interfaces in soil is an ongoing process and that different properties present in artificial soils influenced the bacterial response to the phenanthrene spike., (© 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.)

Extracellular polymeric substances (EPS) are expected to be an important source for the formation of mineral-organic associations in soil. Because such formations affect the composition of mobile and immobile organic matter as well as the reactivity of minerals, we investigated the composition of EPS before and after adsorption to goethite. Raman measurements on EPS extracted from Bacillus subtilis distinguished four fractions rich in proteins, polysaccharides, lipids, or lipids and proteins. Scanning transmission X-ray microscopy identified three different EPS-fractions that varied in their composition in proteins, nonaromatic proteins, and polysaccharides. Reaction of EPS with goethite led to a preferential adsorption of lipids and proteins. The organic coverage was heterogeneous, consisting of ~100 × 200 nm large patches of either lipid-rich or protein-rich material. Nanoscale secondary ion mass spectrometry showed a strong S enrichment in aggregates of ~400 nm in the goethite adsorbed EPS. From our simplified model system, we learned that only a small portion (<10%) of EPS was immobilized via adsorption to goethite. This fraction formed a coating of subμm spaced protein-rich and lipid-rich domains, i.e., of two materials which will strongly differ in their reactive sites. This will finally affect further adsorption, the particle mobility and eventually also colloidal stability.

More than 50% of the world's population feeds on rice. Soils used for rice production are mostly managed under submerged conditions (paddy soils). This management, which favors carbon sequestration, potentially decouples surface from subsurface carbon cycling. The objective of this study was to elucidate the long-term rates of carbon accrual in surface and subsurface soil horizons relative to those of soils under nonpaddy management. We assessed changes in total soil organic as well as of inorganic carbon stocks along a 2000-year chronosequence of soils under paddy and adjacent nonpaddy management in the Yangtze delta, China. The initial organic carbon accumulation phase lasts much longer and is more intensive than previously assumed, e.g., by the Intergovernmental Panel on Climate Change (IPCC). Paddy topsoils accumulated 170-178 kg organic carbon ha(-1) a(-1) in the first 300 years; subsoils lost 29-84 kg organic carbon ha(-1) a(-1) during this period of time. Subsoil carbon losses were largest during the first 50 years after land embankment and again large beyond 700 years of cultivation, due to inorganic carbonate weathering and the lack of organic carbon replenishment. Carbon losses in subsoils may therefore offset soil carbon gains or losses in the surface soils. We strongly recommend including subsoils into global carbon accounting schemes, particularly for paddy fields., (© 2012 Blackwell Publishing Ltd.)

Globally, soil organic matter (SOM) contains more than three times as much carbon as either the atmosphere or terrestrial vegetation. Yet it remains largely unknown why some SOM persists for millennia whereas other SOM decomposes readily--and this limits our ability to predict how soils will respond to climate change. Recent analytical and experimental advances have demonstrated that molecular structure alone does not control SOM stability: in fact, environmental and biological controls predominate. Here we propose ways to include this understanding in a new generation of experiments and soil carbon models, thereby improving predictions of the SOM response to global warming.

In soil and water, ferrihydrite frequently forms in the presence of dissolved organic matter. This disturbs crystal growth and gives rise to coprecipitation of ferrihydrite and organic matter. To compare the chemical fractionation of organic matter during coprecipitation with the fractionation involved in adsorption onto pristine ferrihydrite surfaces we prepared ferrihydrite-organic matter associations by adsorption and coprecipitation using (i) a forest-floor extract or (ii) a sulfonated lignin. The reaction products were studied by (13)C CPMAS NMR, FTIR, and analysis of hydrolyzable neutral polysaccharides. Relative to the original forest-floor extract, the ferrihydrite-associated organic matter was enriched in polysaccharides, especially when adsorption took place. Moreover, mannose and glucose were bound preferentially to ferrihydrite, while fucose, arabinose, xylose, and galactose accumulated in the supernatant. This fractionation of sugar monomers was more pronounced during coprecipitation and led to an enhanced ratio of (galactose + mannose)/(arabinose + xylose). Experiments with lignin revealed that the ferrihydrite-associated material was enriched in its aromatic components but had a lower ratio of phenolic C to aromatic C than the original lignin. A compositional difference between the adsorbed and coprecipitated lignin is obvious from a higher contribution of methoxy C in the coprecipitated material. Coprecipitated organic matter may thus differ in amount and composition from adsorbed organic matter.

A novel PCR primer system that targets a wide range of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase (PAH-RHD(alpha)) genes of both Gram-positive and Gram-negative bacteria was developed and used to study their abundance and diversity in two different soils in response to phenanthrene spiking. The specificities and target ranges of the primers predicted in silico were confirmed experimentally by cloning and sequencing of PAH-RHD(alpha) gene amplicons from soil DNA. Cloning and sequencing showed the dominance of phnAc genes in the contaminated Luvisol. In contrast, high diversity of PAH-RHD(alpha) genes of Gram-positive and Gram-negative bacteria was observed in the phenanthrene-spiked Cambisol. Quantitative real-time PCR based on the same primers revealed that 63 days after phenanthrene spiking, PAH-RHD(alpha) genes were 1 order of magnitude more abundant in the Luvisol than in the Cambisol, while they were not detected in both control soils. In conclusion, sequence analysis of the amplicons obtained confirmed the specificity of the novel primer system and revealed a soil type-dependent response of PAH-RHD(alpha) gene-carrying soil bacteria to phenanthrene spiking.

The relationships between plant carbon resources, soil carbon and nitrogen content, and ectomycorrhizal fungal (EMF) diversity in a monospecific, old-growth beech (Fagus sylvatica) forest were investigated by manipulating carbon flux by girdling. We hypothesized that disruption of the carbon supply would not affect diversity and EMF species numbers if EM fungi can be supplied by plant internal carbohydrate resources or would result in selective disappearance of EMF taxa because of differences in carbon demand of different fungi. Tree carbohydrate status, root demography, EMF colonization, and EMF taxon abundance were measured repeatedly during 1 year after girdling. Girdling did not affect root colonization but decreased EMF species richness of an estimated 79 to 90 taxa to about 40 taxa. Cenococcum geophilum, Lactarius blennius, and Tomentella lapida were dominant, colonizing about 70% of the root tips, and remained unaffected by girdling. Mainly cryptic EMF species disappeared. Therefore, the Shannon-Wiener index (H') decreased but evenness was unaffected. H' was positively correlated with glucose, fructose, and starch concentrations of fine roots and also with the ratio of dissolved organic carbon to dissolved organic nitrogen (DOC/DON), suggesting that both H' and DOC/DON were governed by changes in belowground carbon allocation. Our results suggest that beech maintains numerous rare EMF species by recent photosynthate. These EM fungi may constitute biological insurance for adaptation to changing environmental conditions. The preservation of taxa previously not known to colonize beech may, thus, form an important reservoir for future forest development.

In soils and sediments ferrihydrite often precipitates from solutions containing dissolved organic matter, which affects its crystallinity. To simulate this process we prepared a series of 2-line ferrihydrite-organic matter coprecipitates using water extractable organic matter (OM) from a forest topsoil. The products were characterized byX-ray diffraction, Mössbauer spectroscopy, N2-gas adsorption and transmission electron microscopy. With increasing C/Fe ratios of the initial solution the d-spacings of the two major XRD peaks increased, while peak shoulders at 0.22 and 0.16 nm weakened. The asymmetry of the 0.26 nm peak decreased and disappeared at a C/Fe ratio of 0.78. The quadrupole splitting of the Mössbauer spectra at 300 K increased from 0.78 to 0.90 mm s(-1), the mean magnetic hyperfine field at 4.2 K dropped from 49.5 to 46.0 T, and the superparamagnetic collapse of the magnetic hyperfine splitting was shifted toward lower temperatures. These data reflect a strong interference of OM with crystal growth leading to smaller ferrihydrite crystals, increased lattice spacings, and more distorted Fe(O,OH)6 octahedra. Even small amounts of OM significantly change particle size and structural order of ferrihydrite. Crystallinity and reactivity of natural ferrihydrites will therefore often differ from their synthetic counterparts, formed in the absence of OM.

We present a new analytical procedure for the extraction and determination of natural estrogens in soils based on pressurised liquid extraction and GC-MS determination. After testing twelve solvents, acetone proved to be the most efficient extractant. The optimum extraction temperature is 60 degrees C. Soil extracts have to be purified and concentrated by C-18 solid phase extraction. The dried extracts are derivatised by N-methyl-N-(trimethylsilyl)trifluoro-acetamide before measurement by GC-MS. Recoveries of 79-103% with relative standard deviations

Landfill sites are potential sources of hazardous emissions by degradation and transformation processes of waste organic matter. Its chemical composition and microbial degradability are key factors for risk management, after-care, and estimation of potential emissions. The aim of the study is to provide information about composition and extent of transformation of waste organic matter in four landfill sites in Bavaria, Southern Germany by means of (13)C NMR spectroscopy, acid-hydrolyzable carbohydrates, chloroform-methanol extractable lipids, acid-hydrolyzable proteins, and lignin compounds after CuO oxidation. Ten samples of about 20 to 25 yr, 15 to 20 yr, and 5 to 10 yr of deposition each were taken at 2 m depth intervals by grab drilling till 10-m depth. Increasing temperatures from about 15 degrees C at 2-m depth to >40 degrees C at 10-m depth are found at some of the sites, representing optimum conditions for mesophile methane bacteria. Moisture contents of 160 to 310 g kg(-1) (oven dry), however, provide limiting conditions for anaerobic biodecay. Spectroscopic and chemical variables generally indicate a low extent of biodegradation and transformation at all sites despite a considerable heterogeneity of the samples. Independent of the time and depth of deposition more than 50% of the carbohydrate fraction of the waste organic matter provide a high potential for methane emissions and on-site energy production. There was no significant accumulation of long-chain organic and aromatic compounds, and of lignin degradation products even after more than 25 yr of rotting indicating higher extent of decomposition or stabilization of the waste organic matter. Installation of seepage water cleaning and recirculation systems are recommended to increase suboptimal moisture contents with respect to microbial methanogenesis, energy production, and long-term stabilization of municipal solid waste.

Continued input of airplane de-icing/anti-icing fluids (ADAF) to runway adjacent soils may result in the depletion of soil-borne terminal electron acceptors. We studied the transport and transformation of propylene glycol (PG), the major constituent of many ADAF, in topsoil and subsoil samples using saturated column experiments at 4 degrees C and 20 degrees C. The export of soil-borne DOC was generally high, non-exhaustive and rate limited. Retardation of added PG was negligible. Rapid PG degradation was observed only in topsoil materials high in organic matter at 20 degrees C. At 4 degrees C, no significant degradation was observed. Thus, under unfavorable, i.e., wet and cold conditions typical for winter de-icing operations, PG and its metabolites will be relocated to deeper soil horizons or even to the groundwater. In subsoil materials, PG degradation was very slow and incomplete. We found that subsoil degradation depended on the import of active microorganisms originating from the organic-rich topsoil material. The degradation efficiency is strongly influenced by the flow velocity, i.e., the residence time of PG in the soil column. Poorly crystalline iron(III) and manganese(IV) (hydr)oxides are used during microbial respiration acting as terminal electron acceptors. This results in the formation and effective relocation of reduced and mobile Fe and Mn species. Long-term application of ADAF to runway adjacent soil as well as the lasting consumption of Fe and Mn will tend to decrease the soil redox potential. Without proper counteractive measures, this will eventually favor the development of methanogenic conditions.

Identifying prehistoric irrigated rice fields and characterizing the beginning of paddy soil development are important for a better understanding of human development and agricultural history. In 2003, paddy soils and irrigated rice fields buried at a depth of 100-130 cm were excavated at Chuo-dun-shan in the Yangtze River Delta, close to Suzhou, China. The fields of sizes between 1.4 and 16 m(2) were surrounded with ridges that were connected to ditches/ponds via outlets to control the water level within the fields. Many carbonized and partly carbonized rice grains with an age of 3,903 B.C. (measured (14)C age 5,129+/-45 a BP) were recovered. The surface layers of these buried paddy fields showed a high content of soil organic matter and a considerable high density of rice opals. The latter were identified to derive from Oryza spp. Solid-state (13)C nuclear magnetic resonance spectroscopy revealed aromatic carbon (C) as the predominant organic C form in the fossil surface layer. This is expected, if the major source represents burnt rice and straw. In summary, our data are in agreement with new evidences indicating that in China, paddy soils and irrigated rice cultivation were initiated and developed more than 6,000 years ago.

There is growing concern about environmentally released man-made chemicals suspected to be responsible for a number of adverse effects on endocrine function in wildlife species and possibly also in humans. Sex hormones are of particular interest due to their regulatory role in developmental processes such as sexual differentiation. Endogenous hormones of human or animal origin as well as exogenous sex steroids used for contraception or as anabolics for farm animals are excreted and reach the environment. We investigated the transport of the synthetic growth promoters trenbolone (TbOH) and melengestrol acetate (MGA) in agricultural soil by means of column experiments with aggregated soil materials (Ap and Bt horizons of a Luvisol). Column effluent concentrations and depth profiles of TbOH and MGA were determined with sensitive enzyme immunoassay systems and HPLC (RP-18), respectively. All procedures were confirmed by liquid chromatography-mass spectrometry. Small amounts of TbOH and MGA passed the columns very quickly. However, both hormones exhibited a high affinity to the organic matter of both horizons leading to a high retardation within the upper layers of the soil columns. Although we cannot deduce whether hormones of animal origin reach the ground water under field conditions, our model experiments show that their transition can be presumed., (Copryright 2004 Elsevier B.V.)

Simplified equations are used in common approaches to describe cross polarization (CP) dynamics of solids. The CP behavior may be modulated by several nuclei interactions and physicochemical sample properties. At high magnetic fields and spinning speeds, these modulations can obscure the results. To elucidate their impact on the CP behavior of natural organic materials variable contact time (VCT) experiments were acquired with a high temporal resolution for two coal samples. The measurements were distinctly influenced by interfering fluctuations. Conventional approaches showed insufficient flexibility in terms of degrees of freedom to calculate the CP dynamics. The use of an original fundamental equation as model resulted in sufficient flexibility for such heterogeneous systems. The best results were obtained assuming a two component system. On these conditions a differentiation between amorphous and crystalline domains within the coal samples was enabled.

MALDI-TOF mass spectrometry and 13C NMR spectroscopy were applied to unveil typical characteristics of condensed tannins of leaves and needles from willow (Salix alba), spruce (Picea abies) and beech (Fagus sylvatica) of three tree species that are ubiquitous in German forests and landscapes. For further evaluation, lime (Tilia cordata) was included. The 13C NMR spectroscopy confirmed the purity of the condensed tannin fractions and the efficiency of the procedure used for their extraction. While signals representative for procyanidin units are observable in all liquid-state 13C NMR spectra, resonance lines of prodelphinidin were only detected in those obtained from the condensed tannins of spruce needles and beech leaves. Typical signals in the chemical shift region between 70 and 90 ppm demonstrated the presence of stereoisomers (catechin/epicatechin; gallocatechin/ epigallocatechin). The MALDI-TOF mass spectra of the condensed tannins show signals of polymers of up to undecamers. Supporting the observations from the NMR spectroscopy, the mass spectra of the willow and lime leaf condensed tannins were identified as polymers with mainly procyanidin units, while the polymers of the spruce needle and beech leaves exhibit varying procyanidin/prodelphinidin ratios. Post source decay (PSD) fragmentation lead to a sequential loss of monomers and allowed a detailed characterization and sequencing of individual chains. In the case of the condensed tannins of lime this technique clearly excludes a pelargonidin terminal unit followed by a prodelphinidin unit, which would result in the same molecular masses as a polymer solely built up of procyanidin units.

The use of mining substrates for recultivation purposes is limited due to their low organic matter (OM) contents. In a 1-yr laboratory experiment we evaluated the stabilization of biowaste compost added to a humus-free sandy mining soil to examine the suitability of compost amendment for the formation of stable soil organic matter (SOM). The stabilization process was characterized by measuring enrichment of OM and nitrogen in particle size fractions obtained after dispersion with different amounts of energy (ultrasonication and shaking in water), carbon mineralization, and amount of dissolved organic carbon (DOC). During the experiment, 17.1% of the organic carbon (OC) was mineralized. Organic carbon enrichment in the < 20-micron particle size fraction at the beginning of the experiment was in the range of natural soils with similar texture. Within 12 mo, a distinct OC redistribution from coarse into fine fractions was found with both dispersion methods. The accumulation of OC was more pronounced for the size separates obtained by ultrasonication, where the carbon distribution between 0.45- to 20-micron particle size fractions increased from 30% at the beginning to 71% at the end of the experiment. Dissolved organic carbon contents ranged between 50 and 68 g kg-1 OC and decreased during the incubation. In conclusion, the exponential decrease of carbon mineralization and the OC enrichment in the fine particle size fractions both indicated a distinct OM stabilization in the mining soil.