Formation of mineral-associated organic matter in temperate soils is primarily controlled by mineral type and modified by land use and management intensity.

Formation of mineral-associated organic matter (MAOM) supports the accumulation and stabilization of carbon (C) in soil, and thus, is a key factor in the global C cycle. Little is known about the interplay of mineral type, land use and management intensity in MAOM formation, especially on subdecadal time scales. We exposed mineral containers with goethite or illite, the most abundant iron oxide and phyllosilicate clay in temperate soils, for 5 years in topsoils of 150 forest and 150 grassland sites in three regions across Germany. Results show that irrespective of land use and management intensity, more C accumulated on goethite than illite (on average 0.23 ± 0.10 and 0.06 ± 0.03 mg m-2 mineral surface respectively). Carbon accumulation across regions was consistently higher in coniferous forests than in deciduous forests and grasslands. Structural equation models further showed that thinning and harvesting reduced MAOM formation in forests. Formation of MAOM in grasslands was not affected by grazing. Fertilization had opposite effects on MAOM formation, with the positive effect being mediated by enhanced plant productivity and the negative effect by reduced plant species richness. This highlights the caveat of applying fertilizers as a strategy to increase soil C stocks in temperate grasslands. Overall, we demonstrate that the rate and amount of MAOM formation in soil is primarily driven by mineral type, and can be modulated by land use and management intensity even on subdecadal time scales. Our results suggest that temperate soils dominated by oxides have a higher capacity to accumulate and store C than those dominated by phyllosilicate clays, even under circumneutral pH conditions. Therefore, adopting land use and management practices that increase C inputs into oxide-rich soils that are under their capacity to store C may offer great potential to enhance near-term soil C sequestration.

Correlative Imaging of the Rhizosphere─A Multimethod Workflow for Targeted Mapping of Chemical Gradients.

Examining in situ processes in the soil rhizosphere requires spatial information on physical and chemical properties under undisturbed conditions. We developed a correlative imaging workflow for targeted sampling of roots in their three-dimensional (3D) context and assessed the imprint of roots on chemical properties of the root-soil contact zone at micrometer to millimeter scale. Maize (Zea mays) was grown in 15N-labeled soil columns and pulse-labeled with 13CO2 to visualize the spatial distribution of carbon inputs and nitrogen uptake together with the redistribution of other elements. Soil columns were scanned by X-ray computed tomography (X-ray CT) at low resolution (45 µm) to enable image-guided subsampling of specific root segments. Resin-embedded subsamples were then analyzed by X-ray CT at high resolution (10 µm) for their 3D structure and chemical gradients around roots using micro-X-ray fluorescence spectroscopy (µXRF), nanoscale secondary ion mass spectrometry (NanoSIMS), and laser-ablation isotope ratio mass spectrometry (LA-IRMS). Concentration gradients, particularly of calcium and sulfur, with different spatial extents could be identified by µXRF. NanoSIMS and LA-IRMS detected the release of 13C into soil up to a distance of 100 µm from the root surface, whereas 15N accumulated preferentially in the root cells. We conclude that combining targeted sampling of the soil-root system and correlative microscopy opens new avenues for unraveling rhizosphere processes in situ.

Legacy Effects of Sorption Determine the Formation Efficiency of Mineral-Associated Soil Organic Matter.

Sorption of dissolved organic matter (DOM) is one major pathway in the formation of mineral-associated organic matter (MOM), but there is little information on how previous sorption events feedback to later ones by leaving their imprint on mineral surfaces and solutions ("legacy effect"). In order to conceptualize the role of legacy effects in MOM formation, we conducted sequential sorption experiments with kaolinite and gibbsite as minerals and DOM derived from forest floor materials. The MOM formation efficiency leveled off upon repeated addition of identical DOM solutions to minerals due to the retention of highly sorptive organic molecules (primarily aromatic, nitrogen-poor, hydrogen-poor, and oxygen-rich molecules), which decreased the sorption site availability and simultaneously modified the mineral surface charge. Organic-organic interactions as postulated in multilayer models played a negligible role in MOM formation. Continued exchange between DOM and MOM molecules upon repeated sorption altered the DOM composition but not the MOM formation efficiencies. Sorption-induced depletion of high-affinity compounds from solutions further decreased the MOM formation efficiencies to pristine minerals. Overall, the interplay between the differential sorptivities of DOM components and the mineral surface chemistry explains the legacy effects that contribute to the regulation of fluxes and the distribution of organic matter in the soil.

Variable silicon accumulation in plants affects terrestrial carbon cycling by controlling lignin synthesis.

Current climate and land-use changes affect regional and global cycles of silicon (Si), with yet uncertain consequences for ecosystems. The key role of Si in marine ecology by controlling algae growth is well recognized but research on terrestrial ecosystems neglected Si since not considered an essential plant nutrient. However, grasses and various other plants accumulate large amounts of Si, and recently it has been hypothesized that incorporation of Si as a structural plant component may substitute for the energetically more expensive biosynthesis of lignin. Herein, we provide evidence supporting this hypothesis. We demonstrate that in straw of rice (Oryza sativa) deriving from a large geographic gradient across South-East Asia, the Si concentrations (ranging from 1.6% to 10.7%) are negatively related to the concentrations of carbon (31.3% to 42.5%) and lignin-derived phenols (32 to 102 mg/g carbon). Less lignin may explain results of previous studies that Si-rich straw decomposes faster. Hence, Si seems a significant but hardly recognized factor in organic carbon cycling through grasslands and other ecosystems dominated by Si-accumulating plants.

Temperature response of permafrost soil carbon is attenuated by mineral protection.

Climate change in Arctic ecosystems fosters permafrost thaw and makes massive amounts of ancient soil organic carbon (OC) available to microbial breakdown. However, fractions of the organic matter (OM) may be protected from rapid decomposition by their association with minerals. Little is known about the effects of mineral-organic associations (MOA) on the microbial accessibility of OM in permafrost soils and it is not clear which factors control its temperature sensitivity. In order to investigate if and how permafrost soil OC turnover is affected by mineral controls, the heavy fraction (HF) representing mostly MOA was obtained by density fractionation from 27 permafrost soil profiles of the Siberian Arctic. In parallel laboratory incubations, the unfractionated soils (bulk) and their HF were comparatively incubated for 175 days at 5 and 15°C. The HF was equivalent to 70 ± 9% of the bulk CO2 respiration as compared to a share of 63 ± 1% of bulk OC that was stored in the HF. Significant reduction of OC mineralization was found in all treatments with increasing OC content of the HF (HF-OC), clay-size minerals and Fe or Al oxyhydroxides. Temperature sensitivity (Q10) decreased with increasing soil depth from 2.4 to 1.4 in the bulk soil and from 2.9 to 1.5 in the HF. A concurrent increase in the metal-to-HF-OC ratios with soil depth suggests a stronger bonding of OM to minerals in the subsoil. There, the younger 14 C signature in CO2 than that of the OC indicates a preferential decomposition of the more recent OM and the existence of a MOA fraction with limited access of OM to decomposers. These results indicate strong mineral controls on the decomposability of OM after permafrost thaw and on its temperature sensitivity. Thus, we here provide evidence that OM temperature sensitivity can be attenuated by MOA in permafrost soils.

Microbial nitrogen dynamics in organic and mineral soil horizons along a latitudinal transect in western Siberia.

Soil N availability is constrained by the breakdown of N-containing polymers such as proteins to oligopeptides and amino acids that can be taken up by plants and microorganisms. Excess N is released from microbial cells as ammonium (N mineralization), which in turn can serve as substrate for nitrification. According to stoichiometric theory, N mineralization and nitrification are expected to increase in relation to protein depolymerization with decreasing N limitation, and thus from higher to lower latitudes and from topsoils to subsoils. To test these hypotheses, we compared gross rates of protein depolymerization, N mineralization and nitrification (determined using 15N pool dilution assays) in organic topsoil, mineral topsoil, and mineral subsoil of seven ecosystems along a latitudinal transect in western Siberia, from tundra (67°N) to steppe (54°N). The investigated ecosystems differed strongly in N transformation rates, with highest protein depolymerization and N mineralization rates in middle and southern taiga. All N transformation rates decreased with soil depth following the decrease in organic matter content. Related to protein depolymerization, N mineralization and nitrification were significantly higher in mineral than in organic horizons, supporting a decrease in microbial N limitation with depth. In contrast, we did not find indications for a decrease in microbial N limitation from arctic to temperate ecosystems along the transect. Our findings thus challenge the perception of ubiquitous N limitation at high latitudes, but suggest a transition from N to C limitation of microorganisms with soil depth, even in high-latitude systems such as tundra and boreal forest. KEY POINTS: We compared soil N dynamics of seven ecosystems along a latitudinal transectShifts in N dynamics suggest a decrease in microbial N limitation with depthWe found no decrease in microbial N limitation from arctic to temperate zones.

Microbial community composition shapes enzyme patterns in topsoil and subsoil horizons along a latitudinal transect in Western Siberia.

Soil horizons below 30 cm depth contain about 60% of the organic carbon stored in soils. Although insight into the physical and chemical stabilization of soil organic matter (SOM) and into microbial community composition in these horizons is being gained, information on microbial functions of subsoil microbial communities and on associated microbially-mediated processes remains sparse. To identify possible controls on enzyme patterns, we correlated enzyme patterns with biotic and abiotic soil parameters, as well as with microbial community composition, estimated using phospholipid fatty acid profiles. Enzyme patterns (i.e. distance-matrixes calculated from these enzyme activities) were calculated from the activities of six extracellular enzymes (cellobiohydrolase, leucine-amino-peptidase, N-acetylglucosaminidase, chitotriosidase, phosphatase and phenoloxidase), which had been measured in soil samples from organic topsoil horizons, mineral topsoil horizons, and mineral subsoil horizons from seven ecosystems along a 1500 km latitudinal transect in Western Siberia. We found that hydrolytic enzyme activities decreased rapidly with depth, whereas oxidative enzyme activities in mineral horizons were as high as, or higher than in organic topsoil horizons. Enzyme patterns varied more strongly between ecosystems in mineral subsoil horizons than in organic topsoils. The enzyme patterns in topsoil horizons were correlated with SOM content (i.e., C and N content) and microbial community composition. In contrast, the enzyme patterns in mineral subsoil horizons were related to water content, soil pH and microbial community composition. The lack of correlation between enzyme patterns and SOM quantity in the mineral subsoils suggests that SOM chemistry, spatial separation or physical stabilization of SOM rather than SOM content might determine substrate availability for enzymatic breakdown. The correlation of microbial community composition and enzyme patterns in all horizons, suggests that microbial community composition shapes enzyme patterns and might act as a modifier for the usual dependency of decomposition rates on SOM content or C/N ratios.

Retention of sterically and electrosterically stabilized silver nanoparticles in soils.

The current study investigated the interaction of sterically stabilized OECD standard Ag ENP (AgNM-300k) and silver ions (Ag+) in 25 German arable soils with varying properties (organic carbon concentration of 0.4-25 mg g(-1) and clay content of <0.1-392 mg g(-1)) in 24 h batch retention experiments. A soil subset (n=8) was investigated to test the soil interactions with citrate-stabilized Ag ENP (AgCN30). The adsorption of Ag+ was consistent with the Freundlich model with high KF values (mean KF=2553 L kg(-1), n=25), which suggested a high retention of Ag+. The retention of AgNM-300k followed a linear partitioning model and generally exhibited a low retention for the majority of the investigated soils (group 1, mean Kr, linear=3.7 L kg(-1), n=19), and was correlated with the clay content (relation to log10(Kr, linear), r2=0.40, n=19). Soils showing a high retention of AgNM-300k (group 2, mean Kr, linear=1048 L kg(-1), n=6) either had a low (<5.1) or high pH (>7.0) and generally contained >200 mg g(-1) clay. For the sample subset tested, AgCN30 and AgNM-300k were retained in similar dimensions regarding the same soils. The results suggest that the highest risk of long-term ENP mobilization exists when Ag ENP are applied to agricultural soils with low clay contents (<130 mg g(-1)) and slightly acidic conditions.

Input of easily available organic C and N stimulates microbial decomposition of soil organic matter in arctic permafrost soil.

Rising temperatures in the Arctic can affect soil organic matter (SOM) decomposition directly and indirectly, by increasing plant primary production and thus the allocation of plant-derived organic compounds into the soil. Such compounds, for example root exudates or decaying fine roots, are easily available for microorganisms, and can alter the decomposition of older SOM ("priming effect"). We here report on a SOM priming experiment in the active layer of a permafrost soil from the central Siberian Arctic, comparing responses of organic topsoil, mineral subsoil, and cryoturbated subsoil material (i.e., poorly decomposed topsoil material subducted into the subsoil by freeze-thaw processes) to additions of 13C-labeled glucose, cellulose, a mixture of amino acids, and protein (added at levels corresponding to approximately 1% of soil organic carbon). SOM decomposition in the topsoil was barely affected by higher availability of organic compounds, whereas SOM decomposition in both subsoil horizons responded strongly. In the mineral subsoil, SOM decomposition increased by a factor of two to three after any substrate addition (glucose, cellulose, amino acids, protein), suggesting that the microbial decomposer community was limited in energy to break down more complex components of SOM. In the cryoturbated horizon, SOM decomposition increased by a factor of two after addition of amino acids or protein, but was not significantly affected by glucose or cellulose, indicating nitrogen rather than energy limitation. Since the stimulation of SOM decomposition in cryoturbated material was not connected to microbial growth or to a change in microbial community composition, the additional nitrogen was likely invested in the production of extracellular enzymes required for SOM decomposition. Our findings provide a first mechanistic understanding of priming in permafrost soils and suggest that an increase in the availability of organic carbon or nitrogen, e.g., by increased plant productivity, can change the decomposition of SOM stored in deeper layers of permafrost soils, with possible repercussions on the global climate.