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.

Size, shape, and stability of organic particles formed during freeze-thaw cycles: Model experiments with tannic acid.

HYPOTHESIS: Freeze-thaw cycles (FTC) in soils can cause the aggregation of dissolved organic matter but controlling factors are little understood. EXPERIMENTS: In freeze-thaw experiments with tannic acid (TA) as model substance, we studied the effect of TA concentration, pH, electrolytes (NaCl, CaCl2, AlCl3), and number of FTC on particle formation. Tannic acid (0.005 to 10 g L-1) was exposed to 1-20 FTC at pH 3 and 6. The size and shape of particles was determined by confocal laser scanning microscopy. Particle stability was deduced from the equivalent circle diameter (ECD) obtained in dry state and the hydrodynamic diameter measured in thawing solutions. FINDINGS: Tannic acid particles occurred as plates and veins, resembling the morphology of ice grain boundaries. Low pH and presence of electrolytes favored the formation of large particles. The freeze-concentration effect was most intense at low TA concentrations and increased with the number of FTC. While ECD of particles formed at low TA concentrations were smaller than at high concentrations, it was vice versa in the thawed state. At low TA concentrations, higher crystallization pressure of ice caused enhanced stability of large particles. We conclude that FTC can strongly alter the physical state of dissolved organic matter, with likely consequences for its bioavailability.

Nitrogen dynamics in Turbic Cryosols from Siberia and Greenland.

Turbic Cryosols (permafrost soils characterized by cryoturbation, i.e., by mixing of soil layers due to freezing and thawing) are widespread across the Arctic, and contain large amounts of poorly decomposed organic material buried in the subsoil. This cryoturbated organic matter exhibits retarded decomposition compared to organic material in the topsoil. Since soil organic matter (SOM) decomposition is known to be tightly linked to N availability, we investigated N transformation rates in different soil horizons of three tundra sites in north-eastern Siberia and Greenland. We measured gross rates of protein depolymerization, N mineralization (ammonification) and nitrification, as well as microbial uptake of amino acids and NH4+ using an array of 15N pool dilution approaches. We found that all sites and horizons were characterized by low N availability, as indicated by low N mineralization compared to protein depolymerization rates (with gross N mineralization accounting on average for 14% of gross protein depolymerization). The proportion of organic N mineralized was significantly higher at the Greenland than at the Siberian sites, suggesting differences in N limitation. The proportion of organic N mineralized, however, did not differ significantly between soil horizons, pointing to a similar N demand of the microbial community of each horizon. In contrast, absolute N transformation rates were significantly lower in cryoturbated than in organic horizons, with cryoturbated horizons reaching not more than 32% of the transformation rates in organic horizons. Our results thus indicate a deceleration of the entire N cycle in cryoturbated soil horizons, especially strongly reduced rates of protein depolymerization (16% of organic horizons) which is considered the rate-limiting step in soil N cycling.

Properties and degradability of hydrothermal carbonization products.

Biomass carbonized via hydrothermal carbonization (HTC) yields a liquid and a carbon (C)-rich solid called hydrochar. In soil, hydrochars may act as fertilizers and promote C sequestration. We assumed that the chemical composition of the raw material (woodchips, straw, grass cuttings, or digestate) determines the properties of the liquid and solid HTC products, including their degradability. Additionally, we investigated whether easily mineralizable organic components adsorbed on the hydrochar surface influence the degradability of the hydrochars and could be removed by repetitive washing. Carbon mineralization was measured as CO production over 30 d in aerobic incubation experiments with loamy sand. Chemical analysis revealed that most nutrients were preferably enriched in the liquid phase. The C mineralization of hydrochars from woodchips (2% of total C added), straw (3%), grass (6%), and digestate (14%) were dependent on the raw material carbonized and were significantly lower (by 60-92%; < 0.05) than the mineralization of the corresponding raw materials. Washing of the hydrochars significantly decreased mineralization of digestate-hydrochar (up to 40%) but had no effect on mineralization rates of the other three hydrochars. Variations in C mineralization between different hydrochars could be explained by multiple factors, including differences in the O/C-H/C ratios, C/N ratios, lignin content, amount of oxygen-containing functional groups, and pH. In contrast to the solids, the liquid products were highly degradable, with 61 to 89% of their dissolved organic C being mineralized within 30 d. The liquids may be treated aerobically (e.g., for nutrient recovery).

Extracellular polymeric substances from Bacillus subtilis associated with minerals modify the extent and rate of heavy metal sorption.

Extracellular polymeric substances (EPS) are an important source of organic matter in soil. Once released by microorganisms, a portion may be sorbed to mineral surfaces, thereby altering the mineral̀s ability to immobilize heavy metals. EPS from Bacillus subtilis were reacted with Ca-saturated bentonite and ferrihydrite in 0.01 M KCl at pH 5.0 to follow the preferential uptake of EPS-C, -N, and -P. The sorption kinetics of Pb(2+), Cu(2+), and Zn(2+) to the resulting EPS-mineral composites was studied in single and binary metal batch experiments ([metal](total) = 50 µM, pH 5.0). Bentonite sorbed much more EPS-C (18.5 mg g(-1)) than ferrihydrite (7.9 mg g(-1)). During sorption, EPS were chemically and size fractionated with bentonite favoring the uptake of low-molecular weight components and EPS-N, and ferrihydrite selectively retaining high-molecular weight and P-rich components. Surface area and pore size measurements by N(2) gas adsorption at 77 K indicated that EPS altered the structure of mineral-EPS associations by inducing partial disaggregation of bentonite and aggregation of ferrihydrite. Whereas mineral-bound EPS increased the extent and rate of Pb(2+), Cu(2+), and Zn(2+) sorption for bentonite, either no effect or a decrease in metal uptake was observed for ferrihydrite. The extent of sorption always followed the order Pb(2+) > Cu(2+) > Zn(2+), which also prevailed in binary Pb(2+)/Cu(2+) systems. In consequence, sorption of EPS to different minerals may have contrasting consequences for the immobilization of heavy metals in natural environments by inducing mineral-specific alterations of the pore size distribution and, thus, of available sorption sites.

Microscale carbon distribution around pores and particulate organic matter varies with soil moisture regime.

Soil carbon sequestration arises from the interplay of carbon input and stabilization, which vary in space and time. Assessing the resulting microscale carbon distribution in an intact pore space, however, has so far eluded methodological accessibility. Here, we explore the role of soil moisture regimes in shaping microscale carbon gradients by a novel mapping protocol for particulate organic matter and carbon in the soil matrix based on a combination of Osmium staining, X-ray computed tomography, and machine learning. With three different soil types we show that the moisture regime governs C losses from particulate organic matter and the microscale carbon redistribution and stabilization patterns in the soil matrix. Carbon depletion around pores (aperture > 10 µm) occurs in a much larger soil volume (19-74%) than carbon enrichment around particulate organic matter (1%). Thus, interacting microscale processes shaped by the moisture regime are a decisive factor for overall soil carbon persistence.

Effects of solution chemistry on conformation of self-aggregated tannic acid revealed by laser light scattering.

Inorganic soil solution constituents can alter the charge, size, and conformation of dissolved organic molecules, thus affecting their environmental behavior. Here, we investigated how pH, cation valence and activities induce conformational changes and aggregation-sedimentation reactions of organic polyelectrolytes. For that we determined the hydrodynamic diameter of the model compound tannic acid by laser light scattering at concentrations of 1-30 g L-1 in the pH range from 3 to 10 and with electrolyte additions of CaCl2 and hydroxyl-Al cations. Charge properties were quantified by polyelectrolyte titration and zeta potential measurements. After dispersion by sonication, aggregation was determined in time sequences up to 60 min and suspension stability was traced in sedimentation experiments. Tannic acid was present in ultrapure water in a self-aggregated state. At pH <3 as well as >7.5, its hydrodynamic diameter increased. Whereas at high pH this behavior could be assigned to unfolding of molecular conformations, at low pH it is likely that charge neutralization decreased repulsive forces and facilitated aggregation. At pH 5 and ionic strengths of up to 5 mM, CaCl2 did not affect aggregation state of tannic acid and results resembled those obtained in ultrapure water. Addition of hydroxyl-Al cations broke-up the self-aggregated tannic acid structures under formation of Al-organic coprecipitates. Strong aggregation only occurred at mixing ratios where opposite surface charges were completely balanced. Under natural conditions, self-aggregation of tannic acid can be expected only at higher solution concentrations. However, at acidic pH, hydroxyl-Al cations and tannic acid may form discrete colloidal particles already at low tannic acid concentrations, resulting in the destabilization of suspensions. Our data emphasize that the soil solution composition strongly modifies the physical state of tannic acid, and likely also of other biopolymers, and thus their interactions within environmental matrices.

Production of Organic Acids by Arbuscular Mycorrhizal Fungi and Their Contribution in the Mobilization of Phosphorus Bound to Iron Oxides.

Most plants living in tropical acid soils depend on the arbuscular mycorrhizal (AM) symbiosis for mobilizing low-accessible phosphorus (P), due to its strong bonding by iron (Fe) oxides. The roots release low-molecular-weight organic acids (LMWOAs) as a mechanism to increase soil P availability by ligand exchange or dissolution. However, little is known on the LMWOA production by AM fungi (AMF), since most studies conducted on AM plants do not discriminate on the LMWOA origin. This study aimed to determine whether AMF release significant amounts of LMWOAs to liberate P bound to Fe oxides, which is otherwise unavailable for the plant. Solanum lycopersicum L. plants mycorrhized with Rhizophagus irregularis were placed in a bicompartmental mesocosm, with P sources only accessible by AMF. Fingerprinting of LMWOAs in compartments containing free and goethite-bound orthophosphate (OP or GOE-OP) and phytic acid (PA or GOE-PA) was done. To assess P mobilization via AM symbiosis, P content, photosynthesis, and the degree of mycorrhization were determined in the plant; whereas, AM hyphae abundance was determined using lipid biomarkers. The results showing a higher shoot P content, along with a lower N:P ratio and a higher photosynthetic capacity, may be indicative of a higher photosynthetic P-use efficiency, when AM plants mobilized P from less-accessible sources. The presence of mono-, di-, and tricarboxylic LMWOAs in compartments containing OP or GOE-OP and phytic acid (PA or GOE-PA) points toward the occurrence of reductive dissolution and ligand exchange/dissolution reactions. Furthermore, hyphae grown in goethite loaded with OP and PA exhibited an increased content of unsaturated lipids, pointing to an increased membrane fluidity in order to maintain optimal hyphal functionality and facilitate the incorporation of P. Our results underpin the centrality of AM symbiosis in soil biogeochemical processes, by highlighting the ability of the AMF and accompanying microbiota in releasing significant amounts of LMWOAs to mobilize P bound to Fe oxides.

Transformation of jarosite during simulated remediation of a sandy sulfuric soil.

Aeration of wetland soils containing iron (Fe) sulfides can cause strong acidification due to the generation of large amounts of sulfuric acid and formation of Fe oxyhydroxy sulfate phases such as jarosite. Remediation by re-establishment of anoxic conditions promotes jarosite transformation to Fe oxyhydroxides and/or Fe sulfides, but the driving conditions and mechanisms are largely unresolved. We investigated a sandy, jarosite-containing soil (initial pH = 3.0, Eh ~600 mV) in a laboratory incubation experiment under submerged conditions, either with or without wheat straw addition. Additionally, a model soil composed of synthesized jarosite mixed with quartz sand was used. Eh and pH values were monitored weekly. Solution concentrations of total dissolved organic carbon, Fe, S, and K as well as proportions of Fe2+ and SO42- were analysed at the end of the experiment. Sequential Fe extraction, X-ray diffraction, and Mössbauer spectroscopy were used to characterize the mineral composition of the soils. Only when straw was added to natural and artificial sulfuric soils, the pH increased up to 6.5, and Eh decreased to approx. 0 mV. The release of Fe (mainly Fe2+), K, and S (mainly SO42-) into the soil solution indicated redox- and pH-induced dissolution of jarosite. Mineralogical analyses confirmed jarosite losses in both soils. While lepidocrocite formed in the natural sulfuric soil, goethite was formed in the artificial sulfuric soil. Both soils showed also increases in non-sulfidized, probably organically associated Fe2+/Fe3+, but no (re-)formation of Fe sulfides. Unlike Fe sulfides, the formed Fe oxyhydroxides are not prone to support re-acidification in the case of future aeration. Thus, inducing moderately reductive conditions by controlled supply of organic matter could be a promising way for remediation of soils and sediments acidified by oxidation of sulfuric materials.

Iron oxides and aluminous clays selectively control soil carbon storage and stability in the humid tropics.

Clay minerals and pedogenic metal (oxyhydr)oxides are the most reactive soil mineral constituents controlling the long-term persistence of organic carbon (OC) in terrestrial ecosystems. However, their co-occurrence in most soils complicates direct assessment of their individual contribution to OC persistence. Making use of unique mineralogical combinations in soils located in the East Usambara Mountains of Tanzania, we disentangled the contribution of clay-sized aluminous minerals (kaolinite, gibbsite) and pedogenic Fe (oxyhydr)oxides (predominant goethite and hematite) on OC storage and stabilization under natural forests and croplands. Topsoil samples, varying in contents but not types of aluminous clays and pedogenic Fe (oxyhydr)oxides, were identified by selective extractions, X-ray diffraction, and Mössbauer spectroscopy. Associated abundance of particulate and mineral-associated organic matter (OM) was quantified by density fractionation and their changes during land-use conversion were determined as a measure of OC persistence. Additionally, we assessed the resistance of OC to chemical oxidation as well as microbial decomposition in a 50-day laboratory incubation. We found that the ratio of pedogenic Fe to aluminous clay is more consequential for OC storage and stabilization than their individual contents, despite the fact that Fe (oxyhydr)oxides generally exert a stronger impact on OC than aluminous clays. Conjunction of large amounts of Fe (oxyhydr)oxides with low aluminous clay contents caused the strongest accumulation of mineral-associated OC, a low soil respiration, high OC stability against chemical oxidation, and high OC persistence during land-use change. Our study suggests that certain mineralogical combinations in the humid tropics alleviate OM losses during land conversion because of the strong and selective mineral control on OC stabilization, particular if the weight ratio of pedogenic Fe to aluminous clay exceeds the threshold range of 0.44‒0.56.

Sorption competition with natural organic matter as mechanism controlling silicon mobility in soil.

Growing evidence of silicon (Si) playing an important role in plant health and the global carbon cycle triggered research on its biogeochemistry. In terrestrial soil ecosystems, sorption of silicic acid (H4SiO4) to mineral surfaces is a main control on Si mobility. We examined the competitive sorption of Si, dissolved organic matter, and phosphorus in forest floor leachates (pH 4.1-4.7) to goethite, in order to assess its effects on Si mobility at weathering fronts in acidic topsoil, a decisive zone of nutrient turnover in soil. In batch sorption experiments, we varied the extent of competition between solutes by varying the amount of added goethite (α-FeOOH) and the Si pre-loading of the goethite surfaces. Results suggest weaker competitive strength of Si than of dissolved organic matter and ortho-phosphate. Under highly competitive conditions, hardly any dissolved Si (< 2%) but much of the dissolved organic carbon (48-80%) was sorbed. Pre-loading the goethite surfaces with monomeric Si hardly decreased the sorption of organic carbon and phosphate, whereas up to about 50% of the Si was released from surfaces into solutions, indicating competitive displacement from sorption sites. We conclude sorption competition with dissolved organic matter and other strongly sorbing solutes can promote Si leaching in soil. Such effects should thus be considered in conceptual models on soil Si transport, distribution, and phytoavailability.