Extractability of different forms of mineral-associated phosphorus

The sequential extraction scheme introduced by Hedley et al. (1982) and modified by Tiessen and Moir (2008) has become the preeminent measure for estimating biological availability and binding forms of phosphorus in soil. However, the method’s underlying assumptions, especially on the binding forms, have never been subjected to rigorous testing under defined conditions. We reacted different forms of phosphorus (orthophosphate, phytic acid, RNA) with several potentially phosphorus-binding mineral phases (kaolinite, montmorillonite, goethite, ferrihydrite, amorphous Al hydroxide, allophane) at pH 4. Then, the phosphorus-loaded mineral phases were rinsed for removal of excess phosphorus compounds, shock-frozen in liquid N2 and freeze dried. Each 1 g of phosphorus-loaded samples was then mixed with 9 g of purified quartz (sieved to <63 µm) to mimic relations of reactive and nonreactive mineral phases in soil. All samples were then subjected to sequential extraction in line with the Hedley fractionation scheme (water‒resin extraction, extraction with 0.5 M NaHCO3, extraction with 0.1 M NaOH, extraction with 1 M HCl, extraction with concentrated HCl at 80°C). All extracts were analysed for orthophosphate and total phosphorus. The minerals retained different amounts of phosphorus compounds, with the hydrous metal oxides and allophane binding orthophosphate and most of the organic species most strongly. Clay minerals showed the weakest binding of phosphorus compounds. The water‒resin extraction mobilised surprisingly large portions of orthophosphate from all mineral phases and also some of the organic compounds. The NaHCO3 and NaOH extracts removed increasing portions of phosphorus compounds. Amorphous Al hydroxide largely dissolved in 1 M NaOH; the iron oxides and allophane, however, withstood the alkaline extraction. Treatment with 1 M HCl resulted in further release of phosphorus compounds from all minerals, especially from ferrihydrite. The assumption of the Hedley fraction that the 1 M HCl extraction represents exclusively Ca-bound phosphorus, thus, is obviously wrong. In summary, phosphorus forms bound to different minerals contribute to all extracts. Thus, the individual extraction steps of the Hedley do not represent phosphorus bound to certain compounds but phosphorus bound to various mineral phases via bonds of different strength

Mobilization of phosphorus from secondary minerals by the arbuscular mycorrhiza Rhizophagus irregularis and consequences for carbon sequestration in soils

Phosphorus can be a major limiting factor for plant growth due to its slow diffusion and high degree of immobilization in soils. Understanding the strategies evolved by plant-symbiont couples increasing P uptake is crucial, under the aim of adopting the involved mechanisms by modern sustainable agriculture. This study aims to explore whether tomato plants mycorrhized with the arbuscular mycorrhizal (AM) fungi Rhizophagus irregularis have the ability to mobilize P from secondary minerals and organic sources. Our hypothesis was that AM-bearing plants will invest more carbon to their fungal symbiont in case P must be exploited from less accessible P sources. For this, we carried out a time course experiment (91 days) with split-chamber mesocosms ensuring the mobilization of P by the mycorrhizal partner only. Orthophosphate (OP) and phytic acid (PA) in their free state and adsorbed to goethite (GOE-OP; GOE-PA) have been offered to the host plant. According to our knowledge, this is the first report where an organic P source bonded to a secondary mineral has been tested as a plant P source via the mycorrhizal P uptake pathway. The PLFA 16:1ω5c is known to be part of the membrane constituents and it is considered a good AM biomass estimator (Olsson and Wilhelmsson 2000). In our study it correlated positively with incorporated P and the AM plant root activity (arbuscules %) for all provided P sources. Additionally, those AM plants which accessed OP and GOE-OP also showed a positive significant correlation of the arbuscules percentages, with the incorporated P, the PLFA 18:1ω7c, and in case of GOE-PA also with the PLFA 18:2ω6,9. These two PLFA biomarkers have been previously found in R. irregularis hyphae (Olsson et al. 2002) and might indicate that AM fungi modified their fatty acid composition in the hyphae during the mobilization of P from the different P sources. As fungal energy storage we also measured the NLFA 16:1ω5c. It was significantly higher for both P sources bonded to goethite compared to free OP and PA. These results point towards different C investment to uptake of P though the mycorrhizal pathway having a direct consequence for the carbon sequestration in soils

Particle size as controlling factor of soil microaggregate formation

Aggregates are formed when soil particles connect to larger secondary units. Stable microaggregates in soils are supposed to consist of close associations of Fe-oxides and clay minerals with both components being attracted by electrostatic forces between the oppositely charged particles. However, the geometric preconditions for the formation of stable associations between Fe oxides and clay minerals are poorly known. Therefore, our goal was to determine geometrical constraints resulting from particle size and morphology likely impeding optimum arrangement of particles for shielding of charges during aggregate formation. Aggregation kinetics was determined for nine combinations of each three particle size fractions of goethite and mica in a Zetasizer at pH 6. Experiments were conducted using needle-shape goethites synthesized at 4, 20, and 60°C (lengths of 0.42, 0.46 and 0.84 µm, specific surface areas (SSA) of 87, 75, and 60 m²/g, respectively) and ground platy muscovite separated in fine, medium and coarse clay (diameters of 0.16, 0.80, and 2.9 µm, SSA of 182, 100, and 27 m²/g, respectively). For five combinations even smallest additions of goethite to muscovite facilitated aggregation. By further additions of goethite maximum aggregate sizes up to 5.6 µm were obtained, the respective mixing ratio strongly depending on the type of combination. After that sizes declined. For medium and coarse-sized muscovite, goethite amendments >18% did not facilitate aggregation, indicating the dominance of repulsive forces. In contrast, for fine-sized muscovite aggregation was facilitated up to an addition of 63% fine-sized goethite and of 90% coarse-sized goethite. Here also biggest aggregate sizes were obtained. Based on all examined size fraction combinations, our results suggest a strong impact of particle size on aggregation. Whereas all combinations with fine-sized muscovite facilitated aggregation at very different mixing ratios, the amendment of the finest fraction of goethite to medium- and coarse-sized muscovite facilitated aggregation at small additions only. Aggregation was favored for evenly sized combinations. The quantification of surface charge density of minerals and calculation of charge balances of the combinations is in progress and will help interpreting the observed aggregation patterns. For soils it is likely that aggregation by electrostatic interactions occurs only at certain mineral mixing ratios highly depending on particle morphology

Testing hypotheses on interlinks between silicon and organic matter cycling in rice ecosystems

Recent studies demonstrated that sufficient Si supply enhances the resistance of rice plants against biotic and abiotic stresses. The mechanisms by which Si supports the stress resistance are still under debate. One hypothesis assumes that phytoliths exert similar eco-physiological functions as organic structural compounds. The formation of amorphous Si oxide bodies (`phytoliths`) within the plant tissue, therefore, represents an energy-saving alternative to synthesis of organic structural compounds, such as cellulose and lignin. Hence, Si availability may interact with the recycling of organic matter because rates of plant litter decomposition are regulated by contents of structural organic compounds. We currently test the hypothesis using a large set of rice straw samples collected at 70 paddy fields in Vietnam and the Philippines. Due to the differing portions of weatherable silicate minerals in soil, Si availability varies largely between the fields; the Si concentrations in the straw samples, thus, range from 1.6 to 10.7%. The Si concentrations are significantly negatively related to carbon concentrations, which range from 31.1 to 42.5% (the R2 of the linear relationship is 0.83). In turn, no relationships between Si and nitrogen concentrations were found. These findings support the assumption that Si substitutes N-poor structural compounds in rice plants. Currently, we apply cupric oxide oxidation analysis to the straw samples in order to test for relationships between concentrations Si and lignin. The results will be included into the proposed presentation

Effects of agricultural management on Si cycling in Italian paddy fields

Silicon (Si) is a beneficial nutrient for rice plants; it improves their resistance against biotic and abiotic stresses. Recent research showed that Si availability in soils is, on a large geographic scale, determined by stocks of weatherable silicate minerals. However, also on the smaller regional scale, pronounced differences in Si uptake of rice plants were observed. The reasons for these differences are not yet clear. They might include effects of agricultural management, such as crop residue recycling and irrigation. Here, we test the long-term effects of four different agricultural management practices in Vercelli (Northwest Italy), where one rice crop per year is cultivated from May to September. The experimental platform was installed in 2003 on a Haplic Gleysol known to be under continuous rice cultivation for the last 30 years and having low plant-available Si concentration. The following management practices were considered (i) tillage and crop residue incorporation in spring (ii) post-harvest rice straw burning and tillage in spring, (iii) tillage and crop residue incorporation in autumn, and (iv) tillage and crop residue incorporation in spring followed by dry seeding and delayed flooding. After seven years, in 2010, topsoil and plants were sampled at five points of time during the cropping season. We will examine plant-available Si concentrations in soil and Si uptake by rice. Results will be presented at the conference; they will reveal whether farmers are able to actively improve Si supply to rice plants by their agricultural management

Greening boosts soil formation and soil organic matter accumulation in Maritime Antarctica

Global warming in the Antarctic Peninsula, Maritime Antarctica, within the past 45 years has accelerated rapid glacier retreatment, forming temporal gradients of soil development that concurs with the colonization of the ice-free soils by phototrophs. In the past decade the paradigm emerged that above- and belowground processes are interconnected, e.g. recently gained carbon fuels microbial activity and thus drives soil organic matter built-up and decomposition as well as mineral weathering. Studies of carbon allocation for Antarctic ecosystems, occurring in harsh conditions are lacking. Little is also known about the contribution of bacteria and fungi to decomposition of different soil carbon pools with different turnover rates in these soils, which is of utmost importance for the prediction of the future feedback of the Antarctic carbon balance to climate change. We followed soil horizon formation, soil organic carbon accumulation and carbon exchange with the atmosphere along a gradient of phototrophs of different trophic complexity level at King George Island by combining soil chemical analyses, field CO2 flux measurements, C-13 in situ labeling and molecular methods (PLFA and metabolomics). Our study revealed that colonization of the ice-free soils by vascular plant (Deschampsia antarctica) was leading to the formation of well-developed soil, with high contents of organic carbon and with a relatively high rates of photosynthesis and CO2 soil efflux. The soils sampled under D. antarctica showed the impact of this higher plant on the soil organic matter, containing significantly higher amounts of carbohydrates and amines, presumably as a result of root exudation. As determined by the C-13 labeling experiment more than 15% of the carbon recently assimilated by D. antarctica was transferred belowground, with a major flow into soil fungi. This suggests that not bacteria, but rather fungi preferentially and faster utilize the recently assimilated low molecular compounds allocated to the soil. Probably, successful performance of vascular plants in Maritime Antarctica may significantly foster biological weathering via enhanced microbial activity

To relate surface properties and surface elemental composition - Application of XPS in soil science

Soil particles always are coated by thin layers (nm to µm) of predominantly organic compounds that form the interface between particle and pore space and govern soil functioning (e.g. liquid transport, sorption, respiration). Chemical modification of the surface layer can change surface properties such as wettability (quantified in terms of contact angle CA) with implications for e.g. liquid distribution and sorption capacity. This points to the importance to specifically analyze the coating's chemical composition in order to better understand soil functioning. The shallow analysis depth (max. 10 nm) indicates X ray photoelectron spectroscopy (XPS) as a suitable tool. Here, all elements with Z ≥ 3 will be identified by the binding energy of the photoelectrons emitted after irradiation of the surface by X rays. In sensu stricto only applicable to flat and smooth surfaces our results so far prove applicability of XPS as well to rough surfaces such as soil particles. For XPS no sample pre-treatment is needed, i.e. the surfaces analyzed are those governing e.g. CA and sorption. The relation between surface elemental composition and CA could be demonstrated within a soil chronosequence where the changes of surface element contents due to an increasing coating of the particles by organic compounds and microorganisms were correlated to increasing CA. The surface O/C ratio could be identified as a general parameter linking surface chemical composition and CA for a wide range of different materials including hydrophobized glass slides while the amount of non-polar C species was indicated to define CA. Artificially induced modifications of surface properties became visible by changes in the surface elemental composition. Gentle crushing of soil microaggregates (SMA) resulted in slightly increased N contents hinting on a preferred location of N compounds within SMA. Exposition to HCl gas to decrease soil pH or cleaning of quartz sand by HCl treatment resulted in addition of Cl and removal of Fe, respectively. However, due to its high surface sensitivity XPS measures the presence of C species on all surfaces exposed to the environment (adventitious carbon AC). AC was found to complicate the verification of sorption of small amounts of organic acids to montmorillonite, pointing on the necessity to estimate the influence of AC in certain cases. On the other hand, detection of AC indicates AC as a factor to be considered when discussing surface properties

Structures and properties of bioorgano-clays

Interactions between microbial matter and clays are a common interfacial phenomenon in soil and sediment environments. However, fundamental mechanisms governing the formation and interactions of clay minerals with microbial-derived organic substances are still poorly understood. Therefore, our central aim was to study the formation of bioorgano-clay composites and their specific material properties and compare these properties with those of well-studied organo-clays. Pure organic cations (e.g., alkylammonium homologues) and complex microbial biomass (e.g., fungal biomass from Aphanocladium sp.) were used to prepare organo- and bioorgano-clays by varying the amount of clay (montmorillonite) and organic materials used. Interaction mechanisms between organic materials and clay and the resulting structure and physicochemical properties were explored by multiple experimental methods (e.g. IR spectroscopy, contact angle, zeta potential, X-ray photoelectron spectroscopy, transmission electron microscopy) in a combination with molecular modelling to determine the structure, composition, and properties of the prepared bioorgano-clays. Depending on origin, type, and size of the organic material and the clay, two basic types of bioorgano-clays were found: (i) bioorgano-clays having their clay particles coated by bioorganic matter with only limited or no penetration into interlayer galleries and (ii) bioorgano-clays having bioorganic matter distributed in the interlayer galleries and/or on the external surfaces of clay particles. Both types show heterogeneous arrangements of the amended organic matter inducing differences in shape and size of organo-clay particles. Consequently, changes in pore volumes, stability, and elemental interface properties can be verified. Compared to organo-clays, bioorgano-clays provided e.g. a higher adsorption capacity for uranyl, suggesting that modification of clays by rather unspecific microbial compounds significantly enhanced the number of exchange sites. Bioorganic-clays, although being less specific in nature, might therefore be applied more broadly in situations where a high sorption capacity, e.g., for contaminants, is required

Verteilung und Bindungsformen von Uran in Niedermoorböden

Moorböden gelten als wichtige geochemische Senke für Uran (U). Dennoch wurde die Uranbindung in Moorböden bislang nur unzureichend erforscht. Die potentiellen Mechanismen der Uranfestlegung in organischen Böden sind vielfältig und reichen von der Fällung UIV/VI-haltiger Minerale (z.B. Uraninit, UIVO2) bis zur Komplexierung von UIV/VI auf organischen sowie anorganischen Oberflächen. Das Ziel unserer Arbeit bestand daher in der Erforschung der räumlichen Verteilung sowie der Bindungsmechanismen von geogenem U in alpinen Niedermoorböden (Umax = 335 mg/kg; pH = 4.7-6.6, Eh = -127 bis 463 mV) mittels Synchrotron-basierter Röntgenfluoreszenzspektrometrie sowie Röntgenabsorptionsspektroskopie (XANES und EXAFS). Unsere Ergebnisse zeigen, dass U auf der Mikrometerskala heterogen verteilt und mit partikulärer organischer Substanz assoziiert ist. Mikrofokussierte U L3-Kanten XANES-Messungen von uranreichen Partikeln ergaben 35-68% UIV. Die Auswertungen von U L3-Kanten EXAFS-Spektren ausgewählter Bodenproben belegen, dass sowohl UIV als auch UVI in bidentat-mononuklearen Carboxylatkomplexen gebunden sind. Dabei kann die Bildung organischer UIV-Komplexe mit der Reduktion von organisch komplexiertem UVI im stark anoxischen Milieu erklärt werden. Insgesamt verdeutlichen unsere Untersuchungen, dass die Fällung uranhaltiger Mineralphasen sowie die Adsorption von U auf Sesquioxid- und Schichtsilikatoberflächen am Untersuchungsstandort eine nur untergeordnete Rolle für die Uranfestlegung spielen