Browsing by Person "Rennert, Thilo"

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Associations of short-range ordered aluminosilicates and organic matter: formation, properties and stabilization of organic matter
(2023) Lenhardt, Katharina Raphaela; Rennert, Thilo
Short-range ordered aluminosilicates (SROAS) typically form during the weathering of volcanic ejecta by polymerization of released aluminium (Al) and silicon (Si). These minerals exhibit variable chemical composition and crystallinity. Tubular imogolite is a SROAS with long-range order; its locally defined Si configuration occurs also in poorly ordered SROAS. Interactions of SROAS and organic matter (OM) promote carbon (C) accrual by protecting OM from microbial degradation in the long term; however, the fundamental processes are poorly understood. Stable mineral-organic associations may form by adsorption of dissolved OM (DOM) on SROAS surfaces and by co-precipitation of DOM with SROAS during mineral formation. The objective of this study was to elucidate the chemical interactions between DOM and SROAS by both processes, and to assess the stability of OM sorbed by SROAS. Therefore, the impact of SROAS composition on DOM adsorption, partitioning of OM moieties by adsorption and co-precipitation, the structure of co-precipitates, and the degradability of co-precipitated OM was investigated. A method to synthesize SROAS at ambient conditions was developed to mimic the surface properties of natural weathering products. Characterization of SROAS structure by solid-state 27Al and 29Si nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FTIR) spectroscopy evinced a close similarity of synthetic SROAS to their natural analogues. Aluminium-rich SROAS (molar Al:Si>2) resembled proto-imogolite, with Al mainly in octahedral coordination and ≥38% of Si nuclei exhibiting an imogolite-like configuration. Silicon-rich SROAS (molar Al:Si = 1.4) contained tetrahedral Al and Si existed largely in ill-defined environments. Analyses of the specific surface area by nitrogen adsorption revealed marked aggregation of Al-rich SROAS, which was less pronounced in Si-rich SROAS. These results show that the poor crystallinity of Al-rich SROAS permits a very dense spatial arrangement of mass at the submicron scale, while Si incorporation restricts aggregation. Interactions of SROAS and DOM were studied using natural DOM with heterogeneous composition collected in situ from a Dystric Cambisol at two depths, and by water extraction of litter. Solid-state 13C-NMR and FTIR spectroscopy revealed a major contribution of oxidized aromatic moieties to soil DOM, likely originating from lignin degradation, while litter DOM was predominantly composed of carbohydrates. Soil DOM adsorption was driven by surface accessibility and was thus larger for Si-rich SROAS than for Al-rich SROAS, showing the importance of SROAS physical properties for OM retention. Aromatic products of lignin degradation preferentially adsorbed on SROAS, inducing relative enrichment of aliphatic substances, particularly carbohydrates, in the residual DOM. Topsoil DOM adsorption depended more strongly on contact time (1–168 h) than subsoil DOM adsorption, possibly due to qualitative differences of the aromatic fraction. Associations formed by co-precipitation contained more C than adsorption complexes. As Al interacted preferentially with oxidized aromatic compounds, co-precipitation of DOM increased as a function of aromatic C. Nevertheless, marked sorption of carbohydrates from litter DOM evinced possible retention of substances with low affinity for Al by co-precipitation, in contrast to adsorption. Time-dependent (1–72 h) structural evolution of SROAS in the absence of DOM was examined to resolve the mechanisms of SROAS formation. Irrespective of the initial molar Al:Si ratio, amorphous precursors formed by olation during the first hour. After 72 h, up to 50% of Si nuclei exhibited imogolite-like configuration, showing rapid development of short-range order. Dissolved OM interfered in condensation of Al and Si, causing partial exclusion of Si, and slowed crystallisation of the octahedral Al sheet, promoting ill-defined Si species in the co-precipitates. Hence, DOM likely impedes assembly of precursors into structurally ordered particles, in particular, oxidized aromatic DOM in topsoils. The binding strength of DOM to SROAS surfaces may be affected by Si incorporation due to structure modifications. Thus, a mechanistic adsorption study was conducted with oxalic, salicylic and octanoic acid as models of functional moieties in DOM. Adsorption of oxalic and salicylic acid was up to 80–90% lower for Si-rich SROAS than for Al-rich SROAS. Rapid (<1 min) release of hydroxyls, indicating ligand exchange, was observed only for oxalic and salicylic acid, suggesting octanoic acid interacted electrostatically with SROAS surfaces. Chelate complexes of oxalic acid and partial inner-sphere binding of salicylic acid on both SROAS were identified by FTIR spectroscopy. Fast adsorption kinetics were retraced by changes in electrical conductivity using a stopped-flow technique. Ligand exchange by oxalate proceeded at a similar rate as complexation of monomeric Al3+, showing its binding to octahedral Al. Hence, the much lower susceptibility of Si-rich SROAS to ligand exchange with carboxyl groups is caused by tetrahedral Al. Consequently, little OM may be stabilized by chemical bonds with Si-rich SROAS. The degradability of co-precipitated carbohydrates was tested by addition of b-glucosidase, a microbial extracellular enzyme, at optimal concentration and quantification of the reaction product glucose. Glucose release was analysed for initial DOM, co-precipitated OM and for residual DOM to account for compositional changes by co-precipitation. As a result of carbohydrate enrichment in residual DOM, its degradability by b-glucosidase increased. Minor amounts of glucose were released from co-precipitated carbohydrates, showing their restricted accessibility for enzymes due to occlusion. Formation of SROAS in soils likely induces preferential association of lignin degradation products with the mineral matrix and alters the composition of OM introduced to the subsoil. Otherwise easily degradable OM with low affinity for SROAS surfaces can be effectively protected from mineralization by co-precipitation. As the structure of SROAS reflects formation processes and affects their reactivity, future research characterizing natural SROAS will give mechanistic insights into C sequestration and potentially other vital soil functions.
Formation and properties of inorganic Si-contaminant compounds
(2023) Stein, Mathias; Rennert, Thilo
Environmental contamination is the most pressing issue of our global society. Among others, contamination with potentially toxic elements (PTEs) such as cadmium (Cd), copper (Cu), and lead (Pb) threatens organisms, humans, and entire ecosystems. Silicon (Si) is known to benefit the resilience to such abiotic stresses and its application showed to alleviate PTE toxicity. These beneficial effects are predominantly attributed to in planta processes, but PTE immobilization in soil induced by Si addition has also been reported. However, interactions between silicic acid and Cd, Cu, and Pb at undersaturation of their silicates and other mineral phases remains elusive. Silicic acid, which is dissolved Si, may interact with cationic PTEs in soil, altering their environmental fate. At oversaturation, PTEs and silicic acid may precipitate forming metal silicates, whereas at undersaturation PTEs may be incorporated into the network of polymerized silicic acid or inner-spherically complexed on the negatively charged surface of polymeric silicic acid, forming particulate Si-contaminant compounds. Aiming to elucidate the extent and the mechanism of the potential PTE immobilization, long-term formation experiments in aqueous solution, a soil column experiment, and batch adsorption experiments including isothermal titration calorimetry (ITC) experiments were conducted. Long-term formation experiments in aqueous solution were conducted at undersaturation of PTE silicates and other mineral phases. Time-dependent particle size and charge changes were measured in between 211 days using dynamic light scattering and phase analysis light scattering. Solid phases were characterized by Fourier transform infrared (FTIR) spectroscopy and 29Si nuclear magnetic resonance (NMR) spectroscopy. Particle size measurements revealed a positive effect of cationic PTEs on silicic acid polymerization (Cu>Cd>Pb). However, only traces (2.1‰ Cd, 2‰ Cu and 1.4‰ Pb of the initially added PTEs) were bound during the polymerization of silicic acid. Copper was incorporated in the polymeric network of silicic acid during its polymerization as indicated by FTIR spectra and 29Si NMR relaxation experiments. Cadmium was only outer-spherically adsorbed. The long-term formation experiments revealed that particulate compounds form due to silicic acid/PTE interactions at undersaturation of other mineral phases. Soil column experiments were conducted to investigate the formation of Si-contaminant compounds in an acidic soil (pH 4.6). Therefore, a Haplic Phaeozem was preconditioned with Cu and Cd in the absence and presence of additional monomeric silicic acid and subsequently irrigated with artificial rainwater. Interactions of silicic acid and PTEs were investigated by monitoring the elemental composition of the eluates, and the size and charge of the particles eluted. After irrigation, total and exchangeable Si and PTE contents were analysed. Silicic acid application resulted in larger particles in the eluates, indicating silicic acid polymerization. The molar metal:Si ratios of the eluates and the significant correlation between Si and exchangeable metals indicated that particularly Cu formed Si-contaminant compounds in the soil, enhancing its retention. However, translocation of PTEs in particulate form, associated with polymerized silicic acid, was indicated. The negative charge and the very small size of the formed compounds may facilitate translocation from soil into groundwater. Batch adsorption experiments and ITC experiments were conducted to examine mechanism and extent of PTE adsorption to polymeric silicic acid. These experiments did not reveal any adsorption of the metals on polymeric silicic acid at pH 4 to 6 and after 24 h, which was underpinned by the results of the ITC experiments. However, zeta-potential measurements indicated weak electrostatic interactions between the negatively charged silanol groups and the PTEs. These electrostatic interactions may be the initial step of Si-contaminant compound formation. This thesis elucidates extent and mechanisms of silicic acid, either mono- or polymeric, and PTE interactions, showing the formation of particulate compounds from the reaction between silicic acid and cationic PTEs in aqueous solution and in an acidic soil. Particularly Cu formed stable compounds during silicic acid polymerization. However, the interactions showed a low extent and mainly weak electrostatic interactions, concluding that the addition of monomeric silicic acid to acidic soils may not be a quantitatively effective measure to reduce PTE mobility in soils. Aggregation effects, resulting from freezing/thawing or drying/rewetting, however, could alter the mobility of Si-contaminant compounds. These effects may be subject of future research, as well as the spectroscopic detection of Si-contaminant compounds in soils.
Release of glucose from dissolved and mineral‐bound organic matter by enzymatic hydrolysis
(2023) Lenhardt, Katharina R.; Brandt, Luise; Poll, Christian; Rennert, Thilo; Kandeler, Ellen
Sorption of dissolved organic matter (DOM) by poorly crystalline minerals during their formation may protect large amounts of carbon in soils from mineralization. We investigated the bioavailability of carbohydrates in DOM and after co-precipitation with short-range ordered aluminosilicates. Carbohydrates originated from soil solutions collected in situ at two depths of a Dystric Cambisol, and from litter extracts. Quantification of substrate-specific degradability was achieved by the addition of β-glucosidase at an optimal concentration and subsequent determination of glucose release. Depending on DOM composition, 0.6–41.4 mg g−1 C−1 of glucose was enzymatically released from dissolved carbohydrates. Co-precipitated carbohydrates were partially accessible, resulting in a glucose release of 0.7–5.2 mg g−1 C−1. Restricted enzymatic depolymerization due to co-precipitation may contribute to accumulation of easily degradable substrates in soils.