Persistence of aromatic compounds in soils and sediments : a molecular perspective

This thesis explores open questions regarding molecular forms and interactions of natural and synthetic aromatic compounds present in soils and sediments. Plant biomass-derived black carbon (biochar) generated through incomplete natural and anthropogenic combustion processes is a major source of aromaticity in terrestrial ecosystems. Chapter one represents a detailed account of the variations in the chemical and physical nature of aromatic components of char black carbon. Despite reports showing that aromatic compounds are degraded with relative ease, they are relatively persistent in subsurface environments. Chapter two highlights unique mechanisms of interaction of aromatic π-systems (i.e., π-electron donor-acceptor interactions) by which aromatic molecules adsorb to mineral and organic phases. It is discussed how these interactions may contribute to the sequestration of aromatic compounds in soils and sediments

Assessing the role of reactive metal species in soil organic matter cycling using chemical imaging

Intimate associations with reactive metal species permanently protect soil organic matter (SOM) from microbial access and oxidation, contributing to the build-up of organic carbon (C) stocks in soils. It is increasingly recognized, however, that such associations can be reversible and that reactive metal species might even facilitate the oxidation of SOM. Both processes would increase the potential for soil C loss, prompting questions regarding the environmental conditions under which interactions of SOM with reactive mineral phases are protective, reversible or even facilitate oxidation. One of the foremost challenges in characterizing these interactions is the need to describe the dynamics of both SOM and metals at fine spatial scales without disturbing existing chemical or physical associations. This thesis thus addresses the general question whether non-invasive chemical imaging techniques can be used to distinguish protective interactions between SOM and reactive metal species from those that are susceptible to or facilitate C loss. The following research aimed to identify the nature of the interactions between SOM and two abundant redox-active metals (iron and manganese) in three soil microenvironments: fungal mats, the rhizosphere and the litter layer. The first of the three chapters describes the rapid formation of protective associations between fungal-derived SOM and iron (hydr)oxide precipitates in ectomycorrhizal mats. The second chapter demonstrates how root exudates can reverse such protective associations between SOM and reactive Fe phases, promoting microbial access to SOM and causing C loss in the rhizosphere. The third chapter establishes the functional role of reactive manganese species in the microbial oxidation of aromatic compounds in forest litter decomposition. Combined, this work not only demonstrates the ability of imaging and spectroscopy techniques to probe the nature of interactions between SOM and reactive minerals in soils. It also highlights the need to extend current conceptual models to reversible and oxidative interactions between reactive minerals and SOM and their implications for SOM cycling

Long-Term Litter Decomposition Controlled by Manganese Redox Cycling

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter was paralleled by variations in Mn oxidation state and concentration. A detailed chemical imaging analysis of the litter revealed that fungi recruit and redistribute unreactive Mn2+ provided by fresh plant litter to produce oxidative Mn3+ species at sites of active decay, with Mn eventually accumulating as insoluble Mn3+/4+ oxides. Formation of reactive Mn3+ species coincided with the generation of aromatic oxidation products, providing direct proof of the previously posited role of Mn3+-based oxidizers in the breakdown of litter. Our results suggest that the litter-decomposing machinery at our coniferous forest site depends on the ability of plants and microbes to supply, accumulate, and regenerate short-lived Mn3+ species in the litter layer. This observation indicates that biogeochemical constraints on bioavailability, mobility, and reactivity of Mn in the plant–soil system may have a profound impact on litter decomposition rates

The Ability of Soil Pore Network Metrics to Predict Redox Dynamics Is Scale Dependent

Variations in microbial community structure and metabolic efficiency are governed in part by oxygen availability, which is a function of water content, diffusion distance, and oxygen demand; for this reason, the volume, connectivity, and geometry of soil pores may exert primary controls on spatial metabolic diversity in soil. Here, we combine quantitative pore network metrics derived from X-ray computed tomography (XCT) with measurements of electromotive potentials to assess how the metabolic status of soil depends on variations of the overall pore network architecture. Contrasting pore network architectures were generated using a Mollisol—A horizon, and compared to intact control samples from the same soil. Mesocosms from each structural treatment were instrumented with Pt-electrodes to record available energy dynamics during a regimen of varying moisture conditions. We found that volume-based XCT-metrics were more frequently correlated with metrics describing changes in available energy than medial-axis XCT-metrics. An abundance of significant correlations between pore network metrics and available energy parameters was not only a function of pore architecture, but also of the dimensions of the sub-sample chosen for XCT analysis. Pore network metrics had the greatest power to statistically explain changes in available energy in the smallest volumes analyzed. Our work underscores the importance of scale in observations of natural systems

Shifting mineral and redox controls on carbon cycling in seasonally flooded mineral soils

Although wetland soils represent a relatively small portion of the terrestrial landscape, they account for an estimated 20 %–30 % of the global soil carbon (C) reservoir. C stored in wetland soils that experience seasonal flooding is likely the most vulnerable to increased severity and duration of droughts in response to climate change. Redox conditions, plant root dynamics, and the abundance of protective mineral phases are well-established controls on soil C persistence, but their relative influence in seasonally flooded mineral soils is largely unknown. To address this knowledge gap, we assessed the relative importance of environmental (temperature, soil moisture, and redox potential) and biogeochemical (mineral composition and root biomass) factors in controlling CO2 efflux, C quantity, and organic matter composition along replicated upland–lowland transitions in seasonally flooded mineral soils. Specifically, we contrasted mineral soils under temperature deciduous forests in lowland positions that undergo seasonal flooding with adjacent upland soils that do not, considering both surface (A) and subsurface (B and C) horizons. We found the lowland soils had lower total annual CO2 efflux than the upland soils, with monthly CO2 efflux in lowlands most strongly correlated with redox potential (Eh). Lower CO2 efflux as compared to the uplands corresponded to greater C content and abundance of lignin-rich, higher-molecular-weight, chemically reduced organic compounds in the lowland surface soils (A horizons). In contrast, subsurface soils in the lowland position (Cg horizons) showed lower C content than the upland positions (C horizons), coinciding with lower abundance of root biomass and oxalate-extractable Fe (Feo, a proxy for protective Fe phases). Our linear mixed-effects model showed that Feo served as the strongest measured predictor of C content in upland soils, yet Feo had no predictive power in lowland soils. Instead, our model showed that Eh and oxalate-extractable Al (Alo, a proxy of protective Al phases) became significantly stronger predictors in the lowland soils. Combined, our results suggest that low redox potentials are the primary cause for C accumulation in seasonally flooded surface soils, likely due to selective preservation of organic compounds under anaerobic conditions. In seasonally flooded subsurface soils, however, C accumulation is limited due to lower C inputs through root biomass and the removal of reactive Fe phases under reducing conditions. Our findings demonstrate that C accrual in seasonally flooded mineral soil is primarily due to low redox potential in the surface soil and that the lack of protective metal phases leaves these C stocks highly vulnerable to climate change

Carbon-Dot-Sensitized, Nitrogen-Doped TiO2in Mesoporous Silica for Water Decontamination through Nonhydrophobic Enrichment-Degradation Mode

Mesoporous silica synthesized from the co-condensation of tetraethoxysilane and silylated carbon dot containing amide group has been adopted as the carrier for the in-situ growth of TiO2 through an impregnation-hydrothermal crystallization process. Benefitted from the initial complexing between the titania precursor and carbon dot, highly dispersed anatase TiO2 nanoparticles can be formed inside the mesoporous channel. The hybrid material possesses ordered hexagonal mesostructure with a p6mm symmetry, high specific surface area (446.27 m2g-1), large pore volume (0.57 cm3g-1), uniform pore size (5.11 nm) and a wide absorption band between 300-550 nm. TiO2 nanocrystals are anchored to carbon dot through bonds of Ti-O-N and Ti-O-C as revealed by X-ray photoelectron spectroscopy. Moreover, the nitrogen doping of TiO2 is also verified by the formation of Ti-N bond. This composite shows excellent adsorption capability to organic 2, 4-dichlorophenol and acid orange 7 with electron-deficient aromatic ring through the electron donor-acceptor interaction between carbon dot and organics instead of hydrophobic effect as analyzed by the contact angle analysis, which can be photocatalytically recycled through visible light irradiation after the adsorption. The narrowed bandgap by nitrogen doping and the photosensitization effect of carbon dot are revealed to be co-responsible for the visible-light activity of TiO2. The adsorption capacity does not suffer obvious loss after being recycled 3 times

Redox Properties of Plant Biomass-Derived Black Carbon (Biochar)

Soils and sediments worldwide contain appreciable amounts of thermally altered organic matter (chars) of both natural and industrial origin. Additions of chars into soils are discussed as a strategy to mitigate climate change. Chars contain electroactive quinoid functional groups and polycondensed aromatic sheets that were recently shown to be of biogeochemical and enviro-technical relevance. However, so far no systematic investigation of the redox properties of chars formed under different pyrolysis conditions has been performed. Here, using mediated electrochemical analysis, we show that chars made from different feedstock and over a range of pyrolysis conditions are redox-active and reversibly accept and donate up to 2 mmol electrons per gram of char. The analysis of two thermosequences revealed that chars produced at intermediate to high heat treatment temperatures (HTTs) (400-700°C) show the highest capacities to accept and donate electrons. The electron accepting capacities (EACs) increase with the nominal carbon oxidation state of the chars. Comparable trends of EACs and of quinoid C=O contents with HTT suggest quinoid moieties as major electron acceptors in the chars. We propose to consider chars in environmental engineering applications that require controlled electron transfer reactions. Electroactive char components may also contribute to the redox properties of traditionally defined "humic substances"

Are oxygen limitations under recognized regulators of organic carbon turnover in upland soils?

Understanding the processes controlling organic matter (OM) stocks in upland soils, and the ability to management them, is crucial for maintaining soil fertility and carbon (C) storage as well as projecting change with time. OM inputs are balanced by the mineralization (oxidation) rate, with the difference determining whether the system is aggrading, degrading or at equilibrium with reference to its C storage. In upland soils, it is well recognized that the rate and extent of OM mineralization is affected by climatic factors (particularly temperature and rainfall) in combination with OM chemistry, mineral–organic associations, and physical protection. Here we examine evidence for the existence of persistent anaerobic microsites in upland soils and their effect on microbially mediated OM mineralization rates. We corroborate long-standing assumptions that residence times of OM tend to be greater in soil domains with limited oxygen supply (aggregates or peds). Moreover, the particularly long residence times of reduced organic compounds (e.g., aliphatics) are consistent with thermodynamic constraints on their oxidation under anaerobic conditions. Incorporating (i) pore length and connectivity governing oxygen diffusion rates (and thus oxygen supply) with (ii) ‘hot spots’ of microbial OM decomposition (and thus oxygen consumption), and (iii) kinetic and thermodynamic constraints on OM metabolism under anaerobic conditions will thus improve conceptual and numerical models of C cycling in upland soils. We conclude that constraints on microbial metabolism induced by oxygen limitations act as a largely unrecognized and greatly underestimated control on overall rates of C oxidation in upland soils.Keywords: Anaerobic metabolism, Soil carbon, Soils, Organic matter, Oxygen limitationsKeywords: Anaerobic metabolism, Soil carbon, Soils, Organic matter, Oxygen limitation

A holistic framework integrating plant-microbe-mineral regulation of soil bioavailable nitrogen

Soil organic nitrogen (N) is a critical resource for plants and microbes, but the processes that govern its cycle are not well-described. To promote a holistic understanding of soil N dynamics, we need an integrated model that links soil organic matter (SOM) cycling to bioavailable N in both unmanaged and managed landscapes, including agroecosystems. We present a framework that unifies recent conceptual advances in our understanding of three critical steps in bioavailable N cycling: organic N (ON) depolymerization and solubilization; bioavailable N sorption and desorption on mineral surfaces; and microbial ON turnover including assimilation, mineralization, and the recycling of microbial products. Consideration of the balance between these processes provides insight into the sources, sinks, and flux rates of bioavailable N. By accounting for interactions among the biological, physical, and chemical controls over ON and its availability to plants and microbes, our conceptual model unifies complex mechanisms of ON transformation in a concrete conceptual framework that is amenable to experimental testing and translates into ideas for new management practices. This framework will allow researchers and practitioners to use common measurements of particulate organic matter (POM) and mineral-associated organic matter (MAOM) to design strategic organic N-cycle interventions that optimize ecosystem productivity and minimize environmental N loss

Mineral protection of soil carbon counteracted by root exudates

Multiple lines of existing evidence suggest that climate change enhances root exudation of organic compounds into soils. Recent experimental studies show that increased exudate inputs may cause a net loss of soil carbon. This stimulation of microbial carbon mineralization ('priming') is commonly rationalized by the assumption that exudates provide a readily bioavailable supply of energy for the decomposition of native soil carbon (co-metabolism). Here we show that an alternate mechanism can cause carbon loss of equal or greater magnitude. We find that a common root exudate, oxalic acid, promotes carbon loss by liberating organic compounds from protective associations with minerals. By enhancing microbial access to previously mineral-protected compounds, this indirect mechanism accelerated carbon loss more than simply increasing the supply of energetically more favourable substrates. Our results provide insights into the coupled biotic-abiotic mechanisms underlying the 'priming' phenomenon and challenge the assumption that mineral-associated carbon is protected from microbial cycling over millennial timescales