| 1. |
- Andersson, Erika, et al.
(författare)
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A contrast variation SANS and SAXS study of soil derived dissolved organic matter, and its interactions with hematite nanoparticles
- 2023
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Ingår i: JCIS Open. ; 11
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Tidskriftsartikel (refereegranskat)abstract
- Soil derived dissolved organic matter (DOM) is an important component of the carbon cycle and influences numerous biogeochemical processes, including the formation of mineral-organic associations. DOM ranges in size from small organic molecules to macromolecules and colloidal aggregates. In this study we have used small angle neutron (SANS) and X-ray (SAXS) scattering to characterize the colloidal DOM fraction from the organic layer of a boreal forest soil, and its interactions with hematite (α-Fe2O3) mineral nanoparticles. Comparison between SAXS and contrast variation SANS patterns revealed that the scattering form factor of the colloidal DOM aggregates was essentially independent of the scattering contrast, implying that the colloidal aggregates have an essentially homogeneous chemical composition, down to the nanometre length scale. Variation of the D2O/H2O ratio of the solvent yielded a SANS intensity minimum at ca. 40 vol % D2O, which was consistent with colloids composed of mainly polysaccharides. At pH 5.5 the pure hematite nanoparticles were colloidally stable in water and characterized by a ζ-potential of +25 mV and a hydrodynamic radius of ca. 70 nm. In the presence of DOM, the hematite nanoparticles lost the colloidal stability and aggregated into larger clusters, displaying a negative ζ-potential of ca. −25 mV. The charge reversal suggested that negatively charged polyanions of DOM adsorbed onto the hematite particles, possibly leading to bridging flocculation. Our results suggested that mainly low molecular weight components induced hematite aggregation because no or very limited interactions between DOM colloids and hematite were detected.
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| 2. |
- Andersson, Erika, et al.
(författare)
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Generation and properties of organic colloids extracted by water from the organic horizon of a boreal forest soil
- 2023
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Ingår i: Geoderma. - : Elsevier BV. - 0016-7061. ; 432
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Tidskriftsartikel (refereegranskat)abstract
- Organic colloids are an important part of dissolved organic matter (DOM) yet many of their properties remain elusive. The main aims of this study were to assess how the colloidal properties of DOM extracted with water from an organic boreal soil horizon varied with the extraction protocol, and thereby provide insight into the nature of the DOM colloids and develop a mechanistic understanding of how the colloids were generated from the parent soil aggregates. This was accomplished by systematic variations of extraction temperature (4 °C–100 °C), time, mechanical agitation, and pH, together with a combination of chemical analyses, and light and X-ray scattering. Our results agreed with the previous identification of two main colloidal DOM species, one fractal cluster and a second, smaller colloidal DOM species described as chains or coils. Fractal clusters completely dominated the colloidal DOM in extracts from our soil at room temperature and below. Colloidal coils only existed in DOM extracted above room temperature, and their amount increased significantly between 50 °C–100 °C. Moreover, the temperature variation indicated that the fractal clusters partly dissolved into colloidal coils at elevated temperatures. Mechanical agitation at 4 °C significantly increased the amount of DOM extracted, increasing the concentrations of both fractal clusters and low-molecular weight organic compounds. While the clusters were extracted from agitated and non-agitated soil suspensions, the low molecular weight organics were mainly released by agitation. Based on the experimental observations, we propose a conceptual model where parent soil aggregates contain the fractal clusters in mobile and occluded forms, and that the occluded clusters co-exist with occluded low molecular weight organics. These occluded forms may be released by mechanical forces, increasing pH and temperature. At higher temperatures, the soil aggregates and the fractal clusters start to break up, and subsequently individual colloidal coils, presumably carbohydrates, disperse in the water phase. The model explains the origin and properties of the fractal clusters that completely dominate the colloidal DOM extracted from our soil at room temperature and below.
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| 3. |
- De Beeck, Michiel Op, et al.
(författare)
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Elucidating fungal decomposition of organic matter at sub-micrometer spatial scales using optical photothermal infrared (O-PTIR) microspectroscopy
- 2024
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Ingår i: Applied and Environmental Microbiology. - 0099-2240. ; 90:2
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Tidskriftsartikel (refereegranskat)abstract
- In microbiological studies, a common goal is to link environmental factors to microbial activities. Both environmental factors and microbial activities are typically derived from bulk samples. It is becoming increasingly clear that such bulk environmental parameters poorly represent the microscale environments microorganisms experience. Using infrared (IR) microspectroscopy, the spatial distribution of chemical compound classes can be visualized, making it a useful tool for studying the interactions between microbial cells and their microenvironments. The spatial resolution of conventional IR microspectroscopy has been limited by the diffractionlimit of IR light. The recent development of optical photothermal infrared (O-PTIR) microspectroscopy has pushed the spatial resolution of IR microspectroscopy beyond this diffractionlimit, allowing the distribution of chemical compound classes to be visualized at sub-micrometer spatial scales. To examine the potential and limitations of O-PTIR microspectroscopy to probe the interactions between fungal cells and their immediate environments, we imaged the decomposition of cellulose filmsby cells of the ectomycorrhizal fungus Paxillus involutus and compared O-PTIR results using conventional IR microspectroscopy. Whereas the data collected with conventional IR microspectroscopy indicated that P. involutus has only a very limited ability to decompose cellulose films,O-PTIR data suggested that the ability of P. involutus to decompose cellulose was substantial. Moreover, the O-PTIR method enabled the identificationof a zone located outside the fungal hyphae where the cellulose was decomposed by oxidation. We conclude that O-PTIR can provide valuable new insights into the abilities and mechanisms by which microorganisms interact with their surrounding environments.
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| 4. |
- Ellström, Magnus, et al.
(författare)
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The carbon starvation response of the ectomycorrhizal fungus Paxillus involutus.
- 2015
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Ingår i: FEMS Microbiology Ecology. - : Oxford University Press (OUP). - 1574-6941. ; 91:4
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Tidskriftsartikel (refereegranskat)abstract
- The amounts of carbon allocated to the fungal partner in ectomycorrhizal associations can vary substantially depending on the plant growth and the soil nutrient conditions, and the fungus may frequently be confronted with limitations in carbon. We used chemical analysis and transcriptome profiling to examine the physiological response of the ectomycorrhizal fungus Paxillus involutus to carbon starvation during axenic cultivation. Carbon starvation induced a decrease in the biomass. Concomitantly, ammonium, cell-wall material (chitin) and proteolytic enzymes were released into the medium, which suggest autolysis. Compared with the transcriptome of actively growing hyphae, about 45% of the transcripts analyzed were differentially regulated during C-starvation. Induced during starvation were transcripts encoding extracellular enzymes such as peptidases, chitinases, and laccases. In parallel, transcripts of N-transporters were upregulated, which suggest that some of the released nitrogen compounds were re-assimilated by the mycelium. The observed changes suggest that the carbon-starvation response in P. involutus is associated with complex cellular changes that involves autolysis, recycling of intracellular compounds by autophagy and reabsorption of the extracellular released material. The study provides molecular markers that can be used to examine the role of autolysis for the turnover and survival of the ectomycorrhizal mycelium in soils.
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| 5. |
- Floudas, Dimitrios, et al.
(författare)
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Uncovering the hidden diversity of litter-decomposition mechanisms in mushroom-forming fungi
- 2020
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Ingår i: ISME Journal. - : Springer Science and Business Media LLC. - 1751-7362 .- 1751-7370. ; 14:8, s. 2046-2059
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Tidskriftsartikel (refereegranskat)abstract
- Litter decomposing Agaricales play key role in terrestrial carbon cycling, but little is known about their decomposition mechanisms. We assembled datasets of 42 gene families involved in plant-cell-wall decomposition from seven newly sequenced litter decomposers and 35 other Agaricomycotina members, mostly white-rot and brown-rot species. Using sequence similarity and phylogenetics, we split the families into phylogroups and compared their gene composition across nutritional strategies. Subsequently, we used Raman spectroscopy to examine the ability of litter decomposers, white-rot fungi, and brown-rot fungi to decompose crystalline cellulose. Both litter decomposers and white-rot fungi share the enzymatic cellulose decomposition, whereas brown-rot fungi possess a distinct mechanism that disrupts cellulose crystallinity. However, litter decomposers and white-rot fungi differ with respect to hemicellulose and lignin degradation phylogroups, suggesting adaptation of the former group to the litter environment. Litter decomposers show high phylogroup diversity, which is indicative of high functional versatility within the group, whereas a set of white-rot species shows adaptation to bulk-wood decomposition. In both groups, we detected species that have unique characteristics associated with hitherto unknown adaptations to diverse wood and litter substrates. Our results suggest that the terms white-rot fungi and litter decomposers mask a much larger functional diversity.
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| 6. |
- Floudas, Dimitrios, et al.
(författare)
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X-ray scattering reveals two mechanisms of cellulose microfibril degradation by filamentous fungi
- 2022
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Ingår i: Applied and Environmental Microbiology. - : American Society for Microbiology. - 0099-2240 .- 1098-5336. ; 88:17
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Tidskriftsartikel (refereegranskat)abstract
- Mushroom-forming fungi (Agaricomycetes) employ enzymatic and nonenzymatic cellulose degradation mechanisms, the latter presumably relying on Fenton-generated radicals. The effects of the two mechanisms on the cellulose microfibrils structure remain poorly understood. We examined cellulose degradation caused by litter decomposers and wood decomposers, including brown-rot and white-rot fungi and one fungus with uncertain wood decay type, by combining small- and wide-angle X-ray scattering. We also examined the effects of commercial enzymes and Fenton-generated radicals on cellulose using the same method. We detected two main degradation or modification mechanisms. The first characterized the mechanism used by most fungi and resembled enzymatic cellulose degradation, causing simultaneous microfibril thinning and decreased crystalline cellulose. The second mechanism was detected in one brown-rot fungus and one litter decomposer and was characterized by patchy amorphogenesis of crystalline cellulose without substantial thinning of the fibers. This pattern did not resemble the effect of Fenton-generated radicals, suggesting a more complex mechanism is involved in the destruction of cellulose crystallinity by fungi. Furthermore, our results showed a mismatch between decay classifications and cellulose degradation patterns and that even within litter decomposers two degradation mechanisms were found, suggesting higher functional diversity under current ecological classifications of fungi.IMPORTANCE Cellulose degradation by fungi plays a fundamental role in terrestrial carbon cycling, but the mechanisms by which fungi cope with the crystallinity of cellulose are not fully understood. We used X-ray scattering to analyze how fungi, a commercial enzyme mix, and a Fenton reaction-generated radical alter the crystalline structure of cellulose. Our data revealed two mechanisms involved in crystalline cellulose degradation by fungi: one that results in the thinning of the cellulose fibers, resembling the enzymatic degradation of cellulose, and one that involves amorphogenesis of crystalline cellulose by yet-unknown pathways, resulting in a patchy-like degradation pattern. These results pave the way to a deeper understanding of cellulose degradation and the development of novel ways to utilize crystalline cellulose.
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| 7. |
- Gentile, Luigi, et al.
(författare)
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Ferrihydrite Nanoparticle Aggregation Induced by Dissolved Organic Matter
- 2018
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 122:38, s. 7730-7738
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Tidskriftsartikel (refereegranskat)abstract
- Ferrihydrite (Fh) nanoparticles are omnipresent in nature and often highly mobile because of their colloidal stability. Thus, Fh serves as a vector for iron as well as associated nutrients and contaminants. Here, we demonstrate, using small-angle X-ray scattering combined with cryo-transmission electron microscopy (cryo-TEM), that dissolved organic matter (DOM), extracted from a boreal forest soil, induce aggregation of Fh nanoparticles, of radius 3 nm, into fractal aggregates, having a fractal dimension D = 1.7. The DOM consists of both fractal-like colloids (>100 nm) and small molecular DOM, but the attractive Fh interparticle interaction was mediated by molecular DOM alone as shown by cryo-TEM. This highlights the importance of using soil extracts, including all size fractions, in studies of the colloidal behavior of DOM-mineral aggregates. The Fh nanoparticles also self-assemble during synthesis into aggregates with the same fractal dimension as the DOM-Fh aggregates. We propose that, in both the absence and presence of DOM, the aggregation is controlled by the Fh particle charge, and the process can be viewed as a linear polymerization into a self-avoiding random walk structure. The theoretical D value for this is 5/3, which is in close agreement with our Fh and DOM-Fh results.
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| 8. |
- Gentile, Luigi, et al.
(författare)
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Fungal decomposition and transformation of molecular and colloidal fractions of dissolved organic matter extracted from boreal forest soil
- 2024
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Ingår i: Soil Biology and Biochemistry. - 0038-0717. ; 195
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Tidskriftsartikel (refereegranskat)abstract
- Dissolved organic matter (DOM) plays a central role in soil carbon (C) dynamics, serving as both a substrate for microbial decomposers and a source of material stabilised via physical protection in molecular aggregates and associations with mineral particles. It is well established that soil microorganisms play a key role in mineral-associated C aggregates; however, their impacts on molecular aggregates is not clearly understood. Here, we examined the ability of an ectomycorrhizal fungus (Paxillus involutus) and a saprotrophic fungus (a strain of Gloeophyllum), two major functional groups of fungal decomposers in forest ecosystems, to decompose and process the molecular and colloidal size fractions of DOM. DOM was extracted by water from boreal forest soil, and the chemical composition and colloidal properties were followed over 11 days using nuclear magnetic resonance (NMR) spectroscopy and small-angle light and X-ray scattering techniques. Both fungi decompose various organic compounds into their molecular fractions in the presence of an energy source (i.e. glucose). The decomposition rate was significantly higher for Gloeophyllum than for P. involutus. When glucose was depleted, Gloeophyllum continued to decompose more complex carbohydrates, whereas the decomposition activity of P. involutus almost stopped. A large proportion of the C in the DOM was found in organic colloids. At later stages, Gloeophyllum but not P. involutus, significantly affected the colloids by promoting the formation of larger aggregates. Thus, saprotrophic fungi activity can significantly influence the colloidal properties of DOM. Our results support the view that ectomycorrhizal fungi decompose some of the soil organic C however, their overall capacity for DOM decomposition and transformation is significantly lower than that of saprotrophic fungi.
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| 9. |
- Krumina, Lelde, et al.
(författare)
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Ectomycorrhizal Fungal Transformation of Dissolved Organic Matter : Consequences for Reductive Iron Oxide Dissolution and Fenton-Based Oxidation of Mineral-Associated Organic Matter
- 2022
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Ingår i: Frontiers in Earth Science. - : Frontiers Media SA. - 2296-6463. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Recent studies have shown that dissolved organic matter (DOM) decomposed by ectomycorrhizal (ECM) fungi increases adsorptive properties of organic matter towards soil mineral surfaces. Concomitantly, ECM fungi secrete secondary metabolites with iron reducing capacity that are thought to participate in non-enzymatic Fenton-based decomposition of DOM. The aim of this study was to investigate if the iron reduction induced by the ECM fungus Paxillus involutus during organic matter decomposition was conserved in the decomposed DOM. We explored how the modified DOM reductively dissolved ferrihydrite and goethite nanoparticles and how these processes affected the reactions with H2O2 and the Fenton-based oxidation of mineral-associated organic matter. Culture filtrates were obtained from incubation of the ECM fungus on DOM from forest litter of a spruce forest. This modified DOM was separated by extraction into an ethyl acetate and a water fraction. These fractions were reacted with ferrihydrite and goethite in absence and presence of H2O2. Dissolved Fe2+ and HO• were measured and the reactions at the iron oxide-water interfaces were monitored in real-time with in-situ IR spectroscopy. Experiments showed that decomposition of DOM by P. involutus generated a modified DOM that displayed an increased and persistent reductive capacity. Most of the reductants were isolated in the aromatic- and carboxyl-dominated ethyl acetate fraction but some reduction capacity was also captured in the water fraction mainly containing carbohydrates. Reductive dissolution was more extensive for ferrihydrite than goethite, and this process generated significant oxidation of the DOM-ferrihydrite associations. Oxidation of adsorbed DOM was triggered by H2O2 via heterogenous and homogeneous Fenton reactions. These oxidation processes were favored by ferrihydrite because of a high reduction potential and a high efficiency of heterogeneous Fenton as compared to goethite. An optimal timing between the heterogeneous and homogeneous Fenton processes triggered extensive radical oxidation of the DOM-ferrihydrite associations generating a high concentration of surface-associated oxalate. Overall, the results show that organic matter associated with ferrihydrite may be more susceptible to radical oxidation than on goethite, and that fungal decomposition of DOM in general may have consequences for other important soil processes such as mineral dissolution, adsorption and initiation of radical reactions.
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| 10. |
- Krumina, Lelde, et al.
(författare)
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Oxidation of a Dimethoxyhydroquinone by Ferrihydrite and Goethite Nanoparticles : Iron Reduction versus Surface Catalysis
- 2017
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 51:16, s. 9053-9061
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Tidskriftsartikel (refereegranskat)abstract
- Hydroquinones are important mediators of electron transfer reactions in soils with a capability to reduce Fe(III) minerals and molecular oxygen, and thereby generating Fenton chemistry reagents. This study focused on 2,6-dimethoxy hydroquinone (2,6-DMHQ), an analogue to a common fungal metabolite, and its reaction with ferrihydrite and goethite under variable pH and oxygen concentrations. Combined wet-chemical and spectroscopic analyses showed that both minerals effectively oxidized 2,6-DMHQ in the presence of oxygen. Under anaerobic conditions the first-order oxidation rate constants decreased by one to several orders of magnitude depending on pH and mineral. Comparison between aerobic and anaerobic results showed that ferrihydrite promoted 2,6-DMHQ oxidation both via reductive dissolution and heterogeneous catalysis while goethite mainly caused catalytic oxidation. These results were in agreement with changes in the reduction potential (EH) of the Fe(III) oxide/Fe(II)aq redox couple as a function of dissolved Fe(II) where EH of goethite was lower than ferrihydrite at any given Fe(II) concentration, which makes ferrihydrite more prone to reductive dissolution by the 2,6-DMBQ/2,6-DMHQ redox couple. This study showed that reactions between hydroquinones and iron oxides could produce favorable conditions for formation of reactive oxygen species, which are required for nonenzymatic Fenton-based decomposition of soil organic matter.
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