Dissolved organic matter (DOM) is a major carbon pool and considered the most bioavailable and most mobile fraction of organic matter. DOM is generally defined as the organic matter passing a filter pore size of 0.2 or 0.45 µm, and this size cut off means that DOM not only contains dissolved molecules but also colloidal objects and aggregates up to a few hundred nanometres. The properties of this colloidal DOM fraction, such as for example size, shape, and surface charge, will affect its actual bioavailability and mobility in the environment. Although previously not well studied, there has recently been a growing interest in this colloidal fraction of DOM. We have studied DOM extracted by water from a boreal spruce forest soil, filtered through a 0.2 µm pore size. By using a combination of spectroscopy techniques, such as NMR, and light (SLS, DLS), X-ray (SAXS) and neutron (SANS) scattering techniques, we can access chemical and physical information on both the molecular and colloidal fractions of DOM. Our results show that the colloidal DOM has a homogenous chemical composition, and that carbohydrates is the dominating chemical component in both the colloidal and molecular DOM. The colloids have a mass fractal structure which does not change upon dilution and they are electrostatically stabilised against aggregation. In a lab scale study, we investigated the bacterial decomposition of this DOM during a two-month incubation. The molecular fraction of DOM was quickly decomposed. However, no change was observed for the colloidal DOM, constituting ca. 50% of the carbon, indicating that it persisted bacterial decomposition. Our results suggest that colloidal properties could be an important but hitherto overlooked aspect to the central question of what dictates organic matter reactivity and persistency in different environments and across different time scales. Our current work extends from soil solution to aquatic ecosystems, to assess the ubiquity of the colloidal fraction of DOM.

We have investigated the bacterial decomposition of dissolved organic matter (DOM) extracted from the organic layer of a boreal forest soil and filtered at a pore size of 0.2 µm. This DOM source has previously been extensively characterized and contains approximately equal amounts by carbon of a colloidal fraction, mainly composed of carbohydrates, and a fraction of molecularly dissolved DOM. Here, extracts were inoculated with soil bacteria and the decomposition of DOM was followed over a period of 2 months, during which it was analyzed with scattering methods and 1H NMR, and by measuring the concentration of total organic carbon. A comparison was also made with dialyzed extract. Results showed that while the bacteria fully decomposed the molecular fraction within approximately two weeks, the colloidal fraction was stable with no visible decomposition within the 2 months. The results indicate the importance of distinguishing small molecules from colloidal aggregates in decomposition studies, and demonstrate the usefulness of combining scattering methods with 1H NMR for this purpose.

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 degrees C-100 degrees 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 degrees C-100 degrees C. Moreover, the temperature variation indicated that the fractal clusters partly dissolved into colloidal coils at elevated temperatures. Mechanical agitation at 4 degrees 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.

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.

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.

Components of dissolved organic matter (DOM) span from sub-nm molecules to colloidal aggregates of several hundred nm. The colloidal fraction is important for the transport of organic matter and associated elements in the environment, and for the stability of DOM constituents with respect to microbial decomposition. This study focuses on the colloidal properties of DOM extracted from spruce forest soils of a chronosequence. The DOM samples were obtained by common water extraction procedures at 21 and 100°C, respectively. We applied an experimental approach combining chemical analysis with light and X-ray scattering techniques that informed on the colloidal size, charge, and structure of DOM. Results showed that two main types of colloids were present: semi-flexible cylinders and fractal aggregates. The cylinders consisted of carbohydrates, presumably hemicelluloses, while the aggregates were a composite material containing a large fraction of carbohydrates together with aliphatics and clay particles. These fractal aggregates dominated the cold-water extracts whereas the strong increase in total organic carbon by hot-water extraction caused a concomitantly strong increase of semi-flexible cylinders, which became the predominant species. Comparison between the chronosequence soils showed that with increasing forest age, the amount of carbon extracted per gram of soil declined and the concentration of the semi-flexible cylinders decreased. Thus, the distribution between the fractal aggregates and cylinders in the forest soil DOM samples depends on the composition of the soil organic matter and the leaching temperature. Changes in this distribution may have important implications for the reactivity and stability of DOM colloids.

Cotton production is reaching a global limit, leading to a growing demand for bio-based textile fibers produced by other means. Textile fibers based on regenerated cellulose from wood holds great potential, but in order to produce fibers, the components need to be dissolved in suitable solvents. Furthermore, the dissolution process of cellulose is not yet fully understood. In this study, we investigated the dissolution state of microcrystalline cellulose in aqueous NaOH by using primarily scattering methods. Contrary to previous findings, this study indicated that cellulose concentrations of up to 2 wt % are completely molecularly dissolved in 8 wt % NaOH. Scattering data furthermore revealed the presence of semi-flexible cylinders with stiff segments. In order to improve the dissolution capability of NaOH, the effects of different additives have been of interest. In this study, scattering data indicated that the addition of ZnO decreased the formation of aggregates, while the addition of PEG did not improve the dissolution properties significantly, although preliminary NMR data did suggest a weak attraction between PEG and cellulose. Overall, this study sheds further light on the dissolution of cellulose in NaOH and highlights the use of scattering methods to assess solvent quality.

Dissolved organic matter (DOM) is ubiquitous in terrestrial and aquatic ecosystems where it serves several important functions. It plays a central role in the landscape carbon balance, connects the terrestrial and aquatic environments, and acts as a vector for both nutrients and contaminants. Herein DOM is defined as dissolved molecules and suspended colloidal objects with a size below 0.2 μm. Despite the high interest of DOM, the important connection between the chemical composition of DOM and its colloidal structure are poorly understood. An active discussion in this field of research is how different extraction procedures affect the properties of DOM. Historically, sodium hydroxide extraction has been widely applied but today water extraction, more resembling the natural process, is commonly used. Even when using water as the solvent, the protocol for DOM extraction can differ greatly resulting in the study of different material. We have systematically investigated the effects of extraction temperature and time on the chemical and colloidal properties of DOM extracted with water from a boreal forest soil. Chemical composition was determined using elemental analysis, pH, z-potential and 1H NMR while the colloidal structure was probed using a combination of dynamic and static light scattering (DLS, SLS) and small angle x-ray scattering (SAXS). Our results show that chemically the DOM is dominated by carbohydrates irrespective of extraction time and temperature. Concentration and colloidal structure on the other hand are affected by these parameters. At high temperatures the concentration of all identified components increases, with the most notable difference in the carbohydrates. Also, with increasing extraction temperature the colloidal structure transforms from dense clusters to something resembling flexible polymer chains. Contrast match experiments of DOM using small angle neutron scattering (SANS) have also been performed in preparation for studies on DOM-mineral interactions. The results show that the match point of DOM agrees with that of carbohydrates further confirming our results of the chemical composition. We believe our broad combination of complementary techniques is necessary to advance the understanding of DOM, in particular the correlation between chemical composition and colloidal properties. In the long-term it can help to reveal the importance of DOM size distribution and aggregation of DOM components for biogeochemically important processes in soil.