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  • 1
    In: Environmental Chemistry, CSIRO Publishing, Vol. 11, No. 6 ( 2014), p. 709-
    Kurzfassung: Environmental context The supramolecular structure and resulting physicochemical properties of soil organic matter (SOM) significantly control storage and buffer functions of soils, e.g. for nutrients, organic molecules and water. Multivalent cations, able to form complexes, are suggested to form inter- and intramolecular cross-links in SOM. At present, specific effects of the valence and type of cation on SOM properties are incompletely understood. We investigated changes in SOM interfacial properties, its ability to release mobile colloids in aqueous solutions and its sorption affinity towards organic chemicals in dependence on cation–SOM interactions, temperature and aging time. Abstract The present study aims to improve our understanding on the effect of multivalent cations, temperature treatment and isothermal aging time on interfacial soil organic matter (SOM) properties as major factors that modify its supramolecular structures. A sandy topsoil (LW) and a peat soil (SP) were enriched with Na, Ca or Al, or desalinated in a batch experiment, treated at 25, 40, 60 and 105°C and aged at constant temperature and humidity (20°C, 31% relative humidity). After aging for different periods, contact angles (CAs), sorption properties towards xenobiotics and properties of water dispersible colloids were determined. With increasing valence of the dominant cations fewer and larger colloids were observed, probably attributable to cation cross-links or enhanced aggregation caused by reduced surface charge. Al-enrichment of LW resulted in more abundant or more accessible sorption sites for hydrophobic xenobiotics. But in contrast to expectations, hydrophilic sorption as well as wettability was not significantly affected by the type of adsorbed cation. Increasing the temperature had a major effect on surface properties resulting in rising surface hydrophobisation with increasing solid–water CAs, decreasing surface O/C ratio and decreasing sorption of hydrophilic substances; whereas systematic temperature effects on water dispersible colloids and on hydrophobic sorption were not detected. Aging was found to increase the initial CA of the 25°C treatment and to increase the sorption of phenanthrene to LW for all treatment temperatures. We conclude that aging of SOM is a process that changes surface properties and approaches a new equilibrium state after a disturbance. The aging process may be significantly accelerated for samples treated at elevated temperatures.
    Materialart: Online-Ressource
    ISSN: 1448-2517
    Sprache: Englisch
    Verlag: CSIRO Publishing
    Publikationsdatum: 2014
    ZDB Id: 2150372-2
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Online-Ressource
    Online-Ressource
    CSIRO Publishing ; 2019
    In:  Environmental Chemistry Vol. 16, No. 7 ( 2019), p. 541-
    In: Environmental Chemistry, CSIRO Publishing, Vol. 16, No. 7 ( 2019), p. 541-
    Kurzfassung: Environmental contextImmobilisation of organic chemicals in soil organic matter can strongly influence their availability in the environment. We show that the presence of water clusters, called water molecule bridges, hampers the release of organic molecules from soil organic matter. Moreover, water molecule bridges are sensitive to changes in environmental conditions (e.g., temperature or moisture) which affect the release of organic molecules into the environment. AbstractWater molecule bridges (WaMB) can stabilise the supramolecular structure of soil organic matter (SOM) by connecting individual SOM molecular units. WaMB are hypothesised to act as a desorption barrier and thus to physically immobilise molecules in SOM. To test this hypothesis, we prepared two sets of soil samples – aged samples with WaMB developed, and vacuumed samples, in which WaMB were disrupted . The samples were spiked with phenol and then stored under controlled humidity. The degree of phenol immobilisation in SOM was assessed by desorption kinetics of phenol into a gas phase. This was compared with the thermal stability (T*) of WaMB obtained by modulated differential scanning calorimetry (MDSC) and the results were related to computer modelling, which provided the stability and solvation energies of phenol-WaMB-SOM models. The desorption kinetics of phenol was best described by a first-order model with two time constants ranging between 1 and 10h. In aged samples, the time constants correlated with T*, which showed that the desorption time increased with increasing WaMB stability. Molecular modelling proposed that phenol molecules are preferentially locked in nanovoids with polar OH groups pointed to WaMB in the most stable configurations. Both findings support the hypothesis that WaMB can act as a desorption barrier for phenol.
    Materialart: Online-Ressource
    ISSN: 1448-2517
    Sprache: Englisch
    Verlag: CSIRO Publishing
    Publikationsdatum: 2019
    ZDB Id: 2150372-2
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    In: Environmental Chemistry, CSIRO Publishing, Vol. 17, No. 5 ( 2020), p. 400-
    Kurzfassung: Environmental contextThe fate of silver nanoparticles (AgNPs) in aqueous systems could be influenced by the hydrophobicity of natural organic matter. We observed that the aggregation and dissolution of oppositely charged AgNPs were controlled by the selectivity and dynamics of sorption processes involving the nanoparticle surface and hydrophobic groups on natural organic matter. These findings will be helpful to understand the fate and effects of coated AgNPs in natural systems. AbstractThe fate of silver nanoparticles (AgNPs) released into aquatic environments is significantly affected by natural organic matter (NOM). However, current studies are still insufficient to understand interactions between NOM and AgNPs because they do not explicitly consider the heterogeneity of NOM. We investigated how NOM components with different properties (hydrophobicity, molecular weight, aromaticity, and polarity of functional groups) interact with AgNPs coated with citrate (Cit) and branched polyethylenimine (BPEI) and influence their colloidal stability and dissolution. Pony Lake fulvic acid (PLFA) selected as a model NOM was fractionated into hydrophobic (HPO) and transphilic (TPI) fractions. Sorption of PLFA molecules with a high content of polar functional groups bound to the aromatic rings onto nanoparticles was more favourable in the case of the TPI fraction, which most likely resulted in higher aggregation for both AgNPs and stronger protection of BPEI-AgNPs against dissolution compared with the HPO fraction. Additionally, in contrast to the Cit-AgNPs, resorption of Ag+ ions released from BPEI-AgNPs and/or sorption of Ag+-PLFA complexes to the nanoparticles was most likely a dynamic process, as suggested by the time-dependent changes in the molecular weight of the PLFA fractions sorbed to the BPEI-AgNP surface. These observations suggest that the accessibility of the AgNP surface for the hydrophobicity-based fractions of NOM as well as their colloidal stability and dissolution are controlled by the type and charge of coating materials and by the molecular weight, aromaticity, and content of polar functional groups of NOM.
    Materialart: Online-Ressource
    ISSN: 1448-2517
    Sprache: Englisch
    Verlag: CSIRO Publishing
    Publikationsdatum: 2020
    ZDB Id: 2150372-2
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 4
    Online-Ressource
    Online-Ressource
    CSIRO Publishing ; 2016
    In:  Environmental Chemistry Vol. 13, No. 1 ( 2016), p. 50-
    In: Environmental Chemistry, CSIRO Publishing, Vol. 13, No. 1 ( 2016), p. 50-
    Kurzfassung: Environmental context The mobility of soil organic matter and water molecules has a strong influence on the availability of fertilisers as well as on the fate of pollutants in soil. Magnetic resonance techniques identified two regimes of mobility change on the molecular level occurring on a timescale of 1 year after initially heating the sample. The results can help to understand the effect of soil type and water content for agricultural use and soil protection. Abstract 1H wide-line solid-state NMR methods have been applied to monitor long-term mobility changes in the supramolecular network of soil organic matter and water induced by short thermal treatment. NMR line widths are a direct measure of the mobility of water molecules and organic matter components. For the first time, we obtained an insight into the long-term physical mechanisms in terms of molecular mobility governing soil organic matter–water interactions. All time series reveal a systematic, attenuated proton demobilisation on time scales with a maximum of 1 year that depends on water content and type of soil. Results are discussed in the context of water molecule bridges and are compared with the results of structural transition temperatures obtained from differential scanning calorimetry measurements. The analysis is based on a porous system with random field characteristics. Two major features, a logarithmic time dependence in the first hours and a linear time dependence at longer times after the heating event, are observed in all investigated samples. In peat samples, a temporary increase of mobility was observed, the point in time depending on water content. The soil organic matter physicochemical matrix aging mechanism could also be relevant for the aging of organic chemicals in soil samples, suggesting a long-term reduction in molecular mobility.
    Materialart: Online-Ressource
    ISSN: 1448-2517
    Sprache: Englisch
    Verlag: CSIRO Publishing
    Publikationsdatum: 2016
    ZDB Id: 2150372-2
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
    BibTip Andere fanden auch interessant ...
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