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Berlin Brandenburg

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  • 1
    Language: English
    In: Geochimica et Cosmochimica Acta, 2006, Vol.70(3), pp.595-607
    Description: Anions of polycarboxylic low-molecular-weight organic acids (LMWOA) compete with phosphate for sorption sites of hydrous Fe and Al oxides. To test whether the sorption of LMWOA anions decreases the accessibility of micropores (〈2 nm) of goethite (α-FeOOH) for phosphate, we studied the kinetics of citrate-induced changes in microporosity and the phosphate sorption kinetics of synthetic goethite in the presence and absence of citrate in batch systems for 3 weeks (500 μM of each ion, pH 5). We also used C-coated goethite obtained after sorption of dissolved organic matter in order to simulate organic coatings in the soil. We analyzed our samples with N adsorption and electrophoretic mobility measurements. Citrate clogged the micropores of both adsorbents by up to 13% within 1 h of contact. The micropore volume decreased with increasing concentration and residence time of citrate. In the absence of citrate, phosphate diffused into micropores of the pure and C-coated goethite. The C coating (5.6 μmol C m ) did not impair the intraparticle diffusion of phosphate. In the presence of citrate, the diffusion of phosphate into the micropores of both adsorbents was strongly impaired. We attribute this to the micropore clogging and the ligand-induced dissolution of goethite by citrate. While the diffusion limitation of phosphate by citrate was stronger when citrate was added before phosphate to pure goethite, the order of addition of both ions to C-coated goethite had only a minor effect on the intraparticle diffusion of phosphate. Micropore clogging and dissolution of microporous hydrous Fe and Al oxides may be regarded as potential strategies of plants to cope with phosphate deficiency in addition to ligand-exchange.
    Keywords: Geology
    ISSN: 0016-7037
    E-ISSN: 1872-9533
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  • 2
    Language: English
    In: Soil Science Society of America Journal, Sept-Oct, 2006, Vol.70(5), p.1731(10)
    Description: Uronates are important constituents of maize mucilage and polyuronates are used as a simplified model of the soil--root interface. We tested whether galacturonate (GA) and polygalacturonate (PGA) impair the diffusion of phosphate (P[O.sub.4]) into and out of pores of a synthetic goethite (147 [m.sup.2] [g.sup.-1]) and whether the effect of maize mucigel (MU) is comparable to PGA. We measured the P[O.sub.4] desorption kinetics of goethites in batch experiments over 2 wk at pH 5. One part of the goethite was equilibrated with organic substances before P[O.sub.4] addition, another part after addition of P[O.sub.4]. Before the desorption experiments, the porosity of our samples was analyzed by [N.sub.2] gas adsorption. In each treatment a rapid initial desorption was followed by a slow desorption reaction, which is assigned to the diffusion of P[O.sub.4] out of mineral pores. No consistent relation between the micro- and mesoporosity and the rate of the slow P[O.sub.4] desorption was observed. Compared with the C-free control, only PGA and MU affected the fraction of P[O.sub.4] mobilized by the fast and slow desorption reaction: when PGA was sorbed to goethite before P[O.sub.4], twice as much P[O.sub.4] was mobilized via the fast reaction than in the treatment where P[O.sub.4] was sorbed before PGA, suggesting a decreased accessibility of goethite pores to P[O.sub.4]. Mucigel, however, showed reversed effects, which is ascribed to its differing chemical composition. In conclusion, PGA seems inappropriate as a model substance for maize MU collected from non-axenic sand cultures. Under the experimental conditions chosen, the efficacy of all organic substances to increase P[O.sub.4] solution concentrations by pore clogging and sorption competition is small.
    Keywords: Phosphates -- Research ; Sorption -- Research
    ISSN: 0361-5995
    E-ISSN: 14350661
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  • 3
    Language: English
    In: Soil Science Society of America Journal, Nov-Dec, 2004, Vol.68(6), p.1853(10)
    Description: Recent [N.sub.2] adsorption studies have suggested a 'pore clogging' effect on mineral soil phases caused by organic matter coatings. For methodological reasons, this pore clogging effect has been studied only after drying. Our hypothesis was that pore clogging is affected by drying of organic coatings. In our study, we used AlOOH, which has been equilibrated with dissolved organic matter (DOM) and polygalacturonic acid [[PGA; [([C.sub.6][H.sub.8][O.sub.6]).sup.n]]. To test our hypothesis, we determined the porosity of moist and freeze-dried AlOOH samples. Freeze-dried samples were analyzed by [N.sub.2] adsorption, moist samples by [sup.1]H-nuclear magnetic resonance (NMR). In addition, the samples were characterized by environmental scanning electron microscopy--energy dispersive x-ray spectroscopy (ESEM-EDX). Both, DOM and PGA significantly reduced specific surface area (SS[A.sub.BET]) of AlOOH by 34 [m.sup.2][g.sup.-1](15%) and 77 [m.sup.2] [g.sup.-1] (36%). The reduction in SS[A.sub.BET] normalized to the amount of C sorbed was 1.0 [m.sup.2] [mg.sup.-1] DOM-C and 5.9 [m.sup.2] [mg.sup.-1] PGA-C. Dissolved OM reduced the pore volume of micro- and small mesopores 〈3 nm whereas PGA also reduced the volume of larger pores. The [sup.1]H-NMR results of moist samples showed that PGA sorption reduced the amount of water in pores 〈4 nm. In addition, the pore size maximum of AlOOH increased by 150%. Polygalacturonic acid coatings created new interparticle pores of about 10- to 70-nm size that are not stable upon freeze-drying. Porosity changes upon DOM-treatment were not commensurable by [sup.1]H-NMR. Our results indicate that clogging of micro- and small mesopores is not an artifact of freeze-drying. Polygalacturonic acid seems not only to cover the mouth of AlOOH-nanometer pores but also to fill them.
    Keywords: Soil Mineralogy -- Research
    ISSN: 0361-5995
    E-ISSN: 14350661
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