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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: Journal of Plant Nutrition and Soil Science, April 2017, Vol.180(2), pp.220-230
    Description: Standard procedures to assess P availability in soils are based on batch experiments with various extractants. However, in most soils P nutrition is less limited by bulk stocks but by strong adsorption and transport limitation. The basic principle of root‐phosphate uptake is to strip phosphate locally from the solid phase by forming a radial depletion zone in the soil solution, optionally enhanced by release of mobilizing substances. Microdialysis (MD), a well‐established method in pharmacokinetics, is capable to mimic important characteristics of P root uptake. The sampling is by diffusional exchange through a semipermeable membrane covering the probes with their sub‐mm tubular structure. Additionally, the direct environment of the probe can be chemically modified by adding, ., carboxylates to the perfusate. This study is the first approach to test the applicability of MD in assessing plant available phosphate in soils and to develop a framework for its appropriate use.We used MD in stirred solutions to quantify the effect of pumping rate, concomitant ions, and pH value on phosphate recovery. Furthermore, we measured phosphate yield of top‐soil material from a beech forest, a non‐fertilized grassland, and from a fertilized corn field. Three perfusates have been used based on a 1 mM KNO solution: pure (1), with 0.1 mM citric acid (2), and with 1 mM citric acid (3). Additionally, a radial diffusion model has been parametrized for the stirred solutions and the beech forest soil.Results from the tests in stirred solutions were in good agreement with reported observations obtained for other ionic species. This shows the principal suitability of the experimental setup for phosphate tests. We observed a significant dependency of phosphate uptake into the MD probes on dialysate pumping rate and on ionic strength of the outside solution. In the soils, we observed uptake rates of the probes between 1.5 × 10 and 6.7 × 10 mol s cm in case of no citrate addition. Surprisingly, median uptake rates were mostly independent of the bulk soil stocks, but the P‐fertilized soil revealed a strong tailing towards higher values. This indicates the occurrence of hot P spots in soils. Citrate addition increased P yields only in the higher concentration but not in the forest soil. The order of magnitude of MD uptake rates from the soil samples matched root‐length related uptake rates from other studies. The micro‐radial citrate release in MD reflects the processes controlling phosphate mobilization in the rhizosphere better than measurements based on “flooding” of soil samples with citric acid in batch experiments. Important challenges in MD with phosphate are small volumes of dialysate with extremely low concentrations and a high variability of results due to soil heterogeneity and between‐probe variability. We conclude that MD is a promising tool to complement existing P‐analytical procedures, especially when spatial aspects or the release of mobilizing substances are in focus.
    Keywords: Plant Availability ; Diffusion Limitation ; Spatial Heterogeneity ; Carboxylates
    ISSN: 1436-8730
    E-ISSN: 1522-2624
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  • 3
    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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  • 4
    Language: English
    In: Soil Science Society of America Journal, March-April, 2006, Vol.70(2), p.541(9)
    Description: Biogenetic polysugars may affect the sorption characteristics of soil mineral particles in the rhizosphere. We hypothesized that polygalacturonate [PGA, ([[C.sub.6][H.sub.7][O.sub.6]).sub.n.sup.-]] coatings on goethite reduce the diffusion of phosphate into the pores of the adsorbent. Goethite was preloaded with PGA (0-10 mg C [g.sup.-1]). The samples were characterized by [N.sub.2] and C[O.sub.2] adsorption, electrophoretic mobility measurements, and scanning electron microscopy/energy dispersive X-ray analysis (SEM-EDX). The phosphate sorption kinetics was studied with batch experiments over 2 wk at pH 5 and an initial phosphate concentration of 250 [micro]M. Pore volume and specific surface area of the goethite samples declined after PGA addition. The PGA coatings reduced the [zeta]-potential of goethite from 42.3 to -39.6 mV at the highest C loading. With increasing PGA-C content and decreasing [zeta]-potential the amount of phosphate sorbed after 2 wk decreased linearly (P 〈 0.001). Sorption of phosphate to pure and PGA-coated goethite showed an initial fast sorption followed by a slow sorption reaction. At the smallest C loading (5.5 mg C [g.sup.-1]) the portion of phosphate retained by the slow reaction was smaller than for the treatment without any PGA, while at higher C loadings the fraction of slowly immobilized phosphate increased. Our results suggest that at low C-loadings PGA impaired the intraparticle diffusion of phosphate. In contrast, the slow step-by-step desorption of PGA (〈52% within 2 wk) or the diffusion of phosphate through PGA coatings or both are rate limiting for the slow phosphate reaction at C loadings 〉 5.5 mg C [g.sup.-1].
    Keywords: Soil Phosphorus -- Research ; Soil Chemistry -- Research ; X-ray Analysis
    ISSN: 0361-5995
    E-ISSN: 14350661
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  • 5
    Language: English
    In: Soil Science Society of America Journal, Sept-Oct, 2006, Vol.70(5), p.1547(9)
    Description: Organic coatings on Fe oxides can decrease the accessibility of intraparticle pores for oxyanions like phosphate. We hypothesized that the slow sorption of phosphate to goethite coated with polygalacturonate (PGA) is controlled by the accessibility of external goethite surfaces to phosphate rather than by diffusion of phosphate into micropores ([empty set] 〈 2 nm). We studied the phosphate sorption kinetics of pure and PGA-coated goethites that differed in their microporosity ([N.sub.2] at 77 K, 46 vs. 31 [mm.sup.3] [g.sup.-1]). Because drying may affect the structure or surface coverage of PGA, we also tested the effect of freeze-drying on the slow phosphate sorption. The samples were examined by gas adsorption ([N.sub.2], C[O.sub.2]) and electrophoretic mobility measurements. Phosphate sorption and PGA-C desorption were studied in batch experiments for 3 wk at pH 5. In PGA-coated samples, the slow phosphate sorption was independent of micropore volume. Phosphate displaced on average 57% of PGA-C within 3 wk. Similar to phosphate sorption, the PGA-C desorption comprised a rapid initial desorption, which was followed by a slow C desorption. Sorption competition between phosphate and presorbed PGA depended on the 〈10-nm porosity and the C loading of the adsorbent. The efficacy of phosphate to desorb PGA generally increased after freeze-drying. We conclude for PGA-coated goethites that (i) freeze-drying biased the slow phosphate sorption by changing the structure/surface coverage of PGA, and (ii) within the time frame studied, micropores did not limit the rate of the slow phosphate sorption. Rather, the slow, gradual desorption of PGA and/or the diffusion of phosphate through PGA coatings controlled the slow phosphate sorption to PGA-coated goethite.
    Keywords: Mineralogical Research -- Analysis ; Phosphates -- Research ; Sorption -- Research
    ISSN: 0361-5995
    E-ISSN: 14350661
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  • 6
    Language: English
    In: Journal of Plant Nutrition and Soil Science, December 2000, Vol.163(6), pp.571-575
    Description: It is widely accepted that the fixation of oxyanions is due to diffusion of the ions into the pores and interdomains of iron oxides. Most studies have used batch techniques, which do not allow to clearly differentiate chemisorption from mass transport phenomena. Thus, it is not yet clear, whether strengthening of chemical Mo bonding occurs along with residence time, in addition to diffusion processes. In this study we used pressure jump relaxation (p‐jump), a very fast kinetic technique, to (1) elucidate the Mo/goethite interaction and to (2) analyze the effects of aging the Mo/goethite complex on Mo chemisorption. A synthetic goethite was incubated with Mo solution (1 mM Mo) for 12, 24, and 72 hours at pH 4. At the end of the incubations p‐jump experiments were performed on the suspensions at temperatures ranging from 283 to 303 K. Relaxation kinetics were modelled using a combination of two first order terms. In addition, the amount of Mo sorbed to the goethite after different incubation times was determined by graphite furnace atomic absorption spectroscopy. The MoO/goethite systems revealed a fast relaxation time (= reciprocal of rate constant, about 4 ms), that decreased with increasing temperature and a slow one (about 60 ms) that did not depend on temperature. Activation energy of the fast process was 76 kJ mol. We did not observe any effects of incubation time on the fast process. However, the amount of Mo sorbed to the iron oxide increased with increasing incubation time. We conclude that the fast relaxation represents Mo chemisorption to the goethite. Slow relaxation seems to be due to Mo transport within the suspension. The pressure jump results indicate, that the dominant surface species of Mo sorbed to goethite do not change along with residence time. Mechanismen der Molybdänsorption an Eisenoxide Die Fixierung von Oxyanionen durch Eisenoxide wird im allgemeinen auf die Diffusion von Ionen in die Interdomänenräume von Eisenoxiden zurückgeführt. Weil es mit Hilfe herkömmlicher Batch‐Experimente nicht möglich ist, zwischen Chemisorptions‐ und Massentransport‐Prozessen zu unterscheiden, ist bislang unklar, ob zusätzlich Veränderungen der chemischen Bindung bei längeren Sorptionszeiten für die Festlegung von Oxyanionen verantwortlich sind. Ziel dieser Untersuchung ist es, mittels Druck‐Sprung (p‐jump), einer sehr schnellen kinetischen Methode, die Mechanismen der Mo‐Fixierung an Eisenoxide aufzuklären. Ein synthetischer Goethit wurde bei pH 4 mit molybdathaltiger Lösung (1 mM Mo) 12, 24 und 72 h inkubiert. Nach dieser Vorinkubation wurden p‐jump‐Versuche mit den verschieden lange gealterten Suspensionen bei Temperaturen zwischen 283 und 303 K durchgeführt. Die Relaxationskinetik wurde dabei durch die Kombination zweier Terme erster Ordnung beschrieben. Zusätzlich wurde die Menge an sorbiertem Mo nach den unterschiedlichen Inkubationszeiten bestimmt. Für das Mo/Goethit‐System ergaben sich eine schnelle (ca. 4 ms) und eine langsame (ca. 60 ms) Relaxationszeit (= Kehr‐wert der Geschwindigkeitskonstante). Während die schnelle Relaxation sehr stark temperaturabhängig war, zeigte die langsame Relaxation keinen Temperatureinfluss. Die Aktivierungsenergie für den schnellen Prozess betrug 76 kJ mol. Obwohl die sorbierte Mo‐Menge mit der Inkubationszeit deutlich zunahm, war die Relaxationszeit unabhängig von der Dauer der Vorinkubation. Die Ergebnisse deuten darauf hin, dass die schnelle Relaxation durch die Chemisorption von Mo an den Goethit hervorgerufen wird. Die langsame Relaxation ist vermutlich auf Durchmischungsphänomene innerhalb der Suspensionen zurückzuführen. Die Untersuchung deutet darauf hin, dass Mo‐Fixierung allein auf Transportprozesse, nicht aber auf die Veränderung der chemischen Bindung zurückzuführen ist.
    Keywords: Molybdenum‐Fixation ; Sorption Mechanism ; Kinetic Approach ; P‐Jump ; Diffusion
    ISSN: 1436-8730
    E-ISSN: 1522-2624
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