| 11. |
- Karltun, E., et al.
(author)
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Surface reactivity of poorly-ordered minerals in podzol B horizons
- 2000
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In: Geoderma. - 0016-7061 .- 1872-6259. ; 94:04-feb, s. 265-288
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Journal article (peer-reviewed)abstract
- The surface reactivity of mineral soil horizons from three podzolised forest soils in Scandinavia was examined. The amount of accumulated C was low, between 1.8 and 2.3% in the top of the B horizons. Selective extractions in combination with infrared (IR) spectroscopy and transmission electron microscopy (TEM) indicated a predominance of poorly-ordered imogolite-type materials (ITM) in the oxalate extractable fraction in an examined B horizons. The presence of well-ordered imogolite was only indicated in the Nyanget B3 horizon. A large proportion of free Fe was removed by ammonium oxalate. Comparisons of Mossbauer spectra (both at room temperature and at 4.2 K) before and after treatment with ammonium oxalate showed that the oxalate treatment resulted in a removal of a (super)paramagnetic Fe3+ phase? probably ferrihydrite. A comparison of the Mossbauer Fe3+ parameters at room temperature and 4.2 K indicated a close intergrowth of a ferrihydrite-like oxide with a magnetically neutral matrix, e.g., allophane. The specific surface area (SSA) was determined by N-2 adsorption before and after treatment of the samples with acid ammonium oxalate. The loss of SSA after oxalate treatment was considerable in the B horizon where only between 3.8 to 13.38 of the original SSA remained after treatment. The point of zero charge salt effect (PZSE) increased with depth in the B horizon from between 4.4 and 5.1 in the upper horizons to between 5.7 and 7.7 in the lower part of the B horizon. The increased PZSE with depth paralleled a decrease in the ratio of pyrophosphate soluble C to oxalate soluble Fe + Al. The affinity for SO42-. a goad indicator of the presence of active surface hydroxyls, was measured by comparing the H+ buffering capacity of a sample titrated in 2.5 mM Na2SO4 with a sample titrated in 5 mh I NaNO3,. The buffering capacity of the soil in the Na2SO4, electrolyte was well correlated with the amount of oxalate minus pyrophosphate soluble Fe + Al (r(2) = 0.88). The sulphate exchange capacity was considerably higher than CEC, especially in lower parts of the B horizon. The calculated surface area of the oxalate soluble material (OSM) ranged between 74 and 289 m(2) g(-1) and the calculated surface site density of the same material ranged between 0.6 to 3.3 site nm(-2). It was concluded that the surface reactivity in the B horizons is dominated by the poorly-ordered variable-charge oxides resulting in a low capacity to retain cations but a high capacity for adsorption of weak acid anions like SO42- and organic acids.
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| 12. |
- Lundström, Ulla, et al.
(author)
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Advances in understanding the podzolization process resulting from a multidisciplinary study of three coniferous forest soils in the Nordic Countries
- 2000
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In: Geoderma. - 0016-7061 .- 1872-6259. ; 94:04-feb, s. 335-353
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Journal article (peer-reviewed)abstract
- Geochemical, mineralogical, micromorphological, microbiological, hydrochemical and hpdrological joint investigations were performed at two coniferous podzolic sites in the north of Sweden and at one in the south of Finland. Mycorrhizal fungi were found to create numerous pens (3-10-mu m diameter) in many weatherable mineral grains in the eluvial (E) horizon. During the growing season, identified low molecular weight (LMW) organic acids such as citric, shikimic, oxalic and fumaric acids comprised 0.5-5% of the DOC and 0.5-15% of the total acidity in soil solutions. Between 20% and 40% of the dissolved Al was bound to the identified LMW organic acids. Mineral dissolution via complexing LMW acids, probably exuded in part by the mycorrhiza hyphae, is likely to be a major weathering process in podzols. We found no evidence for a decreasing C/metal ratio of the migrating organo-metal complexes that could explain the precipitation of secondary Fe and AL in the illuvial (B) horizon. Instead, microbial degradation of organic ligands resulting in the release of ionic,Al and Fe to the soil solution may he an important process facilitating the formation of solid Al-SI-OH and Fe-OH phases in the podzol B horizon. However, within the B horizon transport as proto-imogilite (PI) sols might be possible. In the B horizon, the extractable,Al and Fe was predominantly inorganic. The large specific surface area (SSA) removable by oxalate extraction, the high point of zero charge salt effect (PZSE), the low cation exchange capacity (CEC) and the high sulphate exchange capacity (SEC), painted to the presence of short-range ordered variable charge phases. Imogolite type material (ITM) was indeed identified in all B horizons by IR spectroscopy and crystalline imogolite was found in the deep B horizon of one profile. Mossbauer spectroscopy indicated that Fe in the form of ferrihydrite was formed by intergrowth with an Al-Si-OH phase. The high amounts of Fe and Al transported from the O to the E horizon indicate that there could be an upward transport of these elements before they are leached to the B horizon. We hypothesize that the LMW Al complexes an transported by hyphae to the mor (O) layer, partly released and subsequently complexed by high molecular weight (HMW) acids.
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| 13. |
- Sracek, O., et al.
(author)
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Behavior of arsenic and geochemical modeling of arsenic enrichment in aqueous environments
- 2004
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In: Applied Geochemistry. - : Elsevier BV. - 0883-2927 .- 1872-9134. ; 19:2, s. 169-180
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Journal article (peer-reviewed)abstract
- Arsenic is present in aqueous environments in +III and +V oxidation states. In oxidizing environments, the principle attenuation mechanism of As migration is its adsorption on Fe(III) oxide and hydroxides. The adsorption affinity is higher for As(V) under lower pH conditions and for As(III) under higher pH conditions. Ferric oxide and hydroxides can dissolve under low Eh and pH conditions releasing adsorbed As. Oxidation-reduction processes often involve high organic matter content in sediments and also contamination by organics such as BTEX. Arsenic may desorb under high pH conditions. Changes of pH can be related to some redox reactions, cation exchange reactions driving dissolution of carbonates, and dissolution of silicates. In very reducing environments, where SO4 reduction takes place, secondary sulfide minerals like As-bearing pyrite and orpiment, As2S3, can incorporate As. Geochemical modeling can be divided into two principal categories: (a) forward modeling and (b) inverse modeling. Forward modeling is used to predict water chemistry after completion of predetermined reactions. Inverse modeling is used to suggest which processes take place along a flowpath. Complex coupled transport and geochemistry programs, which allow for simulation of As adsorption, are becoming available. A common modeling approach is based on forward modeling with surface complexation modeling (SCM) of As adsorption, which can incorporate the effect of different adsorbent/As ratios, adsorption sites density, area available for adsorption, pH changes and competition of As for adsorption sites with other dissolved species such as phosphate. The adsorption modeling can be performed in both batch and transport modes in codes such as PHREEQC. Inverse modeling is generally used to verify hypotheses on the origin of As. Basic prerequisites of inverse modeling are the knowledge of flow pattern (sampling points used in model have to be hydraulically connected) and information about mineralogy including As mineral phases. Case studies of geochemical modeling including modeling of As adsorption are presented.
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