Jon Petter Gustafsson

Phosphate removal using blast furnace slags and opoka-mechanisms

The abiotic sorption efficiency of on-site wastewater treatment systems can be improved by using a strongly sorbing filter material that, if it retains phosphorus (P) in a plant available way, can ...

Advances in understanding the podzolization process resulting from a multidisciplinary study of three coniferous forest soils in the Nordic Countries

Advances in understanding the podzolisation process resulting from a multidisciplinary study at three coniferous forest soils in the Nordic countries

Podzolisation mechanisms and the synthesis of imogolite in northern Scandinavia

Abstract The nature of the short-range ordered Al and Fe minerals of the spodic B horizons of northern Scandinavia was studied by selective dissolution, transmission electron microscopy, infrared absorption and sulphate adsorption experiments. Imogolite-type materials (proto-imogolite allophane and well-developed imogolite) were the predominant oxalate-extractable Al minerals. Minor amounts of gibbsite and kaolinite were also found. The Fe oxides were less abundant and relatively well crystallized. Imogolite-type materials were the predominant source of positive charge, as evidenced by the amount of sulphate adsorbed. The Fe:AI ratio of the pyrophosphate extracts was positively correlated with the ratio of pyrophosphate-C to oxalate-extractable Al—this observation provides field evidence that imogolite-type materials were particularly unstable in the presence of organic substances. It is hypothesized that most accumulated Al and Fe originated from the congruent dissolution of primary minerals followed by the downward migration and degradation of metal-organic complexes, but incongruent weathering within the B horizon might have made additional contributions to the precipitation of the short-range ordered minerals. Historical climatic change might, to some extent, explain why metal-organic complexes were almost absent in many B horizons.

THE SURFACE CHEMISTRY OF IMOGOLITE

Imogolite is a tubular aluminosilicate which is common in Andosols and Spodosols. The high pH at point-of-zero charge at the outer parts of the tube and the anomalously high chloride adsorption of imogolite suggested that there may be structural charge associated with this mineral. The structural charge may arise because of changes in bond valence imposed by the incorporation of orthosilicate anions in a gibbsite-type sheet. By using a Basic Stem Model approach, it is shown that the surface charge properties of imogolite are explained if the mean Al-O bond valence of the outer -Al2OH groups is higher than the inner -Al2OHSiO3 groups. Hence, a weak positive charge is developed on the outer tube walls whereas a negative charge develops in the tubular pores. The best model fits were obtained where either one or two units of structural charge per unit cell of tube were assumed. The model may also explain why imogolite tubes are normally aggregated in large bundles in close hexagonal packing, because bound counterions may hold the tubes together. However, to arrive at good model descriptions, the deprotonation of -Al2OH groups must occur at a higher pH than that expected when assuming that all surface oxygens form two hydrogen bridges with H2O. A more precise structure of imogolite is required to test fully this hypothesis.

Chromium(III) Complexation to Natural Organic Matter: Mechanisms and Modeling

Chromium is a common soil contaminant, and it often exists as chromium(III). However, limited information exists on the coordination chemistry and stability of chromium(III) complexes with natural organic matter (NOM). Here, the complexation of chromium(III) to mor layer material and to Suwannee River Fulvic Acid (SRFA) was investigated using EXAFS spectroscopy and batch experiments. The EXAFS results showed a predominance of monomeric chromium(III)-NOM complexes at low pH (<5), in which only Cr···C and Cr-O-C interactions were observed in the second coordination shell. At pH > 5 there were polynuclear chromium(III)-NOM complexes with Cr···Cr interactions at 2.98 Å and for SRFA also at 3.57 Å, indicating the presence of dimers (soil) and tetramers (SRFA). The complexation of chromium(III) to NOM was intermediate between that of iron(III) and aluminum(III). Chromium(III) complexation was slow at pH < 4: three months or longer were required to reach equilibrium. The results were used to constrain chromium-NOM complexation in the Stockholm Humic Model (SHM): a monomeric complex dominated at pH < 5, whereas a dimeric complex dominated at higher pH. The optimized constant for the monomeric chromium(III) complex was in between those of the iron(III) and aluminum(III) NOM complexes. Our study suggests that chromium(III)-NOM complexes are important for chromium speciation in many environments.

Chemical Equilibrium Modeling of Organic Acids, pH. Aluminum, and Iron in Swedish Surface Waters

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Modelling lead(II) sorption to ferrihydrite and soil organic matter

Lead(II) adsorption to soil organic matter and iron (hydr)oxides is strong, and may control the geochemical behaviour of this metal. Here, we report the adsorption of Pb(2+) (i) to 2-line ferrihydr ...

Surface reactivity of poorly-ordered minerals in podzol B horizons

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 horizon ...

Mineralogy of poorly crystalline aluminium phases in the B horizon of Podzols in southern Sweden

Poorly crystalline Al components of the clay fraction are often neglected in soil mineralogical studies. In this study 7 B horizons from podzolised soils in Sweden were analysed using a combination of infrared (IR) spectroscopy, transmission electron microscopy (TEM), X-ray diAraction (XRD) and selective extractions. It was found that most Bhs and Bs horizons contained allophane, imogolite and more or less hydroxy-interlayered vermiculite. Some Bhs and Bs horizons also contained small amounts of kaolinite and/or gibbsite. In one acid Bh horizon organically complexed Al was the only reactive Al fraction of importance. The vertical patterns of vermiculite and allophane/imogolite suggested that both had formed during the podzolisation process, but due to diAerent mechanisms. The pattern of kaolinite and gibbsite occurrences indicated that these minerals were mostly inherited from the parent material. Oxalate and pyrophosphate extractions suggested that allophane and imogolite constituted the most important reactive inorganic Al fraction in the soils. This shows that allophane and imogolite seem to be the typical, rather than the occasional, reactive inorganic Al phases that form in the B horizon as a result of podzolisation. # 1999 Elsevier Science Ltd. All rights reserved.

Arsenic geochemistry in forested soil profiles as revealed by solid-phase studies

Abstract Arsenic concentrations in soils may be elevated either because of anthropogenic activity or because of a high natural abundance of the parent material. In the unsaturated zone of seven forest soils in northern Sweden, inorganic As(V) generally dominated the solid-phase speciation while non-NaBH 4 -reducible organic As associated with isolated humic substances (humic As) was present in low amounts. In unpolluted soils, absorbed As(V) was more or less constant through the B and C horizons and did not show any obvious relationship with secondary short-range ordered Fe or Al minerals-this suggested that most As(V) had formed early during pedogenesis as a result of sulphide weathering. When a small amount of As(V) was added to the mineral soils, adsorption was almost complete and the amount of remaining As(V) in solution depended on the ratio of pyrophosphate-C to oxalate-(Fe + Al). On higher As(V) additions, the amount of adsorption sites governed the As solubility. As regards the humic As, the XAD-4 acid fulvates were more enriched with As as compared to the hydrophobic acids. The As content of the forest floor was highly dependent on the distance from the Ronnskarsverken non-ferrous metal smelter, but did not reflect the As content of the underlying horizons; thus, biological uptake of As from the mineral soil appeared to be very low.