F. E. Rhoton

QUANTIFICATION AND CHARACTERIZATION OF MAGHEMITE IN SOILS DERIVED FROM VOLCANIC ROCKS IN SOUTHERN BRAZIL

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

Sediment budgets and source determinations using fallout Cesium-137 in a semiarid rangeland watershed, Arizona, USA.

Analysis of soil redistribution and sediment sources in semiarid and arid watersheds provides information for implementing management practices to improve rangeland conditions and reduce sediment loads to streams. The purpose of this research was to develop sediment budgets and identify potential sediment sources using (137)Cs and other soil properties in a series of small semiarid subwatersheds on the USDA ARS Walnut Gulch Experimental Watershed near Tombstone, Arizona, USA. Soils were sampled in a grid pattern on two small subwatersheds and along transects associated with soils and geomorphology on six larger subwatersheds. Soil samples were analyzed for (137)Cs and selected physical and chemical properties (i.e., bulk density, rocks, particle size, soil organic carbon). Suspended sediment samples collected at measuring flume sites on the Walnut Gulch Experimental Watershed were also analyzed for these properties. Soil redistribution measured using (137)Cs inventories for a small shrub-dominated subwatershed and a small grass-dominated subwatershed found eroding areas in these subwatersheds were losing -5.6 and -3.2tha(-1)yr(-1), respectively; however, a sediment budget for each of these subwatersheds, including depositional areas, found net soil loss to be -4.3tha(-1)yr(-1) from the shrub-dominated subwatershed and -0.1tha(-1)yr(-1) from the grass-dominated subwatershed. Generally, the suspended sediment collected at the flumes of the six other subwatersheds was enriched in silt and clay. Using a mixing model to determine sediment source indicated that shrub-dominated subwatersheds were contributing most of the suspended sediment that was measured at the outlet flume of the Walnut Gulch Experimental Watershed. The two methodologies (sediment budgets and sediment source analyses) indicate that shrub-dominated systems provide more suspended sediment to the stream systems. The sediment budget studies also suggest that sediment yields measured at the outlet of a watershed may be a poor indicator of actual soil redistribution rates within these semiarid watersheds. Management of these semiarid rangelands must consider techniques that will protect grass-dominated areas from shrub invasion to improve rangeland conditions.

Properties of iron oxides in streams draining the Loess Uplands of Mississippi

Abstract Iron oxide precipitates are abundant in small stream systems of NW Mississippi, USA especially during the wet winter months. The properties of these specific materials are unknown even though they have the potential to influence soil physical properties and adsorb chemical pollutants in sediment environments. Streamwater and associated precipitates were collected from 4 representative streams at Cedar Creek (CC), Lees Creek (LC), Spring Creek (SC), and Toby Creek (TC) during winter flow periods. Precipitate specimens were characterized for mineralogy, color, and solubility in oxalate (o), dithionite (d), and HNO 3 . Chemical composition of the water was dominated by Ca, Na, Mg, and K, in that order, at an average pH of 7.0. X-ray diffraction (XRD) and differential scanning calorimeter (DSC) data indicated that the precipitates were primarily poorly ordered ferrihydrite (CC, TC) and lepidocrocite (LC, SC). The Fe o /Fe d ratios were 0.40 (CC), 0.68 (LC), 0.66 (SC), and 0.67 (TC). Organic C contents were 80.6, 38.0, 63.0, and 51.3 g kg −1 for the same samples. Precipitate color was uniform among sites, averaging 6.7 YR 4.8/6.2. After oxalate extraction, redness increased slightly in the CC and SC specimens, and decreased in the others. Extraction with dithionite depleted the red color in all specimens, but had less effect on the CC and SC samples which retained hues at 7.9 and 7.3 YR, respectively. Dithionite extractable P equaled 1.02 (CC), 0.72 (LC), 0.56 (SC), and 0.99 (TC) g kg −1 . The results from this study indicated that: (1) the precipitates are either primarily poorly ordered ferrihydrite or lepidocrocite; (2) the solubility of ferrihydrite in both oxalate and dithionite is influenced by C contents; and (3) the redder, ferrihydrite specimens contain the greatest P concentrations.

Natural Ferrihydrite as an Agent for Reducing Turbidity Caused by Suspended Clays

Biologically impaired waters are often caused by the turbidity associated with elevated suspended sediment concentrations. Turbidity can be reduced by the addition of positively charged compounds that coagulate negatively charged particles in suspension, causing them to flocculate. This research was conducted to determine the effectiveness of ferrihydrite, a poorly crystalline Fe oxide, as a flocculating agent for suspended clays similar to those found in high-turbidity waters of the Mississippi delta. Clay concentrations of 100 mg L(-1) from a Dubbs silt loam (fine silty, mixed, active, thermic Typic Hapludalfs), a Forestdale silty clay loam (fine, smectitic, thermic Typic Hapludalfs), and a Sharkey clay (very fine, smectitic, thermic Chromic Epiaquerts) were suspended in 0.0005 mol L(-1) CaCl(2) solutions at pH 5, 6, 7, or 8. Natural ferrihydrite with a zero point of charge at pH 5.8 was acquired from a drinking water treatment facility and mixed with the suspension at concentrations of 0, 10, 25, and 50 mg L(-1). After settling periods of 24 and 48 h, percent transmittance was measured at a wavelength of 420 nm using a 3-mL sample collected at a depth of 2 cm. The greatest reductions in turbidity after 24-h equilibration were recorded for the pH 5 suspensions of the Dubbs (31%) and Forestdale (37%) clays at a ferrihydrite concentration of 10 mg L(-1) and for the Sharkey clay at a ferrihydrite concentration of 25 mg L(-1) (relative to the 0 ferrihydrite treatment). Water clarity for all samples further increased after 48 h. These results indicate that the effectiveness of ferrihydrite, as a means of reducing turbidity associated with suspended clays, is greatest at pH values below its zero point of charge.