Phosphate compounds of Pb [e.g., pyromorphite Pb 5 (PO 4 ) 3 -(X) where X ) OH, F, or Cl] are comparatively insoluble, and inducing their formation in contaminated soils may be a means of reducing the bioavailability and chemical lability of Pb in soil. Previous research has documented the formation of pyromorphite subsequent to the addition of phosphates, as soluble phosphate (Cotter-Howells,

Previous studies have shown that the interactions of apatite with dissolved Pb are caused by the dissolution of apatite grains concomitant with the precipitation of lead orthophosphates (pyromorphites). The present study extends this work by examining the interactions of selected Pb minerals and a Pbcontaminated soil with apatite. Specimen-grade PbO and PbCO 3 were reacted separately with hydroxylapatite (HA) in controlled pH reactors. Hydroxypyromorphite (HP) formed at the expense of HA, PbO, and PbCO 3 after a reaction period of 2 days, causing significant decreases in aqueous Pb concentrations. The extent of reaction was pH dependent, with more HP formation at pH 5 than at pH 6 or pH 7. Equilibrium modeling with MINEQL + indicated the stoichiometric conversion of the native Pb solids to HP at all pH values examined in laboratory experiments. In companion experiments, particle size and density separation techniques were used to obtain Pb-enriched fractions from a contaminated soil. These were identified as PbO and PbCO 3 with X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Pb-enriched fractions were reacted with HA, and the formation of HP (at the expense of "native" Pb solids) was observed by XRD and SEM. Clearly, apatite amendments to Pb-contaminated soil materials can induce the formation of pyromorphites.

We investigated the effect of fire intensity from slash‐and‐burn agriculture on the mineralogy of Oxisols in the Sepunggur area, Jambi Province, Sumatra, Indonesia, in both field and laboratory experiments. Samples were collected from two depths (0–5 and 5–15 cm) at locations exposed to 100, 300, 600, and >600°C surface temperatures during the burns. Soils under forest and slashed vegetation were collected as controls. The pre‐burn soil mineralogy was dominated by kaolinite, gibbsite, anatase, and goethite. Changes in soil properties with burning were most pronounced in the 0‐ to 5‐cm layer. Burning the topsoil led to coarser textures, especially at temperatures exceeding 600°C. Heat reduced the gibbsite and kaolinite concentrations and converted goethite into ultra‐fine maghemite, thus increasing the magnetic susceptibility of the samples. The conversion of goethite did not take place until water in the samples had vaporized. Addition of organic matter to soil with a low organic C content before heating increased the magnetic susceptibility, indicating that organic matter was necessary (and limiting) for the complete conversion of goethite. Coarse‐grained magnetite particles were present prior to and after the burning and, therefore, were not pyrogenic. Magnetic susceptibility measurements were highly discriminatory among heat treatments, whereas x‐ray diffraction (XRD) was much less sensitive to fire‐induced changes in mineralogy. Our research showed that severe burning had drastic effects on soil mineralogy, but changes should also be expected at lower fire intensities. Further research is needed to determine how important these changes in soil mineralogy are for nutrient availability in the growing season after the burn.

The aqueous concentrations of heavy metals in soils, sediments, and aquatic environments frequently are controlled by the dissolution and precipitation of discrete mineral phases. Contaminant uptake by organisms as well as contaminant transport in natural systems typically occurs through the solution phase. Thus, the thermodynamic solubility of contaminant-containing minerals in these environments can directly inf luence the chemical reactivity, transport, and ecotoxicity of their constituent ions. In many cases, Pb-contaminated soils and sediments contain the minerals anglesite (PbSO 4 ), cerussite (PbCO 3 ), and various lead oxides (e.g., litharge, PbO) as well as Pb 2؉ adsorbed to Fe and Mn (hydr)oxides. Whereas adsorbed Pb can be comparatively inert, the lead oxides, sulfates, and carbonates are all highly soluble in acidic to circumneutral environments, and soil Pb in these forms can pose a significant environmental risk. In contrast, the lead phosphates [e.g., pyromorphite, Pb 5 (PO 4 ) 3 Cl] are much less soluble and geochemically stable over a wide pH range. Application of soluble or solid-phase phosphates (i.e., apatites) to contaminated soils and sediments induces the dissolution of the ''native'' Pb minerals, the desorption of Pb adsorbed by hydrous metal oxides, and the subsequent formation of pyromorphites in situ. This process results in decreases in the chemical lability and bioavailability of the Pb without its removal from the contaminated media. This and analogous approaches may be useful strategies for remediating contaminated soils and sediments.

The molecular-level speciation of arsenic has been determined in a soil profile in the Massif Central near Auzon, France that was impacted by As-based pesticides by combining conventional techniques (XRD, selective chemical extractions) with X-ray absorption spectroscopy (XAS). The arsenic concentration is very high at the top (>7000 mg kg(-1)) and decreases rapidly downward to a few hundreds of milligrams per kilogram. A thin layer of schultenite (PbHAsO4), a lead arsenate commonly used as an insecticide until the middle of the 20th century, was found at 10 cm depth. Despite the occurrence of this As-bearing mineral, oxalate extraction indicated that more than 65% of the arsenic was released upon dissolution of amorphous iron oxides, suggesting a major association of arsenic with these phases within the soil profile. Since oxalate extraction cannot unambiguously distinguish among the various chemical forms of arsenic, these results were confirmed by a direct in situ determination of arsenic speciation using XAS analysis. XANES data indicate that arsenic occurs mainly as As(V) along the soil profile except for the topsoil sample where a minor amount (7%) of As(III) was detected. EXAFS spectra of soil samples were fit by linear combinations of model compounds spectra and by a shell-by-shell method. These procedures clearly confirmed that As(V) is mainly (at least 80 wt %) associated with amorphous Fe(III) oxides as coprecipitates within the soil profile. If any, the proportion of schultenite, which was evidenced by XRD in a separate thin white layer, does not account for more than 10 wt % of arsenic in soil samples. This study emphasizes the importance of iron oxides in restricting arsenic dispersal within soils following dissolution of primary As-bearing solids manufactured for use as pesticides and released into the soils.