Iron(III) reduction and phosphorous solubilization in humid tropical forest soils

Phosphorus is one of the nutrients most commonly limiting net primary production in soils of humid tropical forests, mainly because insoluble Al and Fe phosphates and strong sorption to Fe(III) (hydr)oxides remove P from the bioavailable pool. Recent field studies have suggested, however, that this loss may be balanced by organic P accumulation under a wet moisture regime (>3350 mm annual precipitation). It has been hypothesized that, as the moisture regime changes from dry to mesic to wet, periods of anoxic soil conditions increase in intensity and duration, depleting Fe(III) (hydr)oxides and releasing sorbed P, but also slowing organic matter turnover, thus shifting the repository of soil P from minerals to humus. Almost no quantitative information is available concerning the coupled biogeochemical behavior of Fe and P in highly weathered forest soils that would allow examination of this hypothesis. In this paper, we report a laboratory incubation study of the effects of biotic Fe(III) (hydr)oxide reduction on P solubilization in a humid tropical forest soil (Ultisol) under a wet moisture regime (3000-4000 mm annual rainfall). The objectives of our study were: (1) to quantify Fe(III) reduction and P solubilization processes in a highly weathered forest soil expected to typify the hypothesized mineral dissolution-organic matter accumulation balance; (2) to examine the influence of electron shuttling on these processes using anthraquinone-2,6-disulfonate (AQDS), a well-known surrogate for the semiquinone electron shuttles in humic substances, as an experimental probe; and (3) to characterize the chemical forms of Fe(II) and P produced under anoxic conditions, both with and without AQDS. Two series of short-term incubation experiments were carried out, one without AQDS and another with an initial AQDS concentration of 150 μM. We measured pH, pE, and the production of Fe(II), total Fe [Fe(II) + Fe(III)], inorganic P, total P (inorganic P + organic P), and biogenic gases (CO₂, H₂ and CH₄). The same positive correlation was found between soluble P release and soluble Fe(II) production throughout incubation, implying that reduction of Fe(III) solubilized P. The Fe(II) produced was mainly particulate, evidently due to the formation of Fe(II) solid phases. Thermodynamic calculations indicated that precipitation of siderite and, in the presence of AQDS, vivianite was favored under the anoxic conditions that developed rapidly in the soil suspensions. Inorganic soluble P released during incubation was very small, indicating that the soluble P produced was mainly in organic form, which is consistent with the hypothesis that P accumulates in soil humus. Our net CO₂ production, H₂ consumption, and Fe(II) production data all suggested that reductive dissolution of Fe(III) (hydr)oxides was a terminal electron-accepting process coupled both to H₂ consumption and organic C oxidation by the native population of microorganisms in the soil. Addition of AQDS accelerated the production of Fe(II) and the release of soluble P, while hastening the decline in H₂ gas levels and suppressing CH₄ production. However, throughout incubation, the same quantitative relationships between soluble Fe(II) and P, and between pE and pH, were found, irrespective of AQDS addition. Thus we conclude that, in our soil incubation experiments, added AQDS functioned with the native microbial population solely as an electron shuttle catalyzing Fe(III) reduction. Whether humic substances in the soil also can act as electron shuttles in this way is a matter for future investigation.     

Graves Nunataks 95209: A snapshot of metal segregation and core formation

GRA 95209 may provide our best opportunity to date to understand the earliest stages of core formation in asteroidal bodies. This lodranite preserves a physically, chemically, and mineralogically complex set of metal-sulfide veins. High-resolution X-ray computed tomography revealed three distinct lithologies. The dominant mixed metal-silicate-sulfide matrix is cut by metal-rich, graphite-bearing veins exceeding 1 cm in width and grades into a volumetrically minor metal-poor region. Silicate compositions and modal abundances are typical for lodranites, while the mineralogy of the metal-sulfide component is complex and differs among the three lithologies. Kamacite and troilite occur with chromite, tetrataenite, schreibersite, graphite, and a range of phosphates. An ³⁹Ar-⁴⁰Ar age of 4.521 ± 0.006 Ga measures the time of closure of the K-Ar system. Carbon rosettes within the metal-rich vein are nitrogen-poor, well crystallized, include kamacite sub-grains of composition comparable to the host metal, and are essentially isotopically homogeneous (δ¹³C ∼ −33‰). In contrast, carbon rosettes within metal of the metal-poor lithology are N-poor, poorly crystallized, include kamacite grains that are Ni-poor compared to their host metal, and are isotopically heterogeneous (δ¹³C ranging from −50 to +80‰) even within a single metal grain. The silicate portion of GRA 95209 is similar to the lodranite EET 84302, sharing a common texture, silicate mineral compositions, and Ar-Ar age. GRA 95209 and EET 84302 are intermediate between acapulcoites and lodranites. Both experienced Fe,Ni-FeS melting with extensive melt migration, but record only the onset of silicate partial melting with limited migration of silicate melt. The complex metal-sulfide veins in GRA 95209 resulted from low-degree partial melting and melt migration and intruded the matrix lithology. Reactions between solid minerals and melt, including oxidation-reduction reactions, produced the array of phosphates, schreibersite, and tetrataenite. Extensive reduction in the metal-rich vein resulted from its origin in a hotter portion of the asteroid. This difference in thermal history is supported by the graphite structures and isotopic compositions. The graphite rosettes in the metal-rich vein are consistent with high-temperature igneous processing. In contrast, the carbon in the metal-poor lithology appears to preserve a record of formation in the nebula prior to parent-body formation. Carbon incorporated from the solar nebula into a differentiating asteroid is preferentially incorporated in metal-sulfide melts that form a core, but does not achieve isotopic homogeneity until extensive thermal processing occurs.