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Chadwick, Oliver A.

Publications and source records attributed to Chadwick, Oliver A..

Manganese Oxidation States in Volcanic Soils across Annual Rainfall Gradients

Manganese (Mn) exists as Mn(II), Mn(III), or Mn(IV) in soils, and the Mn oxidation state controls the roles of Mn in numerous environmental processes. However, the variations of Mn oxidation states with climate remain unknown. Here we determined the Mn oxidation states in highly weathered bulk volcanic soils (primary minerals free) across two rainfall gradients covering mean annual precipitation (MAP) of 0.25–5 m in the Hawaiian Islands. With increasing MAP, the soil redox conditions generally shifted from oxic to suboxic and to anoxic despite fluctuating at each site; concurrently, the proportions of Mn(IV) and Mn(II) decreased and increased, respectively. Mn(III) was low at both low and high MAP, but accumulated substantially, up to 80% of total Mn, in soils with prevalent suboxic conditions at intermediate MAP. Mn(III) was likely hosted in Mn(III,IV) and iron(III) oxides or complexed with organic matter, and its distribution among these hosts varied with soil redox potentials and soil pH. Soil redox conditions and rainfall-driven leaching jointly controlled exchangeable Mn(II) in soils, with its concentration peaking at intermediate MAP. The Mn redox chemistry was at disequilibrium, with the oxidation states correlating with long-term average soil redox potentials better than with soil pH. The soil redox conditions likely fluctuated between oxic and anoxic conditions more frequently at intermediate than at low and high MAP, creating biogeochemical hot spots where Mn, Fe, and other redox-sensitive elements may be actively cycled.

36 MATERIALS SCIENCE↗

Potassium isotopic fractionation in a humid and an arid soil–plant system in Hawai‘i

Plants play a critical role in the cycling of potassium (K) and the fractionation of its isotopes. However, little is known about K stable isotopic compositions in natural soil–plant systems and possible fractionation during intra-plant transport and root-soil uptake of K. Herein this study focuses on K isotopic fractionation within a humid and an arid soil–plant system sampled on the windward and leeward sides of Kohala Mountain, Hawai‘i. We determined the K isotopic compositions of < 2-mm bulk soil, soil saturation extraction, and selected plant tissues by multi-collector inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy. We studied soils and individual tissue samples such as roots, stems, barks, shoots (a sum of stems and fresh leaves), leaves (fresh and dead), seeds, and flowers of trees and grasses. The results demonstrated that: (i) tissue δ 41 K values ranged from –1.06 ± 0.06 to 1.15 ± 0.09‰; (ii) within the same plant, stems (barks), dead leaves, and reproductive tissues (flowers and seeds) were isotopically lighter compared to fresh leaves, and to a lesser extent, roots; (iii) δ 41 K values of the humid soil (-0.54 ± 0.07 to –0.49 ± 0.06‰) were lower than those of the arid soil (-0.24 ± 0.07 to –0.14 ± 0.06‰); and (iv) soil bioavailable pool δ 41 K (saturation extracts) ranged from –0.63 ± 0.08 to 0.34 ± 0.08‰ and 0.48 ± 0.08 to 0.54 ± 0.10‰ in the humid and arid soils, respectively. From synchrotron-based analysis of K atoms, we identified two major K-bearing phases co-existing as ionic K + and K-pectate association of different fractions. Based on K isotopic and synchrotron data, we conclude that two dominant processes are responsible for plant-mediated K isotopic fractionation, including (1) K redistribution during intra-plant circulation and (2) uptake at the root-soil interface. For intra-plant circulation of K, there is a high affinity of isotopically lighter K to organic complexes as K-pectate, and K-pectate is particularly enriched in roots and fresh leaves. For K uptake at root-soil interface, isotopically lighter K is preferentially taken by roots from soil bioavailable pools following a low-affinity (passive) transport path. Soil K budget in two sites reflects strong source mixing effects with limited plant imprints. This work provides exploratory data on the biogeochemical fractionation of K isotopes in the soil–plant system.

54 ENVIRONMENTAL SCIENCES↗

Rock-Sourced Nitrogen in Semi-Arid, Shale-Derived California Soils

Models suggest that rock-derived nitrogen (N) inputs are of global importance to ecosystem N budgets; however, field studies demonstrating the significance of rock N inputs are rare. We examined rock-derived N fluxes in soils derived from sedimentary rocks along a catena formed under a semi-arid climate. Our measurements demonstrate that there are distinct and traceable pools of N in the soil and bedrock and that the fraction of rock-derived N declines downslope along the catena. We used geochemical mass balance weathering flux measurements to estimate a rock-derived N flux of 0.145 to 0.896 kg ha -1 yr -1 at the ridgecrest. We also developed independent N flux estimates using a 15 N-based isotope mixing model. While geochemical mass-balance-based estimates fell within the 95% confidence range derived from the isotope mixing model (-1.1 to 44.3 kg ha -1 yr -1 ), this range was large due to uncertainty in values for atmospheric 15 N deposition. Along the catena, N isotopes suggest a diminishing effect of rock-derived N downslope. Overall, we found that despite relatively large N pools within the saprolite and bedrock, slow chemical weathering and landscape denudation limit the influence of rock-derived N, letting atmospheric N deposition (7.1 kg ha -1 yr -1 ) and N fixation (0.9-3.1 kg ha -1 yr -1 ) dominate N inputs to this grassland ecosystem.

54 ENVIRONMENTAL SCIENCES↗

Cellular and extracellular C contributions to respiration after wetting dry soil

Wetting of dry soil triggers a pulse of microbial respiration that has been attributed to two broad mechanisms: (1) recycling of microbial cellular carbon (C), and (2) consumption of extracellular organic C made available to microbes by wetting. We evaluated these two mechanisms by measuring cumulative CO 2 release, changes in the size and chemical composition of microbial biomass, and water-extractable organic carbon (WEOC) concentrations following artificial wetting of soil sampled from two depths at each of seven sites across California spanning a range of geologic parent materials. In samples collected from surface soil (0–10 cm depth), we found that cumulative CO 2 release after wetting in the laboratory was most strongly correlated with microbial biomass. In these samples, the relative abundance of trehalose—a putative microbial osmolyte—decreased from 25% (SD = 12) to 16% (SD = 7) of the chloroform-labile fraction of the microbial biomass after wetting. This suggested a role for osmolyte consumption in generating the respiration pulse. In subsoil (40–50 cm depth, or sampled at contact with rock), however, the cumulative CO2 release after wetting was unrelated to microbial biomass and more strongly related to WEOC. The concentrations of selected microbial biomass constituents (e.g. trehalose and amino acids) in WEOC were negligible (< 1%), suggesting that cell lysis was not important in generating WEOC in this study. The amount of WEOC relative to total organic C was greatest in subsoil, and negatively related to ammonium oxalate-extractable Fe (Pearson’s R = 0.42, p < 0.01), suggesting a role for soil mineralogical properties in controlling WEOC release. Together, these findings suggest that microbial cellular C and extracellular C jointly contribute to the respiration pulse, and that their relative contribution depends on depth.

59 BASIC BIOLOGICAL SCIENCES↗

"Land-Cover Conversion in Amazonia, The Role of ENV" Ironment and Substrate composition in Modifying SOI

LBA research from the first phase of LBA focused on three broad categories: 1) mapping land cover and quantifying rates of change, persistence of pasture, and area of recovering forest; 2) evaluating the role of environmental factors and land-use history on soil biogeochemistry; and 3) quantifying the natural and human controls on stream nutrient concentrations. The focus of the research was regional, concentrating primarily in the state of RondBnia, but also included land-cover mapping in the vicinity of Maraba, Para, and Manaus, Amazonas. Remote sensing analysis utilized Landsat Thematic Mapper (TM) and Multispectral Scanner (MS S) data to map historical patterns of land-cover change. Specific questions addressed by the remote sensing component of the research included: 1) what is the areal extent of dominant land-cover classes? 2) what are the rates of change of dominant land cover through processes of deforestation, disturbance and regeneration? and 3) what are the dynamic properties of each class that characterize temporal variability, duration, and frequency of repeat disturbance? Biogeochemical analysis focused on natural variability and impacts of land-use/land-cover changes on soil and stream biogeochemical properties at the regional scale. An emphasis was given to specific soil properties considered to be primary limiting factors regionally, including phosphorus, nitrogen, base cations and cation-exchange properties. Stream sampling emphasized the relative effects of the rates and timing of land-cover change on stream nutrients, demonstrating that vegetation conversion alone does not impact nutrients as much as subsequent land use and urbanization.

Roberts, Dar A.↗

Geomorphic Processes and Remote Sensing Signatures of Alluvial Fans in the Kun Lun Mountains, China

The timing of alluvial deposition in arid and semiarid areas is tied to land-surface instability caused by regional climate changes. The distribution pattern of dated deposits provides maps of regional land-surface response to past climate change. Sensitivity to differences in surface roughness and composition makes remote sensing techniques useful for regional mapping of alluvial deposits. Radar images from the Spaceborne Radar Laboratory and visible wavelength images from the French SPOT satellite were used to determine remote sensing signatures of alluvial fan units for an area in the Kun Lun Mountains of northwestern China. These data were combined with field observations to compare surface processes and their effects on remote sensing signatures in northwestern China and the southwestern United States. Geomorphic processes affecting alluvial fans in the two areas include aeolian deposition, desert varnish, and fluvial dissection. However, salt weathering is a much more important process in the Kun Lun than in the southwestern United States. This slows the formation of desert varnish and prevents desert pavement from forming. Thus the Kun Lun signatures are characteristic of the dominance of salt weathering, while signatures from the southwestern United States are characteristic of the dominance of desert varnish and pavement processes. Remote sensing signatures are consistent enough in these two regions to be used for mapping fan units over large areas.

Farr, Tom G.↗

The mass balance of soil evolution on late Quaternary marine terraces, northern California

Mass-balance interpretation of a soil chronosequence provides a means of quantifying elemental addition, removal, and transformation that occur in soils from a flight of marine terraces in northern California. Six soil profiles that range in age from several to 240,000 yr are developed in unconsolidated, sandy-marine, and eolian parent material deposited on bedrock marine platforms. Soil evolution is dominated by (1) open-system depletion of Si, Ca, Mg, K, and Na; (2) open-system enrichment of P in surface soil horizons; (3) relative immobility of Fe and Al; and (4) transformation of Fe, Si, and Al in the parent material to secondary clay minerals and sesquioxides. Net mass losses of bases and Si are generally uniform with depth and substantial, in some cases approaching 100 percent; however, the rate of loss of each element differs markedly, causing the ranking of each by relative abundance to shift with time. Loss of Si from the sand fraction by dissolution and particle-size diminution, from about 100 percent to less than 35 percent over 240 ky, mirrors a similar gain in the silt and clay size fractions. The Fe originally present in the sand fraction decreases from greater than 80 percent to less than 10 percent, whereas the amount of Fe present in the clay and crystalline oxyhydroxide fractions increases to 25 percent and 70 percent, respectively.

Merritts, Dorothy J.↗

Deformational mass transport and invasive processes in soil evolution

Channels left in soil by decayed roots and burrowing animals allow organic and inorganic precipitates and detritus to move through soil from above, to depths at which the minuteness of pores restricts further passage. Consecutive translocation-and-root-growth phases stir the soil, constituting an invasive, dilatational process which generates cumulative strains. Below the depths thus affected, mineral dissolution by descending organic acids leads to internal collapse; this softened/condensed precursor horizon is then transformed into soil via biological activity that mixes and expands the evolving residuum through root and micropore-network invasion.

Brimhall, George H.↗

Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region

Pedogenic calcite-crystal coatings on clasts were examined in four soils along an altitudinal gradient on Kyle Canyon alluvium in southern Nevada. Clast coatings were studied rather than matrix carbonate to avoid the effects of soil matrix on crystallization. Six crystal sizes and shapes were recognized and distinguished. Equant micrite was the dominant crystal form with similar abundance at all elevations. The distributions of five categories of spar and microspar appear to be influenced by altitudinally induced changes in effective moisture. In the drier, lower elevation soils, crystals were equant or parallel prismatic with irregular, interlocking boundaries while in the more moist, higher elevation soils they were randomly oriented, euhedral, prismatic, and fibrous. There was little support for the supposition that Mg(+2) substitution or increased (Mg + Ca)/HCO3 ratios in the precipitating solution produced crystal elongation.

Chadwick, Oliver A.↗