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Soils are increasingly perceived as complex systems with properties and biogeochemical functions that vary on millimeter scales. Quantitative information about the resulting biogeochemical heterogeneity is needed to improve process knowledge and to render biogeochemical models more mechanistic. Here we demonstrate how standardized arrays of Pt-electrodes can be used to quantify biogeochemical or ‘functional’ soil heterogeneity, defined as the extent to which the soil is subdivided into microenvironments. Our case study confirmed the validity of this approach for a soil sequence consisting of a well-drained, a moderately well drained and a poorly drained Mollisol. We found that (i) variations in soil moisture content are the immediate cause for variations in functional heterogeneity, with (ii) soil porosity influencing rates and the magnitude of change. We posit that the deployment of standardized arrays of Pt-electrodes will offer an affordable option to monitor the general metabolic state of the soil system and simultaneously quantify the functional heterogeneity of underlying processes at any point in time. Such information should be useful to improve quantitative estimates of processes as diverse as trace gas emissions, trace gas consumption, reductive dehalogenation and mobilization of metals in the subsurface biosphere. We recommend that parameterization of functional soil heterogeneity be included in long-term soil monitoring programs such as Superfund Sites, Critical Zone Observatories, Long Term Ecological Research (LTER) and National Ecological Observatory Network (NEON) sites.

Organic matter decomposition in soils and terrestrial sediments has a prominent role in the global carbon cycle. Carbon stocks in anoxic environments, such as wetlands and the subsurface of floodplains, are large and presumed to decompose slowly. The degree of microbial respiration in anoxic environments is typically thought to depend on the energetics of available terminal electron acceptors such as nitrate or sulfate; microbes couple the reduction of these compounds to the oxidation of organic carbon. However, it is also possible that the energetics of the organic carbon itself can determine whether it is decomposed. Here we examined water-soluble organic carbon by Fourier-transform ion-cyclotron-resonance mass spectrometry to compare the chemical composition and average nominal oxidation state of carbon-A metric reflecting whether microbial oxidation of organic matter is thermodynamically favourable-in anoxic (sulfidic) and oxic (non-sulfidic) floodplain sediments. We observed distinct minima in the average nominal oxidation state of water-soluble carbon in sediments exhibiting anoxic, sulfate-reducing conditions, suggesting preservation of carbon compounds with nominal oxidation states below the threshold that makes microbial sulfate reduction thermodynamically favourable. We conclude that thermodynamic limitations constitute an important complement to other mechanisms of carbon preservation, such as enzymatic restrictions and mineral association, within anaerobic environments.

Understanding the processes controlling organic matter (OM) stocks in upland soils, and the ability to management them, is crucial for maintaining soil fertility and carbon (C) storage as well as projecting change with time. OM inputs are balanced by the mineralization (oxidation) rate, with the difference determining whether the system is aggrading, degrading or at equilibrium with reference to its C storage. In upland soils, it is well recognized that the rate and extent of OM mineralization is affected by climatic factors (particularly temperature and rainfall) in combination with OM chemistry, mineral–organic associations, and physical protection. Here we examine evidence for the existence of persistent anaerobic microsites in upland soils and their effect on microbially mediated OM mineralization rates. We corroborate long-standing assumptions that residence times of OM tend to be greater in soil domains with limited oxygen supply (aggregates or peds). Moreover, the particularly long residence times of reduced organic compounds (e.g., aliphatics) are consistent with thermodynamic constraints on their oxidation under anaerobic conditions. Incorporating (i) pore length and connectivity governing oxygen diffusion rates (and thus oxygen supply) with (ii) ‘hot spots’ of microbial OM decomposition (and thus oxygen consumption), and (iii) kinetic and thermodynamic constraints on OM metabolism under anaerobic conditions will thus improve conceptual and numerical models of C cycling in upland soils. We conclude that constraints on microbial metabolism induced by oxygen limitations act as a largely unrecognized and greatly underestimated control on overall rates of C oxidation in upland soils.

A novel Pseudomonas putida chromate reductase has been purified to homogeneity to clone the chromate reductase-encoding gene and characterized. Bacterial chromate reductases can change soluble and toxic chromate to the insoluble and less toxic Cr(III) and Cr(VI) chromate is a widespread environmental contaminant.

Sediments taken from Coeur d'Alene Lake, ID with -0.5 m gravity cores were found to be highly reduced. The trace elements detected in the sediments are predominantly associated with an operationally defined sulfidic phase. Results point to a possibility that trace elements could move into overlying waters due either to lake eutrophication or the development of a seasonally anoxic hypolimnion. Metal sulfide formation and metal binding with organic material appear to control the mobilization of most trace elements.

Phosphate enhances the mobility of As in well-aerated soils by competing for adsorption sites. Phosphate and As may also coexist in large concentrations in hydric soils, and the influence of P on As in anaerobic systems is largely unknown. To determine the effects of P on As dynamics during a soil flooding and aeration cycle, samples of two soils were amended with [Na.sub.2]HAs[O.sub.4] and [Na.sub.2][HPO.sub.4] and incubated under a [N.sub.2] atmosphere for 41 d, and then reaerated for 7 d. Subsamples were collected intermittently and dissolved As, Fe, Mn, Ca, S, P, and [H.sub.3]As[O.sub.3] concentrations were determined. Arsenic speciation in the soil solids was determined after 14 and 41 d of flooding and then after 13 h of aeration by X-ray absorption near edge structure (XANES) spectroscopy. Arsenic sorption was small under anaerobic conditions, and [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] additions enhanced As(V) reduction rate in both soils and slightly suppressed As sorption in one soil. Arsenopyrite (FeAsS) was identified in the soil solids. Rapid and simultaneous As sorption and Fe precipitation occurred during the first 0.25 d of aeration, suggesting that As was retained on freshly precipitated Fe (hydr)oxides. Manganese precipitation and concomitant As sorption occurred after 1 d of aeration. Arsenopyrite was largely destroyed upon aeration but As(III) persisted. Thus, As is partitioned into the solid phase under both aerobic and anaerobic conditions, although more appreciably under the aerobic conditions of this study, and P has little influence on dissolved As during soil flooding-aeration cycles.

Arsenic (As) cycling within soils and sediments of the Mekong Delta of Cambodia is affected by drastic redox fluctuations caused by seasonal monsoons. Extensive flooding during monsoon seasons creates anoxic soil conditions that favor anaerobic microbial processes, including arsenate [As(V)] respiration-a process contributing to the mobilization of As. Repeated oxidation and reduction in near-surface sediments, which contain 10-40 mg kg−1 As, lead to the eventual downward movement of As to the underlying aquifer. Amplification of a highly conserved functional gene encoding dissimilatory As(V) reductase, arrA, can be used as a molecular marker to detect the genetic potential for As(V) respiration in environmental samples. However, few studies have successfully amplified arrA from sediments without prior enrichment, which can drastically shift community structure. In the present study, we examine the distribution and diversity of arrA genes amplified from multiple sites within the Cambodian Mekong Delta as a function of near-surface depth (10, 50, 100, 200, and 400 cm), where sediments undergo seasonal redox fluctuations. We report successful amplification of 302 arrA gene sequences (72 OTUs) from near-surface Cambodian soils (without prior enrichment or stimulation with carbon amendments), where a large majority (>70%) formed a well-supported clade that is phylogenetically distinct from previously reported sequences from Cambodia and other South and Southeast Asian sediments, with highest sequence similarity to known Geobacter species capable of As(V) respiration, further supporting the potentially important role of Geobacter sp. in arsenic mobilization in these regions. [ABSTRACT FROM AUTHOR]