Soil Redox Processes Research Articles

Co-exposure of microplastics and polychlorinated biphenyls strongly influenced the cycling processes of typical biogenic elements in anoxic soil

The co-exposure of microplastics (MPs) and polychlorinated biphenyls (PCBs) in soil is inevitable, but their combined effect on cycles of typical biogenic elements (e.g. C, N, Fe, S) is still unclear. And the co-exposure of MPs and PCBs caused more severe effects than single exposure to pollution. Therefore, in this study, a 255-day anaerobic incubation experiment was conducted by adding polyethylene microplastics (PE MPs, including 30 ± 10 μm and 500 μm) and PCB138. The presence of PE MPs inhibited the PCB138 degradation. Also, PE MPs addition (1%, w/w) enhanced the methanogenesis, Fe(Ⅲ) reduction, and sulfate reduction while inhibited nitrate reduction and the biodegradation of PCB138. And PCB138 addition (10 mg·kg−1) promoted the methanogenesis and Fe(Ⅲ) reduction, but inhibited sulfate reduction and nitrate reduction. Strikingly, the presence of PE MPs significantly reduced the impact of PCB138 on the soil redox processes. The abundance changes of special microbial communities, including Anaeromyxobate, Geobacter, Bacillus, Desulfitobacterium, Thermodesulfovibrio, Metanobacterium, etc., were consistent with the changes in soil redox processes, revealing that the effect of PE MPs and/or PCB138 on the cycle of typical biogenic elements was mainly achieved by altering the functional microorganisms. This study improves the knowledge of studies on the impact of MPs and combined organic pollutants to soil redox processes, which is greatly important to the stabilization and balance of biogeochemical cycling in ecology.

Iron oxidation coupled with nitrate reduction affects the acetate-assimilating microbial community structure elucidated by stable isotope probing in flooded paddy soil

Acetate is an abundant carbon source that can trigger microbial redox processes in anoxic environments, thereby affecting the microbial community structure, function, and associated element cycling. Here, we investigated the acetate-assimilating microbial community, especially the key microorganisms involved in nitrate-dependent Fe(II) oxidation that are closely associated with soil redox processes in flooded soil. In the present study, DNA-stable isotope probing (DNA-SIP) with labeled acetate (13C) as a carbon source was applied to examine the acetate-assimilating communities associated with nitrate-dependent Fe(II) oxidation. The results showed that NO3− was rapidly reduced in the treatments with NO3− and NO3− + Fe(II). Fe(II) oxidation occurred quickly only in the presence of NO3−. In the treatments with acetate only, the predominant 13C-labeled genera such as Geobacter, Azospira, Azospirillum, Ideonella, and Desulfovibrionia were probably involved in acetate oxidation coupled with the redox processes of NO3−, Fe(III) and SO42− reduction, which are the most important electron acceptors in flooded soils. The addition of NO3− and Fe(II) significantly affected the acetate-assimilating microbial community from the original soil. The enriched genera in 13C heavy fractions were associated with Pseudogulbenkiania, Azospira, Zoogloea, Azoarcus, and Bdellovibrio dominated in the treatments with NO3− and Fe(II). In the treatments with NO3− only, Zoogloea, Azospira, Azoarcus, and Geothrix were the dominant genera. Given the different genera with enrichments in 13C-heavy fractions in different treatments, Zoogloea and Pseudogulbenkiania were identified as key microorganisms associated with NO3− reduction and nitrate-dependent Fe(II) oxidation, respectively. These findings suggest the importance of Zoogloea and Pseudogulbenkiania for C, Fe, and N biogeochemistry and indicate that Fe and N cycling have a great impact on soil biogeochemistry processes.

Dynamic processes in conjunction with microbial response to unveil the attenuation mechanisms of tris (2-chloroethyl) phosphate (TCEP) in non-sanitary landfill soils

Although the environmental and health risks of chlorinated organophosphate esters (OPEs-Cl) have drawn much attention, its environmental behaviors have been insufficiently characterized. As a notable sink of this emerging contaminant, non-sanitary landfills, which may decompose/accumulate OPEs-Cl, is of particular concern. In the present study, the dynamic processes of the typical OPEs-Cl, tris(2-chloroethyl) phosphate (TCEP), in non-sanitary landfill soils were analyzed under anaerobic condition, and the microbial taxa involved in these processes were explored. Our results showed that TCEP could be simultaneously reduced by abiotic and biotic processes, as it was reduced by 73.9% and 65.5% over the 120-day experiment in landfill humus and subsoil, respectively. Notably, the degradation of TCEP was significantly (p < 0.05) enhanced under the stress of a high TCEP concentration (10 μg g−1), while its ecological consequences were found insignificant regarding the microbial diversity and community structure and the typical soil redox processes, including Fe(III)/SO42− reduction and methanogenesis, in both soils. The microbial diversity of subsoil was significantly lower, and acetate was an important factor in changing microbial communities in landfill soils. The microbes in the family Nocardioidaceae and genus Pseudomonas might contribute to in the degradation of TCEP in landfill humus and subsoil, respectively. The metabolism related to sulfur and sulfate respiration were significantly (p < 0.05) correlated with TCEP reduction, and Desulfosporosinus were found as a potentially functional microbial taxon in TCEP degradation in both soils. The results could advance our understanding of the environmental behavior of OPEs-Cl in landfill-like complex environments.

Linkages between soil organic matter and magnetic mineral formation in agricultural fields in southeastern Minnesota, USA

Magnetic properties of soil are widely utilized to study soil development in a variety of settings due to the formation of strongly magnetic iron oxides during pedogenesis. Similarly, soil organic matter (SOM) is commonly measured in soil surveys conducted on agricultural lands due to the essential role SOM plays in the soil ecosystem. Here, we present data from two agricultural fields in southeastern Minnesota that demonstrate a relationship between soil magnetic properties and SOM. In each field, we collected 100 topsoil samples along a 40 m by 20 m grid to determine spatial variability in soil magnetic properties and SOM, as well as two soil cores to constrain variability with depth (∼0–60 cm). Magnetic susceptibility, low-field remanence, and hysteresis properties were used to characterize magnetic mineral abundance and grain-size in the soils. There are strong positive correlations between SOM and three magnetic properties: the frequency dependence of susceptibility (χfd), anhysteretic remanent magnetization (ARM), and the ratio of ARM to isothermal remanent magnetization (ARM/IRM). All three of these magnetic properties (χfd, ARM, and ARM/IRM) are sensitive to the concentration (or relative abundance) of fine-grained (<75 nm) magnetite/maghemite known to form in well-drained soils during pedogenesis. Correlation between SOM and magnetic properties persist in each field despite differences in the management strategy over the past three decades. Our results support a functional link between SOM and soil-formed magnetite/maghemite, where increasing SOM (up to a threshold) enhances the production and stability of soil-formed magnetite due to its role in soil redox processes and iron-organic complexes. Agricultural soils seem particularly well suited to demonstrate correlations between SOM and pedogenic magnetic minerals due to their relatively low SOM and typically well-drained environments, supporting the utility of soil magnetism in agricultural soil survey studies.

Impacts of Redox Conditions on Arsenic and Antimony Transformation in Paddy Soil: Kinetics and Functional Bacteria

Arsenic (As) and antimony (Sb) are known carcinogens and are present as contaminants in paddy soils. However, the complicated dynamics of the mobility of these metalloids have not been well understood due to changing redox conditions in paddy soils. Herein, the kinetics of dissolved As and Sb, and functional bacteria/genes were examined in a paddy soil cultured under aerobic and anaerobic conditions. Under aerobic condition, dissolved As(V) and Sb(V) increased constantly due to sulfide oxidation by O2 and bound As and Sb were released. Under anaerobic condition, the reduction of As(V) and Sb(V) occurred, and the mobility of As and Sb were affected by soil redox processes. The bacteria with functional genes aioA and arrA were responsible for the direct As/Sb transformation, while Fe- and N-related bacteria had an indirect effect on the fate of As/Sb via coupling with the redox processes of Fe and N. These findings improve understanding of the mobility of As and Sb in paddy soil systems under different redox conditions.

Microbial and abiotic factors of flooded soil that affect redox biodegradation of lindane

Pollution induces pressure to soil microorganism; and conversely, the degradation of pollutants is reported largely regulated by the soil microbiome assembly in situ. However, the specific-dependent core taxa of degraders were barely confirmed, which is not conducive to improving the soil remediation strategy. Taking pollution of a typical organochlorine pesticide (OCP), lindane, as an example, we explored the microbial community assembly in flooded soils and simultaneously quantified the corresponding dynamics of typical soil redox processes. Contrasting initial status of microbial diversity was set up by gamma irradiation or not, with additives (acetate, NaNO3, acetate + NaNO3) capable of modifying microbial growth employed simultaneously. Microorganism under lindane stress was reflected by microbial adaptability within complex co-occurrence networks, wherein some environment-dependent core taxa (e.g., Clostridia, Bacteroidia, Bacilli) were highly resilient to pollution and sterilization disturbances. Lindane had higher degradation rate in irradiated soil (0.96 mg kg−1 d−1) than non-irradiated soil (0.83 mg kg−1 d−1). In non-irradiated soil, addition of acetate promoted lindane degradation and methanogenesis, whereas nitrate inhibited lindane degradation but promoted denitrification. No significant differences in lindane degradation were observed in irradiated soils, which exhibited low-diversity microbiomes in parallel to stronger Fe reduction and methanogenesis. The varied corresponding trigger effects on soil redox processes are likely due to differences of soil microbiome, specifically, deterministic or stochastic assembly, in response to pollution stress under high or low initial microbial diversity conditions. Our results improve the knowledge of the adaptability of disturbed microbiomes and their feedback on microbial functional development in OCP-polluted soils, achieving for a more reliable understanding with respect to the ecological risk of soils resided with OCPs under the fact of global microbial diversity loss.

Assembly and variation of root-associated microbiota of rice during their vegetative growth phase with and without lindane pollutant

Soil-derived microbiota associated with plant roots are conducive to plant growth and stress resistance. However, the spatio-temporal dynamics of microbiota in response to organochlorine pollution during the unstable vegetative growth phase of rice is not well understood. In this study, we focused on the rice (Oryza sativa L.) microbiota across the bulk soil, rhizosphere and endosphere compartments during the vegetative growth phase in two different soils with and without lindane pollutant. The results showed that the factors of growth time, soil types and rhizo-compartments had significant influence on the microbial communities of rice, while lindane mostly stimulated the construction of endosphere microbiota at the vegetative phase. Active rice root-soil-microbe interactions induced an inhibition effect on lindane removal at the later vegetative growth phase in rice-growth-dependent anaerobic condition, likely due to the root oxygen loss and microbial mediated co-occurring competitive electron-consuming redox processes in soils. Each rhizo-compartment owned distinct microbial communities, and therefore, presented specific ecologically functional categories, while the moderate functional differences were also affected by plants species and residual pollution stress. This work revealed the underground micro-ecological process of microbiota and especially their potential linkage to the natural attenuation of residual organochlorine such as lindane.

Maize straw biochar addition inhibited pentachlorophenol dechlorination by strengthening the predominant soil reduction processes in flooded soil

Biochar has received increasing attention for its multifunctional applications as a soil amendment. The dual effect of biochar on reductive organic pollutants and soil biogeochemical processes under anaerobic environments in parallel has yet to be fully explored. In this study, anaerobic batch experiments were conducted to examine the effect of biochar on both reductive transformation of pentachlorophenol (PCP) and soil redox processes in flooded soil. Compared to biochar-free controls, the reductive dechlorination of PCP was significantly inhibited following biochar addition, with the inhibition degree increased with increasing amount of biochar. Dissimilatory iron and sulfate reduction, as well as the production of methane, were significantly enhanced following biochar addition. The bacterial and archaeal communities showed a functional selection responded to the addition of biochar and PCP, with the core functional groups at the genus level including Dethiobacter, Clostridium, Geosporobacter, Desulfuromonas, Desulfatitalea, and Methanosarcina. These findings indicated that biochar could affect soil microbial redox processes and may act as an electron mediator altering electron distribution from PCP dechlorination to the predominant soil reduction processes, and increase understanding regarding biochar’s comprehensive effects on the remediation of natural flooded soil polluted by chlorinated organic pollutants that can be degraded reductively.

Improved synergistic dechlorination of PCP in flooded soil microcosms with supplementary electron donors, as revealed by strengthened connections of functional microbial interactome

The enhancement of in situ reductive dechlorination is typically accomplished through the provision of various exogenous electron donors. However, in mixed microbial communities, such as prevail in soils, the addition of electron donors may stimulate the activity of indigenous dechlorinating microorganisms, but they also inevitably affect naturally-coexisting soil redox processes and stimulate co-occurring populations that compete for such donors. In this study, we examined the chemical and microbial interactions between typical soil redox processes and PCP degradation in naturally flooded paddy soils amended with different electron donors (including formate, acetate, pyruvate and lactate) in two different reducing conditions, viz. methanogenic and sulfate-reducing conditions. Among the electron donors tested, pyruvate was most effective in facilitating PCP dechlorination. Together with the Illumina sequencing data on bacterial and archaeal responses in the soil, a co-occurrence network analysis was applied to study the impact of different electron donors on the bacterial and archaeal interactome processing PCP dechlorination in different soil-reducing conditions. The addition of exogenous fermentative electron donors facilitated change in the bacterial and archaeal communities by increasing the relative abundance, and thus strengthening associated connections amongst the core functional microbial community, assembled by fermenting Clostridia, Anaerosolibacter and Alkaliphilus, Desulfosporosinus and Desulfuromonadaceae, and methanogenic Methanosarcina. This consortia might be likely involved in dechlorination and soil redox processes such as iron/sulfate reduction and methanogenesis. Our results provide a comprehensive and new perspective on optimum regulating and facilitating strategies in the degradation of PCP in anaerobic environments.

Nitrate supply and sulfate-reducing suppression facilitate the removal of pentachlorophenol in a flooded mangrove soil

An anaerobic incubation was launched with varying nitrate (1, 5, 10 and 20 mM exogenous NaNO3) and molybdate (20 mM Na2MoO4, a sulfate-reducing inhibitor) additions to investigate the characteristics of PCP dechlorination, as well as the reduction of natural co-occurring electron acceptors, including NO3−, Fe(III) and SO42−, and the responses of microbial community structures under a unique reductive mangrove soil. Regardless of exogenous addition, nitrate was rapidly eliminated in the first 12 days. The reduction process of Fe(III) was inhibited, while that of SO42− reduction depended on addition concentration as compared to the control. PCP was mainly degraded from orth-position, forming the only intermediate 2,3,4,5-TeCP by anaerobic microbes, with the highest PCP removal rate of average 21.9% achieved in 1 and 5 mM NaNO3 as well as 20 mM Na2MoO4 treatments and the lowest of 7.5% in 20 mM NaNO3 treatment. The effects of nitrate on PCP dechlorination depended on addition concentration, while molybdate promoted PCP attenuation significantly. Analyses of the Illumina sequencing data and the relative abundance of dominant microorganisms indicated that the core functional groups regulated PCP removal at genera level likely included Bacillus, Pesudomonas, Dethiobacter, Desulfoporosinus and Desulfovbrio in the nitrate treatments; while that was likely Sedimentibacter and Geosporobacter_Thermotalea in the molybdate treatment. Nitrate supplement but not over supplement, or addition of molybdate are suggested as alternative strategies for better remediation in the nitrate-deficient and sulfur-accumulated soil ecosystem contaminated by PCP, through regulating the growth of core functional groups and thereby coordinating the interaction between dechlorination and its coupled soil redox processes due to shifts of more available electrons to dechlorination. Our results broadened the knowledge regarding microbial PCP degradation and their interactions with natural soil redox processes under anaerobic soil ecosystems.

Arsenic mitigation in paddy soils by using microbial fuel cells

Arsenic (As) behavior in paddy soils couples with the redox process of iron (Fe) minerals. When soil is flooded, Fe oxides are transformed to soluble ferrous ions by accepting the electrons from Fe reducers. This process can significantly affect the fate of As in paddy fields. In this study, we show a novel technique to manipulate the Fe redox processes in paddy soils by deploying soil microbial fuel cells (sMFC). The results showed that the sMFC bioanode can significantly decrease the release of Fe and As into soil porewater. Iron and As contents around sMFC anode were 65.0% and 47.0% of the control respectively at day 50. The observed phenomenon would be explained by a competition for organic substrate between sMFC bioanode and the iron- and arsenic-reducing bacteria in the soils. In the vicinity of bioanode, organic matter removal efficiencies were 10.3% and 14.0% higher than the control for lost on ignition carbon and total organic carbon respectively. Sequencing of the 16S rRNA genes suggested that the influence of bioanodes on bulk soil bacterial community structure was minimal. Moreover, during the experiment a maximum current and power density of 0.31 mA and 12.0 mWm−2 were obtained, respectively. This study shows a novel way to limit the release of Fe and As in soils porewater and simultaneously generate electricity.

Typical Soil Redox Processes in Pentachlorophenol Polluted Soil Following Biochar Addition.

Reductive dechlorination is the primary pathway for environmental removal of pentachlorophenol (PCP) in soil under anaerobic condition. This process has been verified to be coupled with other soil redox processes of typical biogenic elements such as carbon, iron and sulfur. Meanwhile, biochar has received increasing interest in its potential for remediation of contaminated soil, with the effect seldom investigated under anaerobic environment. In this study, a 120-day anaerobic incubation experiment was conducted to investigate the effects of biochar on soil redox processes and thereby the reductive dechlorination of PCP under anaerobic condition. Biochar addition (1%, w/w) enhanced the dissimilatory iron reduction and sulfate reduction while simultaneously decreased the PCP reduction significantly. Instead, the production of methane was not affected by biochar. Interestingly, however, PCP reduction was promoted by biochar when microbial sulfate reduction was suppressed by addition of typical inhibitor molybdate. Together with Illumina sequencing data regarding analysis of soil bacteria and archaea responses, our results suggest that under anaerobic condition, the main competition mechanisms of these typical soil redox processes on the reductive dechlorination of PCP may be different in the presence of biochar. In particularly, the effect of biochar on sulfate reduction process is mainly through promoting the growth of sulfate reducer (Desulfobulbaceae and Desulfobacteraceae) but not as an electron shuttle. With the supplementary addition of molybdate, biochar application is suggested as an improved strategy for a better remediation results by coordinating the interaction between dechlorination and its coupled soil redox processes, with minimum production of toxic sulfur reducing substances and relatively small emission of greenhouse gas (CH4) while maximum removal of PCP.

The mechanisms and consequences of inorganic reactions during the production of ferrous sulphate enriched bamboo biochars

Magnetic biochars are implicated in graphene micro-crystallite formation, soil redox processes and highly adsorbent chars. This study investigates the mechanisms of bamboo charring – when impregnated with FeSO4·7H2O – at 250, 350, 450 and 550 °C, using thermal and static techniques.Impregnation resulted in the oxidation of Fe2+ to mixed Fe3+/Fe2+ (magnetite) oxide forms during pyrolysis. A reaction sequence was proposed in which Fe-sulphates were incorporated with an ammonia catalyst. Sulphur became ubiquitous in both inorganic and organic forms, and additional minerals also formed. Stable aromatics and separation of holo-cellulosic and degraded lignin volatilisation phases were catalysed, and carboxylation was inhibited. Concentrations of C fluctuated more substantially, before stabilising at high HTTs. Pyrolysis temperatures of 450 °C and above appear to maximise stable C concentrations.These observations indicated that this treatment may yield agriculturally engineered chars with enhanced redox potential, more neutral pH, and a range of nutrients.

Pine sawdust biomass and biochars at different pyrolysis temperatures change soil redox processes

To date, no investigation has been carried out to explore the effects of biochars produced at different pyrolysis temperatures on the dynamics of redox potential (EH) and pH in a contaminated floodplain soil. Thus, we aimed to quantify the dynamics of EH and pH in contaminated flooded soils treated with 70tha−1 of pine sawdust biomass (S&BM) and biochars pyrolyzed at 300°C (S&BC300) and 550°C (S&BC550) and pre-incubated for 105days in an automated biogeochemical microcosm system. Microbial community composition was also determined via analyzing phospholipid fatty acid (PLFA).We found that BC300 and BC550 treatments substantially decreased (3–6.5%) and BM increased (~37%) the mean of soil EH compared to the untreated contaminated soil (CS).·The largest EH decline in S&BC550 was at the rate of −80mVh−1 at 10h while it was observed at 25h in S&BC300 and 20–25h in S&BM or CS, respectively. At high EH, a higher total PLFA biomass and microbial groups in the CS (71–87%) were found in comparison to treated soils. Higher aromaticity and ash content in BC550 than BC300 and BM led to the greater PLFA biomass and microbial groups which contributed to higher capacity of accepting and donating electrons in soil slurry and were probably one reason for the largest decrease in EH. Pine sawdust biomass and BCs have a noticeable influence in soil biogeochemical processes relevant to fluctuating redox conditions.

Elemental sulfur amendment decreases bio-available Cr-VI in soils impacted by leather tanneries

This study investigated the potential use of elemental S (S0) to convert Cr-VI to Cr-III which should decrease the bio-availability hence, toxicity of Cr-VI in soils. The bio-available fraction of Cr in soil was measured by phosphate buffer extraction (PBE) and the results showed that the fraction is about 10% of the total Cr-VI and varied from 12.8 to 42.5 mg kg−1. The addition of 4.0 mg g−1 S0 decreased PBE Cr-VI to <0.4 mg kg−1 limit established for Cr-VI toxicity in soils. Synchrotron-based X-ray absorption near-edge structure (XANES), X-ray fluorescence (XRF) and micro-XRD revealed that Cr-III was the dominant species (99% of total Cr) and Cr was retained by hematite and goethite in soil. Fe-containing minerals may have provided sufficient protection to render the dominant Cr-III species biochemically inert to redox processes in soils. It is concluded that S0amendment is a promising approach to remediate Cr-VI contaminated soils.

The Electrochemical Properties of Biochars and How They Affect Soil Redox Properties and Processes

Biochars are complex heterogeneous materials that consist of mineral phases, amorphous C, graphitic C, and labile organic molecules, many of which can be either electron donors or acceptors when placed in soil. Biochar is a reductant, but its electrical and electrochemical properties are a function of both the temperature of production and the concentration and composition of the various redox active mineral and organic phases present. When biochars are added to soils, they interact with plant roots and root hairs, micro-organisms, soil organic matter, proteins and the nutrient-rich water to form complex organo-mineral-biochar complexes Redox reactions can play an important role in the development of these complexes, and can also result in significant changes in the original C matrix. This paper reviews the redox processes that take place in soil and how they may be affected by the addition of biochar. It reviews the available literature on the redox properties of different biochars. It also reviews how biochar redox properties have been measured and presents new methods and data for determining redox properties of fresh biochars and for biochar/soil systems.

The redox processes in Hg-contaminated soils from Descoberto (Minas Gerais, Brazil): Implications for the mercury cycle

Investigations of the redox process and chemical speciation of Hg(II) lead to a better understanding of biogeochemical processes controlling the transformation of Hg(II) into toxic and bioaccumulative monomethyl mercury, mainly in areas contaminated with Hg(0). This study investigates the speciation and redox processes of Hg in soil samples from a small area contaminated with Hg(0) as a result of gold mining activities in the rural municipality of Descoberto (Minas Gerais, Brazil). Soil samples were prepared by adding Hg(0) and HgCl2 separately to dry soil, and the Hg redox process was monitored using thermodesorption coupled to atomic absorption spectrometry. A portion of the Hg(0) added was volatilized (up to 37.4±2.0%) or oxidized (from 36±7% to 88±16%). A correlation with Mn suggests that this oxidation is favored, but many other factors must be evaluated, such as the presence of microorganisms and the types of organic matter present. The interaction of Hg with the matrix is suggested to involve Hg(II)-complexes formed with inorganic and organic sulfur ligands and/or nonspecific adsorption onto oxides of Fe, Al and/or Mn. The kinetics of the oxidation reaction was approximated for two first-order reactions; the faster reaction was attributed to the oxidation of Hg(0)/Hg(I), and the slower reaction corresponded to Hg(I)/Hg(II). The second stage was 43–139 times slower than the first. The samples spiked with Hg(II) showed low volatilization and a shifting of the signal of Hg(II) to lower temperatures. These results show that the extent, rate and type of redox process can be adverse in soils. Descoberto can serve as an example for areas contaminated with Hg(0).

Towards Understanding Temporal and Spatial Patterns of Molybdenum in the Critical Zone

Molybdenum (Mo) is a redox-sensitive element that has been used to constrain paleo-oxygen conditions in marine sediments and could potentially be used similarly in soils. Sedimentary Mo ultimately comes from the terrestrial weathering of rocks during soil development (pedogenesis), but the mechanisms controlling Mo loss and mobility in soils are not well known. Here we present Mo concentration data from soils and specific soil pools across two climatic gradients on the Hawaiian Islands, the Maui climate gradient (MCG) and the Kona climate gradient (KCG). The MCG is a well-established precipitation gradient that exhibits a decrease in soil Eh and Fe content and an increase in organic matter (OM) content with increasing rainfall. We expected to find lower Mo concentrations and lower Mo mobilization in highly reducing (greater rainfall) soils as a result of Fe reduction and near complete loss of Fe-oxyhydroxides. However, we observe higher weak acid leachable Mo concentrations at higher rainfall sites. Since high rainfall coincides with a loss of Fe by reductive dissolution and the accumulation of OM, suggesting a shift from Fe-oxyhydroxide control of Mo at low rainfall sites to predominately OM-control of Mo at high rainfall sites. Selective chemical extractions indicate that Mo concentrations are two orders of magnitude higher in the OM bound pool versus the Fe(Al) bound pool, corroborating the importance of Mo-OM interactions on overall soil Mo pools. We also find evidence for increasing Mo retention in wetter soils along the KCG, which may be a result of increasing OM and Fe and Al oxyhydroxide content. An alternate explanation is that higher rainfall contributes sufficiently greater marine-derived atmospheric input of Mo. The fact that there are consistent patterns with rainfall on both climate gradients illustrate the potential for Mo as a tracer of pedogenic and redox processes in soils and highlight the importance of constraining controls on Mo fluxes.

Soil Aeration Variability as Affected by Reoxidation

The interplay between soil physical parameters during the recovery from anoxic stresses (reoxidation) is largely unrecognized. This study was conducted to characterise the soil aeration status and derive correlations between variable aeration factors during reoxidation. Surface layers (0–30 cm) of three soil types, Haplic Phaeozem, Mollic Gleysol, and Eutric Cambisol (FAO soil group), were selected for analysis. The moisture content was determined for a range of pF values (0, 1.5, 2.2, 2.7, and 3.2), corresponding to the available water for microorganisms and plant roots. The variability of a number of soil aeration parameters, such as water potential (pF), air-filled porosity (Eg), oxygen diffusion rate (ODR), and redox potential (Eh), were investigated. These parameters were found to be interrelated in most cases. There were significant (P < 0.001) negative correlations of pF, Eg, and ODR with Eh. A decrease in water content as a consequence of soil reoxidation was manifested by an increase in the values of aeration factors in the soil environment. These results contributed to understanding of soil redox processes during recovery from flooding and might be useful for development of agricultural techniques aiming at soil reoxidation and soil fertility optimisation.

When Wet Gets Wetter: Decoupling of Moisture, Redox Biogeochemistry, and Greenhouse Gas Fluxes in a Humid Tropical Forest Soil

Upland humid tropical forest soils are often characterized by fluctuating redox dynamics that vary temporally and spatially across the landscape. An increase in the frequency and intensity of rainfall events with climate change is likely to affect soil redox reactions that control the production and emissions of greenhouse gases. We used a 24-day rainfall manipulation experiment to evaluate temporal and spatial trends of surface soil (0‐20 cm) redox-active chemical species and greenhouse gas fluxes in the Luquillo Experimental Forest, Puerto Rico. Treatments consisted of a high rainfall simulation (60 mm day -1 ), afl uctuating rainfall regime, and a control. Water addition generated high temporal and spatial variation in soil moisture (0.3‐0.6 m 3 m -3 ), but had no significant effect on soil oxygen (O2) concentrations. Extractable nitrate (NO3 - ) concentrations decreased with daily water additions and reduced iron (Fe(II)) concentrations increased towards the end of the experiment. Overall, redox indicators displayed a weak, non-deterministic, nonlinear relationship with soil moisture. High concentrations of Fe(II) and manganese (Mn) were present even where moisture was relatively low, and net Mn reduction occurred in all plots including controls. Mean CO2 fluxes were best explained by soil C concentrations and a composite redox indicator, and not water addition. Several plots were CH4 sources irrespective of water addition, whereas other plots oscillated between weak CH4 sources and sinks. Fluxes of N2 Ow ere highest in control plots and were consistently low in water-addition plots. Together, these data suggest (1) a relative decoupling between soil moisture and redox processes at our spatial and temporal scales of measurement, (2) the co-occurrence of aerobic and anaerobic biogeochemical processes in well-drained surface soils, and (3) an absence of threshold effects from sustained precipitation on redox reactions over the scale of weeks. Our data suggest a need to re-evaluate representations of moisture in biogeochemical models.