Iron-reducing Conditions Research Articles

Controlling exposure to As and Cd from rice via irrigation management

Irrigation management controls biogeochemical cycles in rice production. Under flooded paddy conditions, arsenic becomes plant-available as iron-reducing conditions ensue, while oxic conditions lead to increased plant availability of Cd in acidic soils. Because Cd enters rice through Mn transporters, we hypothesized that irrigation resulting in intermediate redox could simultaneously limit both As and Cd in rice grain due to As retention in soil and Mn competition for Cd uptake. In a 2 year field study, we used 6 irrigation managements that varied in extent and frequency of inundation, and we observed strong effects of irrigation management on porewater chemistry, soil redox potentials, plant As and Cd concentrations, plant nutrient concentrations, and methane emissions. Plant As decreased with drier irrigation management, but in the grain this effect was stronger for organic As than for inorganic As. Grain organic As, but not inorganic As, was strongly and positively correlated with cumulative methane emissions. Conversely, plant Cd increased under more aerobic irrigation management and grain Cd was negatively correlated with porewater Mn. A hazard index approach showed that in the tested soil with low levels of As and Cd (5.4 and 0.072 mg/kg, respectively), irrigation management could not simultaneously decrease grain As and Cd. Many soil properties, such as reducible As, available Cd, soil pH, available S, and soil organic matter should be considered when attempting to optimize irrigation management when the goal is decreasing the risk of As and Cd in rice grain.

Fate of sulfamethoxazole in wetland sediment under controlled redox conditions

Redox condition is an important controlling factor for contaminant removal in constructed wetlands; however, the redox-sensitivity of antibiotic removal in wetland sediments under controlled conditions with specific electron acceptors remains unclear. Here, using a 14C radioactive tracer, we explored fate of sulfamethoxazole (SMX) in a wetland sediment slurry under oxic, nitrate-reducing, iron-reducing, and methanogenic conditions. In the sterile treatment, unlike the comparable SMX dissipation from the water phase under four redox conditions, non-extractable residues (NERs) of SMX was highest formed in the sediment under oxic condition, mainly in sequestered and ester/amide-linked forms. Microorganisms markedly promoted SMX transformation in the slurry. The dissipation rate of SMX and its transformation products (TPs) followed the order: oxic ≈ iron-reducing > methanogenic >> nitrate-reducing conditions, being consistent with the dynamics of microbial community in the sediment, where microbial diversity was greater and networks connectivity linking dominant bacteria to SMX transformation were more complex under oxic and iron-reducing conditions. Kinetic modeling indicated that the transformation trend of SMX and its TPs into the endpoint pool NERs depended on the redox conditions. Addition of wetland plant exudates and sediment dissolved organic matter at environmental concentrations affected neither the abiotic nor the biotic transformation of SMX. Overall, the iron-reducing condition was proven the most favorable and eco-friendly for SMX transformation, as it resulted in a high rate of SMX dissipation from water without an increase in toxicity and subsequent formation of significant stable NERs in sediment. Our study comprehensively revealed the abiotic and biotic transformation processes of SMX under controlled redox conditions and demonstrated iron-reducing condition allowing optimal removal of SMX in constructed wetlands.

Influence of redox condition and inoculum on micropollutant biodegradation by soil and activated sludge communities

Micropollutant biodegradation is selected by the interplay among environmental conditions and microbial community composition. This study investigated how different electron acceptors, and different inocula with varying microbial diversity, pre-exposed to distinct redox conditions and micropollutants, affect micropollutant biodegradation. Four tested inocula comprised of agricultural soil (Soil), sediment from a ditch in an agricultural field (Ditch), activated sludge from a municipal WWTP (Mun AS), and activated sludge from an industrial WWTP (Ind AS). Removal of 16 micropollutants was investigated for each inoculum under aerobic, nitrate reducing, iron reducing, sulfate reducing, and methanogenic conditions. Micropollutant biodegradation was highest under aerobic conditions with removal of 12 micropollutants. Most micropollutants were biodegraded by Soil (n = 11) and Mun AS inocula (n = 10). A positive correlation was observed between inoculum community richness and the number of different micropollutants a microbial community initially degraded. The redox conditions to which a microbial community had been exposed appeared to positively affect micropollutant biodegradation performance more than pre-exposure to micropollutants. Additionally, depletion of the organic carbon present in the inocula resulted in lower micropollutant biodegradation and overall microbial activities, suggesting that i) an additional carbon source is needed to promote micropollutant biodegradation; and ii) overall microbial activity can be a good indirect indicator for micropollutant biodegradation activity. These results could help to develop novel micropollutant removal strategies.

Biodegradation of trace sulfonamide antibiotics accelerated by substrates across oxic to anoxic conditions during column infiltration experiments

Frequent occurrence of trace organic contaminants in aquatic environments, such as sulfonamide antibiotics in rivers receiving reclaimed water, is concerning. Natural attenuation by soil and sediment is increasingly relied upon. In the case of riverbank filtration for water purification, the reliability of antibiotic attenuation has been called into question due to incomplete understanding of their degradation processes. This study investigated influence of substrates and redox evolution along infiltration path on biotransformation of sulfonamides. Eight sand columns (length: 28 cm) with a riverbed sediment layer at 3–8 cm were fed by groundwater-sourced tap water spiked with 1 μg/L of sulfadiazine (SDZ), sulfamethazine (SMZ), and sulfamethoxazole (SMX) each, with or without amendments of dissolved organic carbon (5 mg-C/L of 1:1 yeast and humics) or ammonium (5 mg-N/L). Two flow rates were tested over 120 days (0.5 mL/min and 0.1 mL/min). Iron-reducing conditions persisted in all columns for 27 days during the initial high flow period due to respiration of sediment organics, evolving to less reducing conditions until the subsequent low flow period to resume more reducing conditions. With surplus substrates, the spatial and temporal patterns of redox conditions differentiated among columns. The removal of SDZ and SMZ in effluents was usually low (15 ± 11%) even with carbon addition (14 ± 9%), increasing to 33 ± 23% with ammonium addition. By contrast, SMX removal was higher and more consistent among columns (46 ± 21%), with the maximum of 64 ± 9% under iron-reducing conditions. When sulfonamide removal was compared between columns for the same redox zones during infiltration, their enhancements were always associated with the availability of dissolved or particulate substrates, suggesting co-metabolism. Manipulation of the exposure time to optimal redox conditions with substrate amendments, rather than to simply prolong the overall residence time, is recommended for nature-based solutions to tackle target antibiotics.

Influence of clay mineral weathering on green rust formation at iron-reducing conditions

Green rusts (GR) are important drivers for trace metal and nutrient cycling in suboxic environments. We investigated whether green rusts would incorporate aluminum (Al) or other elements from naturally-formed clay minerals containing easily-weatherable clay minerals (e.g. mica, interlayered clays). We isolated the clay minerals from a Matapeake silt loam soil by removal of silt and sand, organic matter, and reducible oxides to study mechanisms of interaction between Fe(II) and soil-sourced clay minerals. We conducted batch Fe(II) sorption experiments at multiple near-neutral pHs (6.5–7.5) and reaction times (2 h–365 days). Mineral transformations were characterized by selective extractions, X-ray diffraction (XRD), and Fe X-ray absorption spectroscopy (XAS) analyzed by shell-fitting and linear combination fitting (LCF) with natural and synthetic standards.Clay mineral fraction contained a mixture of quartz, kaolinite, interlayered vermiculite, mica, and chlorite with significant structural Fe (2.6% wt). Uptake of Fe(II) increased with pH and kinetics were rapid until 5 days, followed by slow continuous Fe(II) uptake. Citrate-bicarbonate desorption kinetics from Fe(II) sorbed clay released more Al and silicon (Si) compared with unreacted soil clay fraction whereas magnesium (Mg) and potassium (K) were unaffected. Citrate-bicarbonate extracted Fe contained more Fe(II) than an ideal GR with an Fe(II)/Fe(III) molar ratio of 5.50. Analysis of the Fe EXAFS by both LCF and shell fitting was best modeled as a combination of Fe(III)-clay reduction to Fe(II) and precipitation of GR and Fe(II)-Al LDH. After 7 days of Fe(II) sorption, LCF identified 55.2% total Fe in clay, 33.4% GR(Cl) and 11.4% Fe(II)-Al LDH. These results provide novel evidence of Fe(II)-Al LDHs precipitating on naturally-formed soil clay minerals as a minor phase to GR. The geochemical implications are that GRs formed in soils and sediments should be considered to have Al and Si as well as Mg substitutions affecting their structure and reactivity.

Modeling the kinetics of perfluorooctanoic and perfluorooctane sulfonic acid biodegradation by Acidimicrobium sp. Strain A6 during the feammox process

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants of concern due to their health effects and persistence in the environment. Although perfluoroalkyl acids (PFAAs), such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are very difficult to biodegrade because they are completely saturated with fluorine, it has recently been shown that Acidimicrobium sp. A6 (A6), which oxidizes ammonium under iron reducing conditions (Feammox process), can defluorinate PFAAs. A kinetic model was developed and tested in this study using results from previously published laboratory experiments, augmented with results from additional incubations, to couple the Feammox process to PFAS defluorination. The experimental results show higher Feammox activity and PFAS degradation in the A6 enrichment cultures than in the highly enriched A6 cultures. The coupled experimental and modeling results show that the PFAS defluorination rate is proportional to the rate of ammonium oxidation. The ammonium oxidation rate and the defluorination rate increase monotonically, but not linearly, with increasing A6 biomass. Given that different experiments had different level of Feammox activity, the parameters required to simulate the Feammox varied between A6 cultures. Nonetheless, the kinetic model was able to simulate an anaerobic incubation system and show that PFAS defluorination is proportional to the Feammox activity.

Biotransformation of 8:2 Fluorotelomer Alcohol in Soil from Aqueous Film-Forming Foams (AFFFs)-Impacted Sites under Nitrate-, Sulfate-, and Iron-Reducing Conditions

The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) remains largely unknown, especially under the conditions representative of natural subsurface systems. In this study, the biotransformation of 8:2 fluorotelomer alcohol (8:2 FTOH), a component of new-generation AFFF formulations and a byproduct in fluorotelomer-based AFFFs, was investigated under nitrate-, iron-, and sulfate-reducing conditions in microcosms prepared with AFFF-impacted soils. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (HRMS) were employed to identify biotransformation products. The biotransformation was much slower under sulfate- and iron-reducing conditions with >60 mol % of initial 8:2 FTOH remaining after ∼400 days compared to a half-life ranging from 12.5 to 36.5 days under nitrate-reducing conditions. Transformation products 8:2 fluorotelomer saturated and unsaturated carboxylic acids (8:2 FTCA and 8:2 FTUA) were detected under all redox conditions, while 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were only observed as transformation products under nitrate-reducing conditions. In addition, 1H-perfluoroheptane (F(CF2)6CF2H) and 3-F-7:3 acid (F(CF2)7CFHCH2COOH) were identified for the first time during 8:2 FTOH biotransformation. Comprehensive biotransformation pathways for 8:2 FTOH are presented, which highlight the importance of accounting for redox condition and the related microbial community in the assessment of PFAS transformations in natural environments.

Anaerobic degradation of benzene and other aromatic hydrocarbons in a tar-derived plume: Nitrate versus iron reducing conditions

The anaerobic degradation of aromatic hydrocarbons in a plume originating from a Pintsch gas tar-DNAPL zone was investigated using molecular, isotopic- and microbial analyses. Benzene concentrations diminished at the relatively small meter scale dimensions of the nitrate reducing plume fringe. The ratio of benzene to toluene, ethylbenzene, xylenes and naphthalene (BTEXN) in the fringe zone compared to the plume zone, indicated relatively more loss of benzene in the fringe zone than TEXN. This was substantiated by changes in relative concentrations of BTEXN, and multi-element compound specific isotope analysis for δ2H and δ13C. This was supported by the presence of (abcA) genes, indicating the presumed benzene carboxylase enzyme in the nitrate-reducing plume fringe. Biodegradation of most hydrocarbon contaminants at iron reducing conditions in the plume core, appears to be quantitatively of greater significance due to the large volume of the plume core, rather than relatively faster biodegradation under nitrate reducing conditions at the smaller volume of the plume fringe. Contaminant concentration reductions by biodegradation processes were shown to vary distinctively between the source, plume (both iron-reducing) and fringe (nitrate-reducing) zones of the plume. High anaerobic microbial activity was detected in the plume zone as well as in the dense non aqueous phase liquid (DNAPL) containing source zone. Biodegradation of most, if not all, other water-soluble Pintsch gas tar aromatic hydrocarbon contaminants occur at the relatively large dimensions of the anoxic plume core. The highest diversity and concentrations of metabolites were detected in the iron-reducing plume core, where the sum of parent compounds of aromatic hydrocarbons was greater than 10 mg/L. The relatively high concentrations of metabolites suggest a hot spot for anaerobic degradation in the core of the plume downgradient but relatively close to the DNAPL containing source zone.

Fe(II) Induced Reduction of Incorporated U(VI) to U(V) in Goethite.

Over 60 years of nuclear activities have resulted in a global legacy of radioactive wastes, with uranium considered a key radionuclide in both disposal and contaminated land scenarios. With the understanding that U has been incorporated into a range of iron (oxyhydr)oxides, these minerals may be considered a secondary barrier to the migration of radionuclides in the environment. However, the long-term stability of U-incorporated iron (oxyhydr)oxides is largely unknown, with the end-fate of incorporated species potentially impacted by biogeochemical processes. In particular, studies show that significant electron transfer may occur between stable iron (oxyhydr)oxides such as goethite and adsorbed Fe(II). These interactions can also induce varying degrees of iron (oxyhydr)oxide recrystallization (<4% to >90%). Here, the fate of U(VI)-incorporated goethite during exposure to Fe(II) was investigated using geochemical analysis and X-ray absorption spectroscopy (XAS). Analysis of XAS spectra revealed that incorporated U(VI) was reduced to U(V) as the reaction with Fe(II) progressed, with minimal recrystallization (approximately 2%) of the goethite phase. These results therefore indicate that U may remain incorporated within goethite as U(V) even under iron-reducing conditions. This develops the concept of iron (oxyhydr)oxides acting as a secondary barrier to radionuclide migration in the environment.

Biogeochemical dynamics and microbial community development under sulfate- and iron-reducing conditions based on electron shuttle amendment.

Iron reduction and sulfate reduction are two of the major biogeochemical processes that occur in anoxic sediments. Microbes that catalyze these reactions are therefore some of the most abundant organisms in the subsurface, and some of the most important. Due to the variety of mechanisms that microbes employ to derive energy from these reactions, including the use of soluble electron shuttles, the dynamics between iron- and sulfate-reducing populations under changing biogeochemical conditions still elude complete characterization. Here, we amended experimental bioreactors comprised of freshwater aquifer sediment with ferric iron, sulfate, acetate, and the model electron shuttle AQDS (9,10-anthraquinone-2,6-disulfonate) and monitored both the changing redox conditions as well as changes in the microbial community over time. The addition of the electron shuttle AQDS did increase the initial rate of FeIII reduction; however, it had little effect on the composition of the microbial community. Our results show that in both AQDS- and AQDS+ systems there was an initial dominance of organisms classified as Geobacter (a genus of dissimilatory FeIII-reducing bacteria), after which sequences classified as Desulfosporosinus (a genus of dissimilatory sulfate-reducing bacteria) came to dominate both experimental systems. Furthermore, most of the ferric iron reduction occurred under this later, ostensibly “sulfate-reducing” phase of the experiment. This calls into question the usefulness of classifying subsurface sediments by the dominant microbial process alone because of their interrelated biogeochemical consequences. To better inform models of microbially-catalyzed subsurface processes, such interactions must be more thoroughly understood under a broad range of conditions.

Functional Interrelationships of Microorganisms in Iron-Based Anaerobic Wastewater Treatment.

This study explicated the functional activities of microorganisms and their interrelationships under four previously reported iron reducing conditions to identify critical factors that governed the performance of these novel iron-dosed anaerobic biological wastewater treatment processes. Various iron-reducing bacteria (FeRB) and sulfate reducing bacteria (SRB) were identified as the predominant species that concurrently facilitated organics oxidation and the main contributors to removal of organics. The high organic contents of wastewater provided sufficient electron donors for active growth of both FeRB and SRB. In addition to the organic content, Fe (III) and sulfate concentrations (expressed by Fe/S ratio) were found to play a significant role in regulating the microbial abundance and functional activities. Various fermentative bacteria contributed to this FeRB-SRB synergy by fermenting larger organic compounds to smaller compounds, which were subsequently used by FeRB and SRB. Feammox (ferric reduction coupled to ammonium oxidation) bacterium was identified in the bioreactor fed with wastewater containing ammonium. Organic substrate level was a critical factor that regulated the competitive relationship between heterotrophic FeRB and Feammox bacteria. There were evidences that suggested a synergistic relationship between FeRB and nitrogen-fixing bacteria (NFB), where ferric iron and organics concentrations both promoted microbial activities of FeRB and NFB. A concept model was developed to illustrate the identified functional interrelationships and their governing factors for further development of the iron-based wastewater treatment systems.

Anaerobic benzene mineralization by natural microbial communities from Niger Delta

The Niger Delta is one of the most damaged ecosystems in the world, mainly due to petroleum contamination by oil exploration accidents. We investigated the natural attenuation potential of Niger Delta subsurface sediment samples for anaerobic hydrocarbon degradation using benzene as a model compound under iron-reducing, sulfate-reducing, and methanogenic conditions. Benzene was slowly mineralized under methanogenic and iron-reducing conditions using nitrilotriacetic acid (NTA)-Fe(III), or poorly crystalline Fe(III) oxyhydroxides as electron acceptors, analyzed by measurement of 13CO2 produced from added 13C-labelled benzene. Highest mineralization rates were observed in microcosms amended with Fe(III) oxyhydroxides. The microbial communities of benzene-mineralizing enrichment cultures were characterized by next-generation sequencing of the genes coding for 16S rRNA and methyl coenzyme M reductase A (mcrA). Abundant phylotypes were affiliated to Betaproteobacteriales, Ignavibacteriales, Desulfuromonadales, and Methanosarcinales of the genera Methanosarcina and Methanothrix, illustrating that the enriched benzene-mineralizing communities were diverse and may contain more than a single benzene degrader. The diversity of the microbial communities was furthermore confirmed by scanning helium-ion microscopy which revealed the presence of various rod-shaped as well as filamentous microbial morphotypes.

Characterization and comparison of groundwater quality and redox conditions in the Arakawa Lowland and Musashino Upland, southern Kanto Plain of the Tokyo Metropolitan area, Japan

Groundwater is essential for the Earth biosphere but is often contaminated by harmful chemical compounds due to both anthropogenic and natural causes. A key factor controlling the fate of harmful chemicals in groundwater is the reduction/oxidation (redox) conditions. The formation factors for the groundwater redox conditions are insufficiently understood. In this study, long-term groundwater quality beneath one of the world megacities was monitored and evaluated. We measured and compared hydrogeochemical conditions including groundwater quality (35 chemical parameters) and redox conditions of five aquifers in the Arakawa Lowland and Musashino Upland, southern Kanto Plain of the Tokyo Metropolitan area, Japan. Monitoring results suggested the following: The main origin of groundwater is precipitation in both the Lowland and Upland areas. The three aquifers in the Arakawa Lowland are likely fully separated, with one unconfined and two confined aquifers under iron reducing and methanogenic conditions, respectively. Oppositely, in the Musashino Upland, the water masses in the two aquifers are likely partly connected, under aerobic conditions, and undergoing the same groundwater recharge and flow processes under similar hydrogeological conditions. The different groundwater redox conditions observed are likely caused by the very different groundwater residence times for the Arakawa Lowland and Musashino Upland.

The Behavior of Low Molecular Weight Organic Carbon-14 Containing Compounds in Contaminated Groundwater During Denitrification and Iron-Reduction

Aqueous low molecular weight organic carbon-14 (14C) substances can be formed by the oxidation of carbide and impurities within nuclear fuel cladding. During reprocessing and interim storage 14C-labeled organic compounds may leak to the shallow subsurface environments at nuclear facilities where denitrifying and iron reducing zones can exist. 14C-labeled organic compounds (acetate, formate, formaldehyde and methanol) were used as electron donors in microcosm experiments, under both denitrification and iron reduction, using glacial outwash sediments and groundwater composition representative of the Sellafield nuclear reprocessing site, UK. In denitrifying microcosms, <6% of the initial 14C-DOC remained 15 days after injection into the microcosm irrespective of the electron donor; with concurrent 14CO2 (g) production. Lack of removal in sterile controls suggests that 14C-organics were metabolized by microorganisms. Under iron-reducing conditions both 14C-carboxylates were removed from solution rapidly, but some formaldehyde and methanol remained in solution 32 days after injection into the microcosm so there is potential that a proportion of 14C-formaldehyde and 14C-methanol may persist for longer in subsurface environments.

Phosphate Induced Arsenic Mobilization as a Potentially Effective In-Situ Remediation Technique—Preliminary Column Tests

Arsenic (As) contamination of groundwater is commonly remediated by pump and treat. However, this technique is difficult to apply or maintain efficiently because the mobility of arsenic varies depending on the geochemical aquifer conditions. Arsenic interacting with the sediment can cause strong retardation, which is counteracted by ions competing for sedimentary sorption sites like silica, bicarbonate and phosphate. Phosphate competes most effectively with arsenic for sorption sites due to its chemical similarity. To accelerate an ongoing but ineffective pump and treat remediation, we examined the competitive effect of increasing phosphate doses on contaminated aquifer material of different depths and thus under distinct geochemical conditions. In the columns with phosphate addition, significant amounts of arsenic were released rapidly under oxic and anoxic conditions. In all tests, the grade of leaching was higher under anoxic conditions than under oxic conditions. As(III) was the dominant species, in particular during the first release peaks and the anoxic tests. Higher amounts of phosphate did not trigger the arsenic release further and led to a shift of arsenic species. We suggest that the competitive surface complexation is the major process of arsenic release especially when higher amounts of phosphate are used. Commonly arsenic release is described at iron reducing conditions. In contrast, we observed that a change in prevailing redox potential towards manganese reducing conditions in the oxic tests and iron reducing conditions in the anoxic column took place later and thus independently of arsenic release. The reduction of As(V) to As(III) under both redox conditions is presumed to be an effect of microbial detoxification. A loss of sulphate in all columns with phosphate indicates an increased microbial activity, which might play a significant role in the process of arsenic release. Preliminary tests with sediment material from a contaminated site showed that phosphate additions did not change the pH value significantly. Therefore, a release of other metals is not likely. Our results indicate that in-situ application of phosphate amendments to arsenic-contaminated sites could accelerate and enhance arsenic mobility to improve the efficiency of pump and treat remediation without negative side effects. The novelty of this approach is the use of only small amounts of phosphate in order to stimulate microbial activity in addition to surface complexation. Therefore, this method might become an innovative and cost-effective remediation for arsenic contaminated sites.

Anaerobic phenanthrene biodegradation with four kinds of electron acceptors enriched from the same mixed inoculum and exploration of metabolic pathways

Polycyclic aromatic hydrocarbons (PAHs) are widespread and persistent contaminants worldwide, especially in environments devoid of molecular oxygen. For lack of molecular oxygen, researchers enhanced anaerobic zones PAHs biodegradation by adding sulfate, bicarbonate, nitrate, and iron. However, microbial community reports of them were limited, and information of metabolites was poor except two-ring PAH, naphthalene. Here, we reported on four phenanthrene-degrading enrichment cultures with sulfate, bicarbonate, nitrate, and iron as electron acceptors from the same initial inoculum. The high-to-low order of the anaerobic phenanthrene biodegradation rate was the nitrate-reducing conditions>sulfate-reducing conditions>methanogenic conditions>iron-reducing conditions. The dominant bacteria populations were Desulfobacteraceae, Anaerolinaceae, and Thermodesulfobiaceae under sulfate-reducing conditions; Moraxellaceae, Clostridiaceae, and Comamonadaceae under methanogenic conditions; Rhodobacteraceae, Planococcaceae, and Xanthomonadaceae under nitrate-reducing conditions; and Geobacteraceae, Carnobacteriaceae, and Anaerolinaceae under iron-reducing conditions, respectively. Principal component analysis (PCA) indicated that bacteria populations of longtime enriched cultures with four electron acceptors all obtained significant changes from original inoculum, and bacterial communities were similar under nitrate-reducing and iron-reducing conditions. Archaea accounted for a high percentage under iron-reducing and methanogenic conditions, and Methanosarcinaceae and Methanobacteriaceae, as well as Methanobacteriaceae, were the dominant archaea populations under iron-reducing and methanogenic conditions. The key steps of phenanthrene biodegradation under four reducing conditions were carboxylation, further ring system reduction, and ring cleavage.

Degradation of tetra- and trichloroethylene under iron reducing conditions by Acidimicrobiaceae sp. A6

The degradation of trichloroethylene (TCE) and tetrachloroethylene (PCE), in incubations where ammonium was oxidized while iron was being reduced indicates that these compounds can be degraded during the Feammox process by Acidimicrobiaceae sp. A6 (ATCC, PTA-122488). None of these compounds were degraded in incubations to which no ammonium was added, indicating that they were degraded during the oxidation of ammonium. Degradation of TCE and PCE (ranging between 32% and 55%) was observed in incubations with a pure Acidimicrobiaceae sp. A6 culture as well as an Acidimicrobiaceae sp. A6 enrichment culture over a 2-week period. In addition to these batch studies, a column study, with a 5-h hydraulic residence time, was conducted contrasting the degradation of TCE in iron-rich soil columns that were either seeded with a pure or an enrichment culture of Acidimicrobiaceae sp. A6 to achieve ammonium oxidation under iron reduction, and a control column that was initially not seeded and later seeded with Geobacter metallireducens. While there was ∼22% TCE removal in the columns seeded with Acidimicrobiaceae sp. A6, there was no removal in the unseeded column or the column seeded with G. metallireducens which was being operated under iron reducing conditions. Feammox is an anoxic process that requires acidic conditions. Hence, these results indicate that this process might be harnessed where other bioremediation strategies are difficult, since many require neutral or alkaline conditions, and supplying ammonium to an anoxic aquifer is relatively easy, since there are not many processes that will oxidize ammonium in the absence of dissolved oxygen.

The electrifying physiology of Geobacter bacteria, 30 years on.

The family Geobacteraceae, with its only valid genus Geobacter, comprises deltaproteobacteria ubiquitous in soil, sediments, and subsurface environments where metal reduction is an active process. Research for almost three decades has provided novel insights into environmental processes and biogeochemical reactions not previously known to be carried out by microorganisms. At the heart of the environmental roles played by Geobacter bacteria is their ability to integrate redox pathways and regulatory checkpoints that maximize growth efficiency with electron donors derived from the decomposition of organic matter while respiring metal oxides, particularly the often abundant oxides of ferric iron. This metabolic specialization is complemented by versatile metabolic reactions, respiratory chains, and sensory networks that allow specific members to adaptively respond to environmental cues to integrate organic and inorganic contaminants in their oxidative and reductive metabolism, respectively. Thus, Geobacteraceae are important members of the microbial communities that degrade hydrocarbon contaminants under iron-reducing conditions and that contribute, directly or indirectly, to the reduction of radionuclides, toxic metals, and oxidized species of nitrogen. Their ability to produce conductive pili as nanowires for discharging respiratory electrons to solid-phase electron acceptors and radionuclides, or for wiring cells in current-harvesting biofilms highlights the unique physiological traits that make these organisms attractive biological platforms for bioremediation, bioenergy, and bioelectronics application. Here we review some of the most notable physiological features described in Geobacter species since the first model representatives were recovered in pure culture. We provide a historical account of the environmental research that has set the foundation for numerous physiological studies and the laboratory tools that had provided novel insights into the role of Geobacter in the functioning of microbial communities from pristine and contaminated environments. We pay particular attention to latest research, both basic and applied, that has served to expand the field into new directions and to advance interdisciplinary knowledge. The electrifying physiology of Geobacter, it seems, is alive and well 30 years on.

Stability of Ferrihydrite-Humic Acid Coprecipitates under Iron-Reducing Conditions.

Recent studies have suggested the potential for release of iron (hydr)oxide-bound organic carbon (OC) during dissimilatory iron oxide reduction (DIR). However, the stability of iron (hydr)oxide-bound OC in the presence of a natural microbial consortium capable of driving both OC metabolism and DIR has not been resolved. Pure ferrihydrite (Fhy) and Fhy-humic acid coprecipitates (Fhy-HA) were inoculated with a small quantity of freshwater sediment and incubated under anoxic conditions in the presence and absence of H2 or glucose as electron donors for DIR. H2 promoted DIR led to release of ca. 1 mM dissolved organic carbon (DOC). However, comparable amounts of DOC were released from both pure Fhy and Fhy-HA, similar to DOC levels in mineral-free, inoculum-only controls. These results suggest that the observed DOC release during H2-promoted DIR originated from OC contained in the inoculum as opposed to the much larger pool (ca. 38 mM) of OC in the Fhy-HA. Thus, DIR preferentially released sorbed OC with low aromaticity (inoculum OC) versus highly aromatic OC (HA) coprecipitated with iron oxide. Our findings provide new insight into the extent and mechanisms by which DIR is likely to influence aqueous/solid-phase OC partitioning in anoxic soils and sediments.

Alteration of gaseous nitrogen losses via anaerobic ammonium oxidation coupled with ferric reduction from paddy soils in Southern China

The bacteria-mediated anaerobic ammonium oxidation under iron reducing conditions, termed feammox, represents a process for alleviating N accumulation in anoxic soils. Fertilization, as an important agricultural strategy, needs to be investigated in order to determine its effects on nitrogen (N) removal via the feammox process in paddy soils. In this study, a slurry incubation experiment was conducted in fertilized paddy soils with a gradient of microbial reducible Fe(III) levels obtained from Southern China using 15N-isotope tracing techniques. Four fertilizer treatments were examined: an un-fertilized control (NF), chemical fertilizers (CF), chemical fertilizers plus manure (CMF) and chemical fertilizers plus crop straw (CSF). It was estimated that the potential N losses linked with feammox were 3.6–24.9 kg N ha−1 y−1 in all the examined soils. Compared to the unfertilized soil (NF), fertilization stimulated feammox and led to higher (3.4–5.8 times) N losses. We postulate that the variations in the extent and rate of feammox between the unfertilized and fertilized soils were most likely due to differences in the abundance of the Acidimicrobiaceae bacterium A6 and the amounts of microbial reducible Fe(III). Further, the variations between soil treated with fertilizer (CF) only and soils coupled organic-chemical fertilizer (CMF and CSF) were due to the differences in the electron transfer mechanism mediated by electron shuttles from bacteria to Fe(III) minerals arising from the organic carbon applied. Overall, this study clearly illustrated the stimulatory effects of fertilization on feammox that resulted in higher N losses and suggested that feammox could be a crucial N removal pathway in paddy soils.