ALBERT

Description: Anaerobic nitrate-dependent Fe(II) oxidation (NDFeO) is widespread in various aquatic environments and plays a major role in iron and nitrogen redox dynamics. However, evidence for truly enzymatic, autotrophic NDFeO remains limited, with alternative explanations involving the coupling of heterotrophic denitrification with the abiotic oxidation of structurally bound or aqueous Fe(II) by reactive intermediate nitrogen (N) species (chemodenitrification). The extent to which chemodenitrification is caused (or enhanced) by ex vivo surface catalytic effects has not been directly tested to date. To determine whether the presence of either an Fe(II)-bearing mineral or dead biomass (DB) catalyses chemodenitrification, two different sets of anoxic batch experiments were conducted: 2 mM Fe(II) was added to a low-phosphate medium, resulting in the precipitation of vivianite (Fe3(PO4)2), to which 2 mM nitrite (NO2-) was later added, with or without an autoclaved cell suspension (∼1.96×108 cells mL−1) of Shewanella oneidensis MR-1. Concentrations of nitrite (NO2-), nitrous oxide (N2O), and iron (Fe2+, Fetot) were monitored over time in both set-ups to assess the impact of Fe(II) minerals and/or DB as catalysts of chemodenitrification. In addition, the natural-abundance isotope ratios of NO2- and N2O (δ15N and δ18O) were analysed to constrain the associated isotope effects. Up to 90 % of the Fe(II) was oxidized in the presence of DB, whereas only ∼65 % of the Fe(II) was oxidized under mineral-only conditions, suggesting an overall lower reactivity of the mineral-only set-up. Similarly, the average NO2- reduction rate in the mineral-only experiments (0.004±0.003 mmol L−1 d−1) was much lower than in the experiments with both mineral and DB (0.053±0.013 mmol L−1 d−1), as was N2O production (204.02±60.29 nmol L−1 d−1). The N2O yield per mole NO2- reduced was higher in the mineral-only set-ups (4 %) than in the experiments with DB (1 %), suggesting the catalysis-dependent differential formation of NO. N-NO2- isotope ratio measurements indicated a clear difference between both experimental conditions: in contrast to the marked 15N isotope enrichment during active NO2- reduction (15εNO2=+10.3 ‰) observed in the presence of DB, NO2- loss in the mineral-only experiments exhibited only a small N isotope effect (

Description: Iron plaque on rice roots represents a sink and source of iron in paddy fields. However, the extent of iron plaque in impacting paddy field iron cycling is not yet fully deciphered. Here, we followed iron plaque formation during plant growth in laboratory-controlled setups containing a transparent soil matrix. Using image analysis, microsensor measurements, and mineral extractions, we demonstrate that radial oxygen loss (ROL) is the main driver for rhizosphere iron oxidation. While O2 was restricted to the vicinity of roots, root tips showed highest spatio-temporal variation in ROL (30% of the total root surface corresponding to 60–180 mg Fe(III) per gram dried root and gradually transformed from low-crystalline minerals (e.g., ferrihydrite) on root tips, to 〉20% higher-crystalline minerals (e.g., goethite) within 40 days. Iron plaque exposed to an Fe(III)-reducing Geobacter spp. culture resulted in 30% Fe(II) remobilization and 〉50% microbial transformation to Fe(II) minerals (e.g., siderite, vivianite, and Fe–S phases) or persisted by 〉15% as Fe(III) minerals. Based on the collected data, we estimated that iron plaque formation and reductive dissolution can impact more than 5% of the rhizosphere iron budget which has consequences for the (im)mobilization of soil contaminants and nutrients.

Description: Chloroform (CF) is an environmental contaminant that can be naturally formed in various environments ranging from forest soils to salt lakes. Here we investigated CF removal potential in sediments obtained from hypersaline lakes in Western Australia. Reductive dechlorination of CF to dichloromethane (DCM) was observed in enrichment cultures derived from sediments of Lake Strawbridge, which has been reported as a natural source of CF. No CF removal was observed in abiotic control cultures without artificial electron donors, indicating biotic CF dechlorination in the enrichment cultures. Increasing vitamin B12 concentration from 0.04 to 4 µM in enrichment cultures enhanced CF removal and reduced DCM formation. In cultures amended with 4 µM vitamin B12 and 13C labelled CF, formation of 13CO2 was detected. Known organohalide-respiring bacteria and reductive dehalogenase genes were neither detected using quantitative PCR nor metagenomic analysis of the enrichment cultures. Rather, members of the order Clostridiales, known to co-metabolically transform CF to DCM and CO2, were detected. Accordingly, metagenome-assembled genomes of Clostridiales encoded enzymatic repertoires for the Wood-Ljungdahl pathway and cobalamin biosynthesis, which are known to be involved in fortuitous and nonspecific CF transformation. This study indicates that hypersaline lake microbiomes may act as a filter to reduce CF emission to the atmosphere.

Description: Soil organic matter (SOM), including humic substances (HS), is redox-active, can be microbially reduced, and transfers electrons in an abiotic reaction to Fe(III) minerals thus serving as electron shuttle. The standard procedure to extract HS from soil and separate them into humic acids (HA) and fulvic acids (FA) involves alkaline and acidic solutions potentially leading to unwanted changes in SOM chemical and redox properties. To determine the effects of extraction conditions on the redox and electron shuttling properties of SOM extracts, we prepared HS and SOM extracts from a forest soil applying either a combination of 0.1 M NaOH and 6 M HCl, or water (pH 7). Both chemical extractions (NaOH / HCl) and water extractions were done in separate setups under either oxic or anoxic conditions. Furthermore, we applied the NaOH / HCl treatment to a subsample of the water-extracted-SOM. We found that soil extraction with NaOH lead to ca. 100 times more extracted C and the extracted HS had 2–3 times higher electron exchange capacities (EEC) than SOM extracted by water. For water-extracted SOM, anoxic extraction conditions lead to about 7 times more extracted C and 1.5 times higher EEC than under oxic extraction conditions. This difference was probably due to the occurrence of microbial reduction and dissolution of Fe(III) minerals in the soil during the water extraction at neutral pH and the concomitant release of Fe(III) mineral-bound organic matter. NaOH / HCl treatment of the water-extracted SOM lead to 2 times higher EEC values in the HA isolated from the SOM compared to the water-extracted SOM itself, suggesting the chemical treatment with NaOH and HCl caused changes of redox-active functional groups of the extracted organic compounds. Higher EEC of extracts in turn resulted in a higher stimulation of microbial Fe(III) mineral reduction by electron shuttling, i.e. faster initial Fe(III) reduction rates, and in most cases also in higher reduction extents. Our findings suggest that SOM extracted with water at neutral pH should be used to better reflect environmental SOM redox processes in lab experiments and that potential artefacts of the chemical extraction method and anoxic extraction condition need to be considered when evaluating and comparing abiotic and microbial SOM redox processes.

Description: Soil organic matter (SOM) is redox-active, can be microbially reduced, and transfers electrons in an abiotic reaction to Fe(III) minerals, thus serving as an electron shuttle. The standard procedure to isolate organic matter (OM) from soil involves the use of alkaline and acidic solutions and the separation of humic acids (HAs) and fulvic acids (FAs). This process potentially leads to unwanted changes in SOM chemical and redox properties. To determine the effects of extraction conditions on the redox and electron-shuttling properties of SOM extracts, we prepared HA, FA, and water-extractable organic matter (OM) extracts, applying either a combination of 0.1 M NaOH and 6 M HCl or ultrapure water (pH 7), from soil samples collected from the subsoil (0–15 cm, A horizon, pH 6.5–6.8) in Schönbuch forest, Baden-Württemberg, Germany. Both chemical extractions (NaOH∕HCl) and water extractions were done in separate experiments under either oxic or anoxic conditions. Furthermore, we applied the NaOH∕HCl treatment to a subsample of the water-extractable OM to separate HA and FA from the water-extractable OM. When comparing the amount of carbon extracted from soil by different extraction methods, we found that FA and HA chemically extracted from the soil can make up to 34 %–40 % of the soil organic carbon pool while the water-extractable OM only represents 0.41 %–2.74 % of the total soil organic carbon. The higher extraction efficiency of the chemical extraction is probably due to the deprotonation of carboxyl and phenol functional groups under high pH. Anoxic extraction conditions also led to more extracted carbon. For water-extractable OM, 7 times more C was extracted under anoxic conditions compared to oxic conditions. This difference was probably due to the occurrence of microbial reduction and dissolution of Fe(III) minerals in the soil during the anoxic water extraction and thus the concomitant release of Fe(III) mineral-bound organic matter. To compare the redox activity of different SOM extracts, the electron-exchange capacity (EEC) of all extracted HA, FA, and water-extractable OM was analyzed and our results showed that, under anoxic extraction conditions, the HA chemically isolated from the water-extractable OM had 2 times higher EEC values compare to the water-extractable OM itself, suggesting the potential formation of redox-active aromatic functional groups during the extraction with NaOH under anoxic conditions by condensation reactions between amino acids, aldehydes, and hydroxyl- and catechol-containing molecules. We also performed a microbial Fe(III) reduction experiment with all extracts and found that higher EEC of extracts in turn resulted in a higher stimulation of microbial Fe(III) mineral reduction by electron shuttling, i.e., faster initial Fe(III) reduction rates, and in most cases also in higher reduction extents. Our findings suggest that OM extracted with water at neutral pH should be used to better reflect environmental SOM redox processes in lab experiments and that potential artefacts of the chemical extraction method and anoxic extraction condition need to be considered when evaluating and comparing abiotic and microbial SOM redox processes.