Microbial processes are known to mediate selenium (Se) oxidation-reduction reactions, strongly influencing Se speciation, bioavailability, and transport throughout the environment. While these processes have commonly been studied in anaerobic bacteria, the role that aerobic fungi play in Se redox reactions could be important for Se-rich soil systems, dominated by microbial activity. We quantified fungal growth, aerobic Se(IV, VI) reduction, and Se immobilization and volatilization in the presence of six, metal-tolerant Ascomycete fungi. We found that the removal of dissolved Se was dependent on the fungal species, Se form (i.e., selenite or selenate), and Se concentration. All six species grew and removed dissolved Se(IV) or Se(VI) from solution, with five species reducing both oxyanions to Se(0) biominerals, and all six species removing at least 15%-20% of the supplied Se via volatilization. Growth rates of all fungi, however, decreased with increasing Se(IV,VI) concentrations. All fungi removed 85%-93% of the dissolved Se(IV) within 10 d in the presence of 0.01 mm Se(IV), although only about 20%-30% Se(VI) was removed when grown with 0.01 mm Se(VI). Fungi-produced biominerals were typically 50- to 300-nm-diameter amorphous or paracrystalline spherical Se(0) nanoparticles. Our results demonstrate that activity of common soil fungi can influence Se form and distribution, and these organisms may therefore play a role in detoxifying Se-polluted environments.

Selenium (Se) redox chemistry is a determining factor for its environmental toxicity and mobility. Currently, millions of people are impacted by Se deficiency or toxicity, and in geologic history, several mass extinctions have been linked to extreme Se deficiency. Importantly, microbial activity and interactions with other biogeochemically active elements can drastically alter Se oxidation state and form, impacting its bioavailability. Here, we use wet geochemistry, spectroscopy, and electron microscopy to identify a cryptic, or hidden, Se cycle involving the reoxidation of biogenic volatile Se compounds in the presence of biogenic manganese [Mn­(III, IV)] oxides and oxyhydroxides (hereafter referred to as “Mn oxides”). Using two common environmental Ascomycete fungi, Paraconiothyrium sporulosum and Stagonospora sp., we observed that aerobic Se­(IV and VI) bioreduction to Se(0) and Se­(-II) occurs simultaneously alongside the opposite redox biomineralization process of mycogenic Mn­(II) oxidation to Mn oxides. Selenium bioreduction produced stable Se(0) nanoparticles and organoselenium compounds. However, mycogenic Mn oxides rapidly oxidized volatile Se products, recycling these compounds back to soluble forms. Given their abundance in natural systems, biogenic Mn oxides likely play an important role mediating Se biogeochemistry. Elucidating this cryptic Se cycle is essential for understanding and predicting Se behavior in diverse environmental systems.

Selenium contamination in natural environments is of great concern globally, and microbial processes are known to mediate Se transformations. Such transformations alter Se mobility, bioavailability, and toxicity, which can amplify or mitigate Se pollution. To date, nearly all studies investigating Se-microbe interactions have used culture-based approaches with anaerobic bacteria despite growing knowledge that (i) aerobic Se transformations can occur, (ii) such transformations can be mediated by microorganisms other than bacteria, and (iii) microbial community dynamics, rather than individual organismal activities, are important for metal(loid) cycling in natural environments. We examined bacterial and fungal communities in Se-contaminated reclaimed mine soils and found significant declines in diversity at high Se concentrations. Additionally, we identified specific taxonomic groups that tolerate excess Se and may be useful for bioremediation purposes. These patterns were similar across mines of different ages, suggesting that microbial community impacts may persist long after physicochemical parameters indicate complete site recovery.

This study reexamines the common expectations that in freshwater systems, sulfur plays a minor role in carbon cycling, and aerobic processes dominate methane oxidation. In anoxic sediments of a sulfate‐impacted wetland‐stream system in Minnesota (USA), a reactive transport model calibrated to geochemical observations predicted sulfate reduction to be the major terminal electron accepting process, and it showed that anaerobic oxidation of methane predominantly coupled with sulfate reduction attenuated methane concentrations near the sediment‐water interface. Consistent with model results, 16S rRNA microbiome analysis revealed a high relative abundance of taxa capable of dissimilatory sulfate reduction. It further supported the conclusion that high simulated sulfate reduction rates could be maintained by a “cryptic” sulfur cycle coupled to iron and methane. Low relative abundance of known iron reducing bacteria raised the possibility of abiotic ferric iron (Fe) reduction driving sulfide reoxidation to intermediate‐valence sulfur forms; widespread potential for microbially mediated disproportionation, oxidation, and reduction of sulfur intermediates provided mechanisms for completing redox cycles; and archaea comprising up to 25% of the microbial community could include consortia capable of anaerobic oxidation of methane. These biogeochemical processes were found to be controlled by hyporheic fluxes. Lower‐magnitude fluxes in wetland compared to channel sediments created sharper geochemical gradients that generated greater heterogeneity in microbial distributions and reaction rates. Changes in upward flux caused fluctuations in sulfate concentrations that led to alternating simulations of methane production and transport. Our work supports the importance of hyporheic flux‐driven iron‐sulfur‐methane cycling in sulfate‐impacted wetlands and prompts further investigations under freshwater conditions.

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Selenium (Se) is an essential element for most organisms yet can cause severe negative biological consequences at elevated levels. The oxidized forms of Se, selenate [Se(VI)] and selenite [Se(IV)], are more mobile, toxic, and bioavailable than the reduced forms of Se such as volatile or solid phases. Thus, selenate and selenite pose a greater threat to ecosystems and human health. As current Se remediation technologies have varying efficiencies and costs, novel strategies to remove elevated Se levels from environments impacted by anthropogenic activities are desirable. Some common soil fungi quickly remove Se (IV and VI) from solution by aerobic reduction to solid or volatile forms. Here, we perform bench-scale culture experiments of two Se-reducing Ascomycota to determine their Se removal capacity in growth media conditions containing either Se(IV) or Se(VI) as well as in Se-containing municipal (∼25 µg/L Se) and industrial (∼2000 µg/L Se) wastewaters. Dissolved Se was measured throughout the experiments to assess Se concentration and removal rates. Additionally, solid-associated Se was quantified at the end of each experiment to determine the amount of Se removed to solid phases (e.g., Se(0) nanoparticles, biomass-adsorbed Se, or internal organic selenoproteins). Results show that under optimal conditions, fungi more efficiently remove Se(IV) from solution compared to Se(VI). Additionally, both fungi remove a higher percentage of Se from the filtered municipal wastewater compared to the industrial wastewater, though cultures in industrial wastewater retained a greater amount of solid-associated Se. Additional wastewater experiments were conducted with supplemental carbohydrate-or glycerin-based carbon products and additional nitrogenand phosphorous-containing nutrients in some cases to enhance fungal growth. Relative to unamended wastewater experiments, supplemental carbohydrates promote Se removal from municipal wastewater but minimally impact industrial wastewater removal. This demonstrates that carbon availability and source impacts fungal Se reduction and removal from solution. Calculations to assess the leaching potential of solid-associated Se from fungal biomass show that wastewater Se release will not exceed regulatory limits. This study highlights the considerable potential for the mycoremediation of Se-contaminated wastewaters.

Metal contaminants in soils can persist for millennia, causing lasting negative impacts on local ecosystems. Long-term contaminant bioavailability is related to soil pH and to the strength and stability of solid-phase associations. We combined physical density separation with synchrotron-based microspectroscopy to reduce solid-phase complexity and to study Zn speciation in field-contaminated soils. We also investigated Zn uptake in two Zn-hyperaccumulating ecotypes of (Ganges and Prayon). Soils were either moderately contaminated (500-800 mg Zn kg via contaminated biosolids application) or grossly enriched (26,000 mg Zn kg via geogenic enrichment). Soils were separated using sodium polytungstate into three fractions: light fraction (LF) (<1.6 g cm), medium fraction (MF) (1.6-2.8 g cm), and heavy fraction (HF) (>2.8 g cm). Approximately 45% of the total Zn was associated with MF in biosolids-contaminated soils. From these data, we infer redistribution to the MF after biosolids application because Zn in biosolids is principally associated with HF and LF. Our results suggest that increasing proportions of HF-associated Zn in soils may be related to greater relative Zn removal by Zn hyperaccumulating plants. Using density fractions enabled assessment of Zn speciation on a microscale despite incomplete fractionation. Analyzing both density fractions and whole soils revealed certain phases (e.g., ZnS, Zn coprecipitated with Fe oxides) that were not obvious in all analyses, indicating multiple views of the same soils enable a more complete understanding of Zn speciation.

Stormwater is a vital resource and dynamic driver of terrestrial ecosystem processes. However, processes controlling interactions during and shortly after storms are often poorly seen and poorly sensed when direct observations are substituted with technological ones. We discuss how human observations complement technological ones and the benefits of scientists spending more time in the storm. Human observation can reveal ephemeral storm-related phenomena such as biogeochemical hot moments, organismal responses, and sedimentary processes that can then be explored in greater resolution using sensors and virtual experiments. Storm-related phenomena trigger lasting, oversized impacts on hydrologic and biogeochemical processes, organismal traits or functions, and ecosystem services at all scales. We provide examples of phenomena in forests, across disciplines and scales, that have been overlooked in past research to inspire mindful, holistic observation of ecosystems during storms. We conclude that technological observations alone are insufficient to trace the process complexity and unpredictability of fleeting biogeochemical or ecological events without the shower thoughts produced by scientists’ human sensory and cognitive systems during storms.