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Coupled abiotic and biotic processes in the hyporheic zone, where surface water and groundwater mix, play a critical role in the biogeochemical cycling of carbon, nutrients, and trace elements in streams and wetlands. Dynamic hydrologic conditions and anthropogenic pollution can impact redox gradients and biogeochemical response, although few studies examine the resulting hydrobiogeochemical interactions generated within the hyporheic zone. This study examines the effect of hyporheic flux dynamics and anthropogenic sulfate loading on the biogeochemistry of a riparian wetland and stream system. The hydrologic gradient as well as sediment, surface water, and porewater geochemistry chemistry was characterized at multiple points throughout the 2017 spring-summer-fall season at a sulfate-impacted stream flanked by wetlands in northern Minnesota. Results show that organic-rich sediments largely buffer the geochemical responses to brief or low magnitude changes in hydrologic gradient, but sustained or higher magnitude fluxes may variably alter the redox regime and, ultimately, the environmental geochemistry. This has implications for a changing climate that is expected to dramatically alter the hydrological cycle. Further, increased sulfate loading and dissolved or adsorbed ferric iron complexes in the hyporheic zone may induce a cryptic sulfur cycle linked to iron and carbon cycling, as indicated by the abundance of intermediate valence sulfur compounds (

Inorganic arsenic (As) is a toxic and carcinogenic pollutant that has long-term impacts on environmental quality and human health. Pteris vittata plants hyperaccumulate As from soils. Soil bacteria are critical for As-uptake by P. vittata. We examined the use of taxonomically diverse soil bacteria to modulate As speciation in soil and their effect on As-uptake by P. vittata. Aqueous media inoculated with Pseudomonas putida MK800041, P. monteilii MK344656, P. plecoglossicida MK345459, Ochrobactrum intermedium MK346993 or Agrobacterium tumefaciens MK346997 resulted in the oxidation of 5-30% As(III) and a 49-79% reduction of As(V). Soil inoculated with P. monteilii increased extractable As(III) and As(V) from 0.5 and 0.09 in controls to 0.9 and 0.39 mg As kg-1 soil dry weight, respectively. Moreover, and P. vittata plants inoculated with P. monteilii, P. plecoglossicida, O. intermedium strains, and A. tumefaciens strains MK344655, MK346994, MK346997, significantly increased As-uptake by 43, 32, 12, 18, 16, and 14%, respectively, compared to controls. The greatest As-accumulation (1.9 ± 0.04 g kg-1 frond Dwt) and bioconcentration factor (16.3 ± 0.35) was achieved in plants inoculated with P. monteilii. Our findings indicate that the tested bacterial strains can increase As-availability in soils, thus enhancing As-accumulation by P. vittata. Novelty statementPteris vittata, a well-known As-hyperaccumulator, has the remarkable ability to accumulate higher levels of As in their above-ground biomass. The As-tolerant bacteria-plant interactions play a significant role in bioremediation by mediating As-redox and controlling As-availability and uptake by P. vittata. Our studies indicated that most of the tested bacterial strains isolated from As-impacted soil significantly enhanced As-uptake by P. vittata. P. monteilii oxidized 20% of As(III) and reduced 50% of As(V), increased As-extraction from soils, and increased As-uptake by 43% greater compared with control. Therefore, these strains associated with P. vittata can be used in large-scale field applications to remediate As-contaminated soil.

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 nitrogen- and 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.

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

Manganese (Mn) oxide minerals influence the availability of organic carbon, nutrients and metals in the environment. Oxidation of Mn(II) to Mn(III/IV) oxides is largely promoted by the direct and indirect activity of microorganisms. Studies of biogenic Mn(II) oxidation have focused on bacteria and fungi, with phototrophic organisms (phototrophs) being generally overlooked. Here, we isolated phototrophs from Mn removal beds in Pennsylvania, USA, including fourteen Chlorophyta (green algae), three Bacillariophyta (diatoms) and one cyanobacterium, all of which consistently formed Mn(III/IV) oxides. Isolates produced cell-specific oxides (coating some cells but not others), diffuse biofilm oxides, and internal diatom-specific Mn-rich nodules. Phototrophic Mn(II) oxidation had been previously attributed to abiotic oxidation mediated by photosynthesis-driven pH increases, but we found a decoupling of Mn oxide formation and pH alteration in several cases. Furthermore, cell-free filtrates of some isolates produced Mn oxides at specific time points, but this activity was not induced by Mn(II). Manganese oxide formation in cell-free filtrates occurred via reaction with the oxygen radical superoxide produced by soluble extracellular proteins. Given the known widespread ability of phototrophs to produce superoxide, the contribution of phototrophs to Mn(II) oxidation in the environment may be greater and more nuanced than previously thought.

Manganese oxides, which may be biogenically produced in both pristine and contaminated environments, have a large affinity for many trace metals. In this study, water and Mn oxide-bearing biofilm samples were collected from the components of a pump and treat remediation system at a superfund site. To better understand the factors leading to their formation and their effects on potentially toxic metal fate, we conducted a chemical, microscopic, and spectroscopic characterization of these biofilm samples. Scanning electron microscopy revealed the presence of Mn oxides in close association with biological structures with morphologies consistent with fungi. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) revealed the oxides to be a mixture of layer and tunnel structure Mn(iv) oxides. In addition, XAS suggested that Ba, Co, and Zn all primarily bind to oxides in the biofilm in a manner that is analogous to synthetic or laboratory grown bacteriogenic Mn oxides. The results indicate that Mn oxides produced by organisms in the system may effectively scavenge metals, thus highlighting the potential utility of these organisms in designed remediation systems.

An extensive culture-dependent and –independent study was conducted to identify microorganisms contributing to the biogeochemical cycling of manganese (Mn) in Ashumet Pond, a freshwater pond in Massachusetts currently undergoing remediation. A variety of bacteria (including Gamma-, Beta-, and Alpha-proteobacteria, Firmicutes, and Bacteroides) and Ascoymete fungi were isolated from the pond that promote Mn(II) oxidation and subsequent formation of Mn(III/IV) oxide minerals. Targeted-amplicon pyrosequencing of the bacterial and fungal communities associated with Mn oxide-encrusted samples show a highly diverse microbial community, of which the cultured phylotypes represent a minor proportion. This suggests a larger community, not identified through culturing, contributes to Mn oxide formation within the Pond.

The upper Tennessee River Basin contains the highest density of our nation's caves; yet, little is known regarding speleogenesis or Fe and Mn biomineralization in these predominantly epigenic systems. Mn:Fe ratios of Mn and Fe oxide-rich biofilms, coatings, and mineral crusts that were abundant in several different caves ranged from ca. 0.1 to 1.0 as measured using ICP-OES. At sites where the Mn:Fe ratio approached 1.0 this represented an order of magnitude increase above the bulk bedrock ratio, suggesting that biomineralization processes play an important role in the formation of these cave ferromanganese deposits. Estimates of total bacterial SSU rRNA genes in ferromanganese biofilms, coatings, and crusts measured approximately 7×107–9×109 cells/g wet weight sample. A SSU-rRNA based molecular survey of biofilm material revealed that 21% of the 34 recovered dominant (non-singleton) OTUs were closely related to known metal-oxidizing bacteria or clones isolated from oxidized metal deposits. Several differe...

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.

Oxic limestone beds are commonly used for the passive removal of Mn(II) from coal mine drainage (CMD). Aqueous Mn(II) is removed via oxidative precipitation of Mn(III/IV) oxides catalyzed by Mn(II)oxidizing microbes and Mn oxide (MnOx) surfaces. The relative importance of these two processes for Mn removal was examined in laboratory experiments conducted with sediments and CMD collected from eight Mn(II)-removal beds in Pennsylvania and Tennessee, USA. Sterile and non-sterile sediments were incubated in the presence/absence of air and presence/absence of fungicides to operationally define the relative contributions of Mn removal processes. Relatively fast rates of Mn removal were measured in four of the eight sediments where 63–99% of Mn removal was due to biological oxidation. In contrast, in the four sediments with slow rates of Mn(II) removal, 25–63% was due to biological oxidation. Laboratory rates of Mn(II) removal were correlated (R 2 = 0.62) to bacterial biomass concentration (measured

Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four di!erent species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerinastrain DS2psM2a2, Pyrenochaetasp. DS3sAY3a,Stagonosporasp. SRC1lsM3a, andAcremonium strictumstrain DS1bioAY4a) isolated from acid mine drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling syntheticd-MnO 2 . The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictumstrain DS1bioAY4a) and triclinic birnessite (Stagonosporasp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large di!erences in the reactivity of the Mn oxide phases.

Biologically active, passive treatment systems are commonly employed for removing high concentrations of dissolved Mn(II) from coal mine drainage (CMD). Studies of microbial communities contributing to Mn attenuation through the oxidation of Mn(II) to sparingly soluble Mn(III/IV) oxide minerals, however, have been sparse to date. This study reveals a diverse community of Mn(II)-oxidizing fungi and bacteria existing in several CMD treatment systems.

Microbial communities inhabiting subseafloor ocean crust were analyzed using culture-dependent and -independent techniques of volcanic basement drill-cores from various locations in the Pacific Ocean. Our results suggest that a low-diversity community of bacteria belonging to the Betaproteobacteria, Alphaproteobacteria, and Bacteroidetes exists in this rocky habitat. Drilling-related contamination was observed, however, identification of these phylotypes was (and will continue to be) beneficial for distinguishing indigenous from contamination-related communities. Due to difficulties in accessing the subseafloor crustal environment, this study further highlights the necessity for innovative approaches in future drilling-based microbiological studies conducted in ocean crust.

Hydrothermal venting associated with mid-ocean ridge volcanism is globally widespread. This venting is responsible for a dissolved iron flux to the ocean that is approximately equal to that associated with continental riverine runoff. For hydrothermal fluxes, it has long been assumed that most of the iron entering the oceans is precipitated in inorganic forms. However, the possibility of globally significant fluxes of iron escaping these mass precipitation events and entering open-ocean cycles is now being debated, and two recent studies suggest that dissolved organic ligands might influence the fate of hydrothermally vented metals. Here we present spectromicroscopic measurements of iron and carbon in hydrothermal plume particles at the East Pacific Rise mid-ocean ridge. We show that organic carbon-rich matrices, containing evenly dispersed iron(II)-rich materials, are pervasive in hydrothermal plume particles. The absence of discrete iron(II) particles suggests that the carbon and iron associate through sorption or complexation. We suggest that these carbon matrices stabilize iron(II) released from hydrothermal vents in the region, preventing its oxidation and/or precipitation as insoluble minerals. Our findings have implications for deep-sea biogeochemical cycling of iron, a widely recognized limiting nutrient in the oceans.

Mercury (Hg) is a toxic heavy metal that poses significant environmental and human health risks. Soils and sediments, where Hg can exist as the Hg sulfide mineral metacinnabar (β-HgS), represent major Hg reservoirs in aquatic environments. Metacinnabar has historically been considered a sink for Hg in all but severely acidic environments, and thus disregarded as a potential source of Hg back to aqueous or gaseous pools. Here, we conducted a combination of field and laboratory incubations to identify the potential for metacinnabar as a source of dissolved Hg within near neutral pH environments and the underpinning (a)biotic mechanisms at play. We show that the abundant and widespread sulfur-oxidizing bacteria of the genus Thiobacillus extensively colonized metacinnabar chips incubated within aerobic, near neutral pH creek sediments. Laboratory incubations of axenic Thiobacillus thioparus cultures led to the release of metacinnabar-hosted Hg(II) and subsequent volatilization to Hg(0). This dissolution and volatilization was greatly enhanced in the presence of thiosulfate, which served a dual role by enhancing HgS dissolution through Hg complexation and providing an additional metabolic substrate for Thiobacillus. These findings reveal a new coupled abiotic-biotic pathway for the transformation of metacinnabar-bound Hg(II) to Hg(0), while expanding the sulfide substrates available for neutrophilic chemosynthetic bacteria to Hg-laden sulfides. They also point to mineral-hosted Hg as an underappreciated source of gaseous elemental Hg to the environment.

Mid-ocean ridge hydrothermal venting creates sulfide deposits containing gradients in mineralogy, fluid chemistry, and temperature. Even when hydrothermal circulation ceases, sulfides are known to host microbial communities. The relationship between mineralogy and microbial community composition in low-temperature, rock-hosted systems has not been resolved at any spatial scale, local or global. To examine the hypothesis that geochemistry of seafloor deposits is a dominant parameter driving environmental pressure for bacterial communities at low-temperature, the shared community membership, richness, and structure was measured using 16S rRNA gene sequences. The focus of the study was on hydrothermally inactive seafloor deposits from multiple locations within one deposit (e.g., single extinct chimney), within one vent field (intra-vent field), and among globally distributed vent fields from three ocean basins (inter-vent field). Distinct mineral substrates, such as hydrothermally inactive sulfides versus ba...