Redox Gradients Research Articles

Lifestyle-specific S-nitrosylation of protein cysteine thiols regulates Escherichia coli biofilm formation and resistance to oxidative stress

Communities of bacteria called biofilms are characterized by reduced diffusion, steep oxygen, and redox gradients and specific properties compared to individualized planktonic bacteria. In this study, we investigated whether signaling via nitrosylation of protein cysteine thiols (S-nitrosylation), regulating a wide range of functions in eukaryotes, could also specifically occur in biofilms and contribute to bacterial adaptation to this widespread lifestyle. We used a redox proteomic approach to compare cysteine S-nitrosylation in aerobic and anaerobic biofilm and planktonic Escherichia coli cultures and we identified proteins with biofilm-specific S-nitrosylation status. Using bacterial genetics and various phenotypic screens, we showed that impairing S-nitrosylation in proteins involved in redox homeostasis and amino acid synthesis such as OxyR, KatG, and GltD altered important biofilm properties, including motility, biofilm maturation, or resistance to oxidative stress. Our study therefore revealed that S-nitrosylation constitutes a physiological basis underlying functions critical for E. coli adaptation to the biofilm environment.

Cycling of redox-sensitive trace metals in barrier island freshwater lenses

Freshwater lenses connect the terrestrial and marine realm via groundwater discharge at the edges of islands and serve as drinking water resources. We studied the redox-sensitive metals U, Mo, V, and Tl along the redox gradient of fresh groundwater lenses on Spiekeroog Island, northern Germany. Groundwater solute concentrations were linked to groundwater age and redox characteristics. We further quantified the contribution of precipitation, sea spray, and aquifer matrix to the groundwater metal concentrations and evaluated the sink and source function of the aquifer under oxic and reducing conditions.We found that biogeochemical processes altered the concentrations of the trace metals. In young, oxygen to nitrate reducing zones, the aquifer matrix represented the major metal source to the groundwater. For Tl, rain was an additional important (anthropogenic) source. Under manganese and iron oxide to sulfate reducing conditions, U and Tl were sensitive to redox dependent removal, whereas Mo and V were less affected by reductive precipitation/adsorption. In detail, 99% of dissolved Tl, 88% of U, 66% of Mo, and 44% of V were removed to the solid phase in comparison to values from less reducing zones. Large parts of the western freshwater lens on Spiekeroog were anoxic. For this reason, the delivery of aquifer derived metals to the ocean via fresh groundwater discharge appeared to be limited. Higher U, Mo, V, and Tl concentrations were observed in the presently developing young freshwater lens in the east of Spiekeroog Island. This suggests that less reducing groundwater lenses may be a source of these metals to the adjacent beach/coastal seawater. Especially for V, freshwater discharge from sandy coastal aquifers may be important, as groundwater concentrations exceeded seawater concentration under oxic as well as anoxic conditions. Regarding the suitability of the freshwater as drinking water, all measured trace metal concentrations were classified as uncritical.

Mercury methylation by metabolically versatile and cosmopolitan marine bacteria

Microbes transform aqueous mercury (Hg) into methylmercury (MeHg), a potent neurotoxin that accumulates in terrestrial and marine food webs, with potential impacts on human health. This process requires the gene pair hgcAB, which encodes for proteins that actuate Hg methylation, and has been well described for anoxic environments. However, recent studies report potential MeHg formation in suboxic seawater, although the microorganisms involved remain poorly understood. In this study, we conducted large-scale multi-omic analyses to search for putative microbial Hg methylators along defined redox gradients in Saanich Inlet, British Columbia, a model natural ecosystem with previously measured Hg and MeHg concentration profiles. Analysis of gene expression profiles along the redoxcline identified several putative Hg methylating microbial groups, including Calditrichaeota, SAR324 and Marinimicrobia, with the last the most active based on hgc transcription levels. Marinimicrobia hgc genes were identified from multiple publicly available marine metagenomes, consistent with a potential key role in marine Hg methylation. Computational homology modelling predicts that Marinimicrobia HgcAB proteins contain the highly conserved amino acid sites and folding structures required for functional Hg methylation. Furthermore, a number of terminal oxidases from aerobic respiratory chains were associated with several putative novel Hg methylators. Our findings thus reveal potential novel marine Hg-methylating microorganisms with a greater oxygen tolerance and broader habitat range than previously recognized.

Microbial niche differentiation explains nitrite oxidation in marine oxygen minimum zones

Nitrite is a pivotal component of the marine nitrogen cycle. The fate of nitrite determines the loss or retention of fixed nitrogen, an essential nutrient for all organisms. Loss occurs via anaerobic nitrite reduction to gases during denitrification and anammox, while retention occurs via nitrite oxidation to nitrate. Nitrite oxidation is usually represented in biogeochemical models by one kinetic parameter and one oxygen threshold, below which nitrite oxidation is set to zero. Here we find that the responses of nitrite oxidation to nitrite and oxygen concentrations vary along a redox gradient in a Pacific Ocean oxygen minimum zone, indicating niche differentiation of nitrite-oxidizing assemblages. Notably, we observe the full inhibition of nitrite oxidation by oxygen addition and nitrite oxidation coupled with nitrogen loss in the absence of oxygen consumption in samples collected from anoxic waters. Nitrite-oxidizing bacteria, including novel clades with high relative abundance in anoxic depths, were also detected in the same samples. Mechanisms corresponding to niche differentiation of nitrite-oxidizing bacteria across the redox gradient are considered. Implementing these mechanisms in biogeochemical models has a significant effect on the estimated fixed nitrogen budget.

New minerals and the first mineral occurrences in the Kupferschiefer (U, REE, HgS, chloride minerals PtAs2, Pt(Sb,Bi)2, PtBi2), Poland, and their genetic meaning

Abstract Main U minerals in the Lubin and Polkowice mines in decreasing order of abundance are: uraninite, brannerite, metazunerite, metauranospinite, uranospinite, thucholite, monazite-huttonite, coffinite, and becquerelite. All these minerals are associated mainly with noble metal mineralization at the redox interfaces. Main minerals of REE are: (i) brannerite, monazite-huttonite in Noble Metals Bearing Shale (NMBS), (ii) florencite in Mo-Re shales and (iii) minor phospates in Cu-black shales derived from oxidation of organic matter. The latter, however, are controlling no more than 1/5 of the REE budget. Chloride minerals and sulphates are ubiquitous phases associated with Cu sulphides. They are represented by chlorargylite, cotunnite and penfieldite. Halite and sylvite form cubic inclusions in gypsum, up to 3 mm in chevrel compound, where they occur together with thiosulphates, anna-bergite and erithrite and Ni-Co-diarsenides. Sylvite is most common in lensoidal accumulations of semi massive kaolinite + chalcocite + gypsum at the contact between black shale and the top part of white sandstone. Such lenses have been traced over a distance of up to 30 m in the Lubin West and Polkowice East mines. Sylvite and halite have been so far overlooked during investigations of the Kupferschiefer because of applying standard cuƫng and polishing procedures using water as a lubricant. The Au content in native gold may reach exceptionally up to 97.40 wt% in a dolomitic reef from the Lubin West Mine. Gold forms four characteristic micro to nano-textures. Organic matrix of thucholite indicates correlation of Pt-Ni-V suggesting substitution of Pt in tetrapyrrole ring. Sperrylite, geversite and insizwaite appear at the western perimeter of Cu-sulphide deposit, where the redox gradient is so strong that almost all organic matter is gone. Platinum has forms its own minerals trapped in microfractures in anilite-digenite-spionkopite-yarrowite-bornite composite grains present in the reddened NMBS. Celestine-barite solid solution is one of the main accessory minerals in the Kupferschiefer. It has Sr/Ba ratio around 2.5 and 7.5. Euhedral uraninite associated with celestine-barite yielded U/Pb age of 84 ± 1 Ma, based on four grains measurements.

Groundwater–Stream Connectivity Mediates Metal(loid) Geochemistry in the Hyporheic Zone of Streams Impacted by Historic Mining and Acid Rock Drainage

High concentrations of trace metal(loid)s exported from abandoned mine wastes and acid rock drainage pose a risk to the health of aquatic ecosystems. To determine if and when the hyporheic zone mediates metal(loid) export, we investigated the relationship between streamflow, groundwater–stream connectivity, and subsurface metal(loid) concentrations in two ~1-km stream reaches within the Bonita Peak Mining District, a US Environmental Protection Agency Superfund site located near Silverton, Colorado, USA. The hyporheic zones of reaches in two streams—Mineral Creek and Cement Creek—were characterized using a combination of salt-tracer injection tests, transient-storage modeling, and geochemical sampling of the shallow streambed (<0.7 m). Based on these data, we present two conceptual models for subsurface metal(loid) behavior in the hyporheic zones, including (1) well-connected systems characterized by strong hyporheic mixing of infiltrating stream water and upwelling groundwater and (2) poorly connected systems delineated by physical barriers that limit hyporheic mixing. The comparatively large hyporheic zone and high hydraulic conductivities of Mineral Creek created a connected stream–groundwater system, where mixing of oxygen-rich stream water and metal-rich groundwater facilitated the precipitation of metal colloids in the shallow subsurface. In Cement Creek, the precipitation of iron oxides at depth (~0.4 m) created a low-hydraulic-conductivity barrier between surface water and groundwater. Cemented iron oxides were an important regulator of metal(loid) concentrations in this poorly connected stream–groundwater system due to the formation of strong redox gradients induced by a relatively small hyporheic zone and high fluid residence times. A comparison of conceptual models to stream concentration–discharge relationships exhibited a clear link between geochemical processes occurring within the hyporheic zone of the well-connected system and export of particulate Al, Cu, Fe, and Mn, while the poorly connected system did not have a notable influence on metal concentration–discharge trends. Mineral Creek is an example of a hyporheic system that serves as a natural dissolved metal(loid) sink, whereas poorly connected systems such as Cement Creek may require a combination of subsurface remediation of sediments and mitigation of upstream, iron-rich mine drainages to reduce metal export.

Spatiotemporal Organization of Chemotaxis Pathways in Magnetospirillum gryphiswaldense.

Magnetospirillum gryphiswaldense employs iron-rich nanoparticles for magnetic navigation within environmental redox gradients. This behavior termed magneto-aerotaxis was previously shown to rely on the sensory pathway CheOp1, but the precise localization of CheOp1-related chemoreceptor arrays during the cell cycle and its possible interconnection with three other chemotaxis pathways have remained unstudied. Here, we analyzed the localization of chemoreceptor-associated adaptor protein CheW1 and histidine kinase CheA1 by superresolution microscopy in a spatiotemporal manner. CheW1 localized in dynamic clusters that undergo occasional segregation and fusion events at lateral sites of both cell poles. Newly formed smaller clusters originating at midcell before completion of cytokinesis were found to grow in size during the cell cycle. Bipolar CheA1 localization and formation of aerotactic swim halos were affected depending on the fluorescent protein tag, indicating that CheA1 localization is important for aerotaxis. Furthermore, polar CheW1 localization was independent of cheOp2 to cheOp4 but lost in the absence of cheOp1 or cheA1 Results were corroborated by the detection of a direct protein interaction between CheA1 and CheW1 and by the observation that cheOp2- and cheOp3-encoded CheW paralogs localized in spatially distinct smaller clusters at the cell boundary. Although the findings of a minor aerotaxis-related CheOp4 phenotype and weak protein interactions between CheOp1 and CheOp4 by two-hybrid analysis implied that CheW1 and CheW4 might be part of the same chemoreceptor array, CheW4 was localized in spatially distinct polar-lateral arrays independent of CheOp1, suggesting that CheOp1 and CheOp4 are also not connected at the molecular level.IMPORTANCE Magnetotactic bacteria (MTB) use the geomagnetic field for navigation in aquatic redox gradients. However, the highly complex signal transduction networks in these environmental microbes are poorly understood. Here, we analyzed the localization of selected chemotaxis proteins to spatially and temporally resolve chemotaxis array localization in Magnetospirillum gryphiswaldense Our findings suggest that bipolar localization of chemotaxis arrays related to the key signaling pathway CheOp1 is important for aerotaxis and that CheOp1 signaling units assemble independent of the three other chemotaxis pathways present in M. gryphiswaldense Overall, our results provide deeper insights into the complex organization of signaling pathways in MTB and add to the general understanding of environmental bacteria possessing multiple chemotaxis pathways.

Endogenous Stimuli-Responsive DNA Nanostructures Toward Cancer Theranostics

Nanostructures specifically responsive to endogenous biomolecules hold great potential in accurate diagnosis and precision therapy of cancers. In the pool of nanostructures with responsiveness to unique triggers, nanomaterials derived from DNA self-assembly have drawn particular attention due to their intrinsic biocompatibility and structural programmability, enabling the selective bioimaging, and site-specific drug delivery in cancer cells and tumor tissues. In this mini review, we summarize the most recent advances in the development of endogenous stimuli-responsive DNA nanostructures featured with precise self-assembly, targeted delivery, and controlled drug release for cancer theranostics. This mini review briefly discusses the diverse dynamic DNA nanostructures aiming at bioimaging and biomedicine, including DNA self-assembling materials, DNA origami structures, DNA hydrogels, etc. We then elaborate the working principles of DNA nanostructures activated by biomarkers (e.g., miRNA, mRNA, and proteins) in tumor cells and microenvironments of tumor tissue (e.g., pH, ATP, and redox gradient). Subsequently, applications of the endogenous stimuli-responsive DNA nanostructures in biological imaging probes for detecting cancer hallmarks as well as intelligent carriers for drug release in vivo are discussed. In the end, we highlight the current challenges of DNA nanotechnology and the further development of this promising research direction.

Candidatus Sulfurimonas marisnigri sp. nov. and Candidatus Sulfurimonas baltica sp. nov., thiotrophic manganese oxide reducing chemolithoautotrophs of the class Campylobacteria isolated from the pelagic redoxclines of the Black Sea and the Baltic Sea

Species of the genus Sulfurimonas are reported and isolated from terrestrial habitats and marine sediments and water columns with steep redox gradients. Here we report on the isolation of strains SoZ1 and GD2 from the pelagic redoxcline of the Black Sea and the Baltic Sea, respectively. Both strains are gram-stain-negative and appear as short and slightly curved motile rods. The autecological preferences for growth of strain SoZ1 were 0–25°C (optimum 20°C), pH 6.5–9.0 (optimum pH 7.5–8.0) and salinity 10–40gL−1 (optimum 25gL−1). Preferences for growth of strain GD2 were 0–20°C (optimum 15°C), pH 7.0–8.0 (optimum pH 7.0–7.5) and salinity 5–40gL−1 (optimum 21gL−1). Strain SoZ1 grew chemolithoautotrophically, while strain GD2 also showed heterotrophic growth with short chained fatty acids as carbon source. Both species utilized hydrogen (H2), sulfide (H2S here taken as the sum of H2S, HS− and S2−), elemental sulfur (S0) and thiosulfate (S2O32−) as electron donors and nitrate (NO3−), oxygen (O2) and particulate manganese oxide (MnO2) as electron acceptors. Based on 16S rRNA gene sequence similarity, both strains cluster within the genus Sulfurimonas with Sulfurimonas gotlandica GD1T as the closest cultured relative species with a sequence similarity of 96.74% and 96.41% for strain SoZ1 and strain GD2, respectively. Strains SoZ1 and GD2 share a ribosomal 16S sequence similarity of 99.27% and were demarcated based on average nucleotide identity and average amino acid identity of the whole genome sequence. These calculations have been applied to the whole genus. We propose the names Candidatus Sulfurimonas marisnigri sp. nov. and Candidatus Sulfurimonas baltica sp. nov. for the thiotrophic manganese reducing culture isolates from the Black Sea and Baltic Sea, respectively.

Potential virus-mediated nitrogen cycling in oxygen-depleted oceanic waters

Viruses play an important role in the ecology and biogeochemistry of marine ecosystems. Beyond mortality and gene transfer, viruses can reprogram microbial metabolism during infection by expressing auxiliary metabolic genes (AMGs) involved in photosynthesis, central carbon metabolism, and nutrient cycling. While previous studies have focused on AMG diversity in the sunlit and dark ocean, less is known about the role of viruses in shaping metabolic networks along redox gradients associated with marine oxygen minimum zones (OMZs). Here, we analyzed relatively quantitative viral metagenomic datasets that profiled the oxygen gradient across Eastern Tropical South Pacific (ETSP) OMZ waters, assessing whether OMZ viruses might impact nitrogen (N) cycling via AMGs. Identified viral genomes encoded six N-cycle AMGs associated with denitrification, nitrification, assimilatory nitrate reduction, and nitrite transport. The majority of these AMGs (80%) were identified in T4-like Myoviridae phages, predicted to infect Cyanobacteria and Proteobacteria, or in unclassified archaeal viruses predicted to infect Thaumarchaeota. Four AMGs were exclusive to anoxic waters and had distributions that paralleled homologous microbial genes. Together, these findings suggest viruses modulate N-cycling processes within the ETSP OMZ and may contribute to nitrogen loss throughout the global oceans thus providing a baseline for their inclusion in the ecosystem and geochemical models.

An isotopic study of abiotic nitrite oxidation by ligand-bound manganese (III)

Redox transformations of nitrogen (N) play a critical role in determining its speciation and biological availability, thus defining the magnitude and extent of productivity in many ecosystems. A range of important nitrogen transformations often co-occur in regions hosting other redox-active elements, including sulfur, iron, and manganese (Mn), especially along sharp redox gradients within aquatic sediments. This proximity in “redox real estate” produces conditions under which multi-element interactions and coupled cycling are thermodynamically favored. While previous work has reported anoxic nitrification linked to the presence of manganese (Mn) oxides in sediments, a clear connection between the cycling of Mn and N has remained elusive. Soluble Mn(III), which is stabilized via ligand-complexation, has recently been shown to represent the dominant dissolved Mn species in many environments. Here, we examined the reactivity of ligand-stabilized Mn(III) with nitrite, using natural abundance stable nitrogen and oxygen isotopes to explore reaction dynamics under a range of conditions. Oxidation of nitrite to nitrate by Mn(III)-pyrophosphate proceeded abiotically under both oxygen replete and nitrogen-purged conditions. Kinetics and isotope systematics of this reaction were measured over a range of pH (5–8), with reaction rates decreasing with increasing pH. Under all treatments, an inverse kinetic isotope effect of −19.9 ± 0.7‰ was observed for N, remarkably similar to previously documented fractionation by nitrite-oxidizing organisms. Experiments using 18O-labeled water confirmed that the source of the additional oxygen atom was from water. These findings suggest that nitrite oxidation in environments hosting abundant ligand-bound Mn(III), including porewaters, estuaries, and coastal waters, may be facilitated in part by abiotic reactions with Mn, even under functionally anoxic conditions.

Diverse origins of “soil marker” bacteriohopanepolyols in marine oxygen deficient zones

Bacteriohopanepolyols (BHPs) that are commonly associated with soil and peat environments (“soil marker” BHPs), were analyzed along redox gradients in marine oxygen deficient zones (ODZs). The latter included suspended particulate organic matter (POM) from two fjords on Vancouver Island (Canada) and the Black Sea, as well as sinking POM collected in sediment trap time-series deployed in the Cariaco Basin. Our results show that the so-called “soil marker” BHPs occur in all ODZ settings. They have distributions that are best explained by in situ chemotrophic production within the chemocline and in anoxic/euxinic waters, rather than exclusive supply from soils. In particular, adenosylhopane, adenosylhopane-type2 and 2Me-adenosylhopane-type2, appear to be produced within a common biogeochemical niche in the water column, irrespective of setting. On the other hand, 2Me-adenosylhopane, adenosylhopane-type3 and 2Me-adenosylhopane-type3 may be supplied partly from the continent, as they are also abundant in surface water suspended POM on Vancouver Island and accumulate almost exclusively in the shallower (upper chemocline) trap in the Cariaco Basin. However, their water column suspended POM distributions and time-series sinking POM fluxes also indicate additional chemotrophic sources that have spatially and temporally diverse origins.Our study suggests that caution is warranted when using “soil marker” BHPs and their associated soil input proxies in ODZ settings, as the diverse microbial community in these settings produces BHP signatures similar to those found in soils.

Arsenic behavior across soil-water interfaces in paddy soils: Coupling, decoupling and speciation

The sharp redox gradient at soil-water interfaces (SWI) plays a key role in controlling arsenic (As) translocation and transformation in paddy soils. When Eh drops, As is released to porewater from solid iron (Fe) and manganese (Mn) minerals and reduced to arsenite. However, the coupling or decoupling processes operating within the redox gradient at the SWI in flooded paddy soils remain poorly constrained due to the lack of direct evidence. In this paper, we reported the mm-scale mapping of Fe, As and other associated elements across the redox gradient in the SWI of five different paddy soils. The results showed a strong positive linear relationship between dissolved Fe, Mn, As, and phosphorus (P) in 4 out of the 5 paddy soils, indicating the general coupling of these elements. However, decoupling of Fe, Mn and As was observed in one of the paddy soils. In this soil, distinct releasing profiles of Mn, As and Fe were observed, and the releasing order followed the redox ladder. Further investigation of As species showed the ratio of arsenite to total As dropped from 100% to 75.5% and then kept stable along depth of the soil profile, which indicates a dynamic equilibrium between arsenite oxidization and arsenate reduction. This study provides direct evidence of multi-elements’ interaction along redox gradient of SWI in paddy soils.

Aquifer-Scale Observations of Iron Redox Transformations in Arsenic-Impacted Environments to Predict Future Contamination.

Iron oxides control the mobility of a host of contaminants in aquifer systems, and the microbial reduction of iron oxides in the subsurface is linked to high levels of arsenic in groundwater that affects greater than 150 million people globally. Paired observations of groundwater and solid-phase aquifer composition are critical to understand spatial and temporal trends in contamination and effectively manage changing water resources, yet field-representative mineralogical data are sparse across redox gradients relevant to arsenic contamination. We characterize iron mineralogy using X-ray absorption spectroscopy across a natural gradient of groundwater arsenic contamination in Vietnam. Hierarchical cluster analysis classifies sediments into meaningful groups delineating weathering and redox changes, diagnostic of depositional history, in this first direct characterization of redox transformations in the field. Notably, these groupings reveal a signature of iron minerals undergoing active reduction before the onset of arsenic contamination in groundwater. Pleistocene sediments undergoing postdepositional reduction may be more extensive than previously recognized due to previous misclassification. By upscaling to similar environments in South and Southeast Asia via multinomial logistic regression modeling, we show that active iron reduction, and therefore susceptibility to future arsenic contamination, is more widely distributed in presumably pristine aquifers than anticipated.

Trace and rare earth elements geochemistry of sedimentary rocks in the Ediacaran-Cambrian transition from the Tarim Basin, Northwest China: Constraints for redox environments

Spatiotemporal variations in the redox conditions during the Ediacaran-Cambrian (E-C) transition are closely related to the extinction of Ediacaran biota and the Cambrian explosion. However, the detailed variations in the ocean redox gradients remain a controversial issue. In this study, a large dataset of major and trace elements was obtained from the leachates of carbonate rocks sampled from three sections of the E-C transition in the Tarim Basin, northwest China. The Ce anomaly in the late Ediacaran Qigebulage Formation exhibited a regular gradient from anoxic conditions at its base to oxic conditions at its top, suggesting a gradually oxidizing environment. This could have been a beneficial factor that led to the diversification of late Ediacaran fauna. In addition, significantly negative carbon isotope excursions within the E-C boundary of the three sections studied were identified at the base of the Yuertusi Formation. This is coincident with the extinction of Ediacaran biota due to an anoxic sedimentary environment. The base of the Yuertusi Formation was deposited under anoxic or/and euxinic conditions and intense hydrothermal activity during the early Cambrian. The upper layers of this formation exhibited significant Ce anomalies following a general increase in the oxidation level, which reflected an environment transitioning from anoxic/euxinic to oxic following the early Cambrian transgression. A significantly negative δ13Ccarb excursion was evidence of the Redlichiid-Olenellid Extinction Carbon isotopic Excursion event recorded at the boundary of the Cambrian Series 2 and Cambrian Miaolingian. From the Cambrian Series 2 Xiaoerbulak Formation to the Cambrian Miaolingian Awatage Formation, carbonate rocks were deposited in deep water conditions and an anoxic environment. Redox fluctuations could be ascribed to widespread early Cambrian transgressions and tectonic activity, such as the formation of the Tianshan Ocean during the early Cambrian, and the accompanying volcanic activity in the Tarim Basin. Marine redox fluctuations coupled with the paleontological records indicate that the increased concentration of oxygen in the water promoted evolutionary transitions and accelerated the diversification of species during the E-C transition.

Effect of redox gradients on Cu and Zn concentrations in water of Blanakan River, West Java

Metal concentrations in water threat adjacent ecosystems due to the potential of metal mobilization and the subsequent uptake into water. Here, contents of heavy metals Cu and Zn were determined for river waters. We used factorial analysis (FA) to determine the metal contents in relation to environmental factors such as redox potential (Eh), dissolved oxygen (DO), pH, salinity, temperature and turbidity in the Blanakan river. The Zn was ranging from 0.44 to 2.13 mg/L. The FA categorized Zn with salinity and temperature. Meanwhile, the Cu was ranging from 0.02 to 0.05 mg/L. The FA categorized Cu with Eh, turbidity, DO and pH. Such discrepancy in metal concentrations highlighted that redox gradient has more effects on Cu than Zn. Respectively, decrease of Eh from -38 to -41 mV can increase the Cu up to 0.05 mg/L. Correlation of Eh with Cu contents indicating that Cu was influenced by terrestrial inputs. Conversely, correlation of temperature and salinity with Zn contents indicating that Zn was influenced by aquatic inputs.

Seasonal mixing from intermittent flow drives concentration‐discharge behaviour in a stream affected by coal mine drainage

AbstractAbandoned mining operations continue to severely degrade many ecosystems worldwide by releasing acidic water and/or heavy metals into surface and groundwater. Contaminant concentrations in affected streams vary with discharge in patterns that reflect both geochemical reactions and variable mixing of contaminated and non‐contaminated waters. However, controls on concentration‐discharge (C‐Q) patterns remain unclear, particularly for constituents that experience changing solubility across redox and pH gradients. Understanding the C‐Q behaviour of contaminants aids in predicting both downstream transport and effects on aquatic life under variable flow. Here, we examined the C‐Q behaviours of non‐reactive (Na, K, Ca, Mg, Cl−) and reactive (Fe, Mn, Al, H+, SO42−) solutes in a stream contaminated with acid mine drainage in northeastern Ohio, USA. Concentration‐discharge patterns at the watershed outlet primarily reflected mixing of contaminated baseflow with intermittent inputs of high pH water draining from a passive limestone treatment system into the stream. The treatment system acted as an ephemeral tributary that mitigated contamination in the stream by diluting solutes, raising pH, and driving metal precipitation, but only when flow was present during wet seasons. Consequently, AMD‐derived reactive solutes (H+, Fe, Mn, Al) decreased with increasing stream discharge while relatively conservative solutes (e.g., Ca, Mg, K, Na) decreased only slightly or were chemostatic. This study highlights both the unique C‐Q patterns of reactive solutes when compared to those of non‐reactive solutes and the potential for intermittent streams to control C‐Q behaviour in headwater catchments.

Persistence of plastic debris and its colonization by bacterial communities after two decades on the abyssal seafloor

The fate of plastic debris entering the oceans is largely unconstrained. Currently, intensified research is devoted to the abiotic and microbial degradation of plastic floating near the ocean surface for an extended period of time. In contrast, the impacts of environmental conditions in the deep sea on polymer properties and rigidity are virtually unknown. Here, we present unique results of plastic items identified to have been introduced into deep-sea sediments at a water depth of 4150 m in the eastern equatorial Pacific Ocean more than two decades ago. The results, including optical, spectroscopic, physical and microbial analyses, clearly demonstrate that the bulk polymer materials show no apparent sign of physical or chemical degradation. Solely the polymer surface layers showed reduced hydrophobicity, presumably caused by microbial colonization. The bacterial community present on the plastic items differed significantly (p < 0.1%) from those of the adjacent natural environment by a dominant presence of groups requiring steep redox gradients (Mesorhizobium, Sulfurimonas) and a remarkable decrease in diversity. The establishment of chemical gradients across the polymer surfaces presumably caused these conditions. Our findings suggest that plastic is stable over extended times under deep-sea conditions and that prolonged deposition of polymer items at the seafloor may induce local oxygen depletion at the sediment-water interface.

Mitochondrial lactate metabolism: history and implications for exercise and disease.

Mitochondrial structures were probably observed microscopically in the 1840s, but the idea of oxidative phosphorylation (OXPHOS) within mitochondria did not appear until the 1930s. The foundation for research into energetics arose from Meyerhof's experiments on oxidation of lactate in isolated muscles recovering from electrical contractions in an O2 atmosphere. Today, we know that mitochondria are actually reticula and that the energy released from electron pairs being passed along the electron transport chain from NADH to O2 generates a membrane potential and pH gradient of protons that can enter the molecular machine of ATP synthase to resynthesize ATP. Lactate stands at the crossroads of glycolytic and oxidative energy metabolism. Based on reported research and our own modelling in silico, we contend that lactate is not directly oxidized in the mitochondrial matrix. Instead, the interim glycolytic products (pyruvate and NADH) are held in cytosolic equilibrium with the products of the lactate dehydrogenase (LDH) reaction and the intermediates of the malate-aspartate and glycerol 3-phosphate shuttles. This equilibrium supplies the glycolytic products to the mitochondrial matrix for OXPHOS. LDH in the mitochondrial matrix is not compatible with the cytoplasmic/matrix redox gradient; its presence would drain matrix reducing power and substantially dissipate the proton motive force. OXPHOS requires O2 as the final electron acceptor, but O2 supply is sufficient in most situations, including exercise and often acute illness. Recent studies suggest that atmospheric normoxia may constitute a cellular hyperoxia in mitochondrial disease. As research proceeds appropriate oxygenation levels should be carefully considered.

Novel bioelectrochemical strategies for domesticating the electron flow in constructed wetlands

Constructed wetlands are an effective biofilter-based technology for treating wastewater in a sustainable way; however, their main disadvantage is a large area footprint. To cope with this limitation a new generation of constructed wetlands, the METlands®, have been recently reported. METlands® replace gravel with a granular electrically conductive material to enhance the oxidative metabolisms of electroactive bacteria by facilitating the flux of electron through the material and, consequently, increase bioremediation rates. In this work we evaluated the performance of a new electron sink (e-sink) device with the purpose of controlling and enhancing the electrochemical consumption of electrons from microbial metabolism without energy consumption. The e-sink device was integrated inside the biofilter bed and was tested using different electron acceptors with high redox potentials, like oxygen and hypochlorite. Interestingly, the presence of the e-sink allowed novel redox gradients to form inside the METland® and, consequently, a new electron flow was demonstrated by measuring both the electric potential and current density profiles of the bed. Three independent biofilters were constructed and operated under flooded conditions. Ec-coke and electroconductive biochar (ec-biochar) were used as electrically conductive bed materials, while gravel was used as an inert control. Furthermore, e-sink integration inside the electrically conductive bed outperformed METlands® for removing pollutants, already much more efficient than standard gravel biofilters. COD removal was increased from 90% in METland® to 95% in the e-sink METland® as compared to 75% for the control, while total nitrogen removal was enhanced from 64% in METland® to 71% in e-sink METland® as compared to 55% for the control. Our results indicate that increasing the electrochemical availability of electron acceptors by using the e-sink will be a suitable method for controlling the electron flow inside the filter bed and can be integrated in full scale METlands® for achieving high removal rates.