Redox Zones Research Articles

A geologically-based approach to map arsenic risk in crystalline aquifers: Analysis of the Tampere region, Finland

The study illustrates the critical role of accurate geological structural mapping to delineate crystalline aquifer zones more prone to high health risk due to elevated dissolved As in drinking wells. The analysis revisits the results from more than 1200 groundwater samples collected over ten years from domestic wells across the Tampere region (Finland). It is demonstrated that the highest dissolved As concentrations in the region (up to 2230 μg/L) are exclusively found near major faults and deformation zones (FDZs) detected via geophysical and geological surveys, and that a clear correlation exists between dissolved concentrations and the distance from the FDZs (r). Almost all values exceeding the drinking water limit (10 μg/L) occur at r < 8 km, while concentrations above 100 μg/L occur at r < 4 km. Solid-phase As concentrations in bedrock show less dependency on FDZ than aqueous concentrations. This behavior is explained considering different mechanisms, which include enhanced sulfide oxidation and fracture connectivity, promoting preferential transport of dissolved As to FDZs and mixing of waters from different redox zones, mobilizing preferentially As(III) or As(V). Fe hydro-oxides may also precipitate/dissolve preferentially because of FDZs, while residence time may influence the contact time between water and As-bearing minerals. It is concluded that the accurate mapping of FDZs, and in general of structural geology, provides an important preliminary information to identify where localized, site-specific characterization of hydrogeology and geochemistry is more urgent to reduce As-related health risk from groundwater intake.

The Role of Redox Potential Measurement in Oak Barrel Wine Maturation

Redox potential measurement was efficiently used for monitoring the two-year maturation process of cultivar Blau Fränkisch wine in 225-L oak barrels. Redox potential of maturing wine was measured at six levels from the top to the bottom of the barrel. During the process of wine maturation, the formation and heterogeneity of redox layers, as well as the formation of various oxidoreductive zones were indicated. The end of barrel maturation process was represented with homogeneity of all redox zones where no differences in all measured levels were indicated.

Response of microbial community structure to the hydrochemical evolution during riverbank filtration: a case study in Shenyang, China

Microorganisms are widely involved in the transformation process of physical and chemical properties in the geological and hydrogeological environment. Active participation of microorganisms is important features of the biogeochemical reactions during groundwater exploiting along the riverbank filtration. Hydrodynamic condition has a direct or indirect difference control of the biological effectiveness, chemical activity and mobility of the pollution components, which can affect biogeochemical process. In different biogeochemistry, there will be some exclusive functional bacteria, which is of great significance to understand the biogeochemical mechanism of river water infiltration. This study confirms that there are two main different flow paths from river to the center of the depression cone due to different hydrodynamic conditions and spatial characteristics and scaling effects of redox zonation during riverbank filtration. In different flow paths, the microbial abundance shows obvious spatial heterogeneity. The microbial abundance and species similarity degree of the riverbed and deep flow path sediments has significant correlation. There is a significant correlation between the dominant bacteria and the environmental factors in different hydrodynamic conditions on a spatial scale. This study is the first to reveal the response of microbial community structure to water chemical evolution during riparian filtration. Due to significant positive correlation between the Fe/Mn and As, it brings the potential danger for drinking water.

Sulfurimonas subgroup GD17 cells accumulate polyphosphate under fluctuating redox conditions in the Baltic Sea: possible implications for their ecology.

The central Baltic Sea is characterized by a pelagic redox zone exhibiting high dark CO2 fixation rates below the chemocline. These rates are mainly driven by chemolithoautotrophic and denitrifying Sulfurimonas GD17 subgroup cells which are motile and fast-reacting r-strategists. Baltic Sea redox zones are unstable and a measurable overlap of nitrate and reduced sulfur, essential for chemosynthesis, is often only available on small scales and short times due to local mixing events. This raises the question of how GD17 cells gain access to electron donors or acceptors over longer term periods and under substrate deficiency. One possible answer is that GD17 cells store high-energy-containing polyphosphate during favorable nutrient conditions to survive periods of nutrient starvation. We used scanning electron microscopy with energy-dispersive X-ray spectroscopy to investigate potential substrate enrichments in single GD17 cells collected from Baltic Sea redox zones. More specific substrate enrichment features were identified in experiments using Sulfurimonas gotlandica GD1T, a GD17 representative. Sulfurimonas cells accumulated polyphosphate both in situ and in vitro. Combined genome and culture-dependent analyses suggest that polyphosphate serves as an energy reservoir to maintain cellular integrity at unfavorable substrate conditions. This redox-independent energy supply would be a precondition for sustaining the r-strategy lifestyle of GD17 and may represent a newly identified survival strategy for chemolithoautotrophic prokaryotes occupying eutrophic redox zones.

Multiscale Framework for Modeling Multicomponent Reactive Transport in Stream Corridors

AbstractTravel time‐based representations of transport, a highly successful strategy for modeling conservative tracer transport in stream corridors, are extended to accommodate multicomponent reactive transport. Specifically, convolution representations used to model exchange of solute with the hyporheic zone are shown to be equivalent to solving one‐dimensional subgrid models in Lagrangian form coupled to the advection dispersion equation for the stream channel. Unlike the convolution‐based representations of previous travel time‐based stream transport models, the subgrid model generalizes to include multicomponent reactive transport with general nonlinear reactions. An example involving biomass growth, the establishment of redox zonation, and the resulting impact on denitrification rates demonstrate reach‐scale application of the new approach. Although simplified, those example simulations show some of the key phenomena associated with hyporheic zone denitrification that are not represented with conventional first‐order estimates.

Geochemical Exports to River From the Intrameander Hyporheic Zone Under Transient Hydrologic Conditions: East River Mountainous Watershed, Colorado

AbstractTo understand how redox processes influence carbon, nitrogen, and iron cycling within the intrameander hyporheic zone, we developed a biotic and abiotic reaction network and incorporated it into the reactive transport simulator PFLOTRAN. Two‐dimensional reactive flow and transport simulations were performed (1) to evaluate how transient hydrological conditions control the lateral redox zonation within an intrameander region of the East River in Colorado and (2) to quantify the impact of a single meander on subsurface exports of carbon and other geochemical species to the river. The meander's overall contribution to the river was quantified by integrating geochemical outfluxes along the outside of the meander bend. The model was able to capture the field‐observed trends of dissolved oxygen, nitrate, iron, pH, and total inorganic carbon along a 2‐D transect. Consistent with field observations, simulated dissolved oxygen and nitrate decreased along the intrameander flow paths while iron (Fe2+) concentration increased. The simulation results further demonstrated that the reductive potential of the lateral redox zonation was controlled by groundwater velocities resulting from river stage fluctuations, with low‐water conditions promoting reducing conditions. The sensitivity analysis results showed that permeability had a more significant impact on biogeochemical zonation compared to the reaction pathways under transient hydrologic conditions. The simulation results further indicated that the meander acted as a sink for organic and inorganic carbon as well as iron during the extended baseflow and high‐water conditions; however, these geochemical species were released into the river during the falling limb of the hydrograph.

Natural spatial variability of depositional conditions, biogeochemical processes and element fluxes in sediments of the eastern Clarion-Clipperton Zone, Pacific Ocean

The manganese nodule belt within the Clarion and Clipperton Fracture Zones (CCZ) in the abyssal NE Pacific Ocean is characterized by numerous seamounts, low organic matter (OM) depositional fluxes and meter-scale oxygen penetration depths (OPD) into the sediment. The region hosts contract areas for the exploration of polymetallic nodules and Areas of Particular Environmental Interest (APEI) as protected areas. In order to assess the impact of potential mining on these deep-sea sediments and ecosystems, a thorough determination of the natural spatial variability of depositional and geochemical conditions as well as biogeochemical processes and element fluxes in the different exploration areas is required.Here, we present a comparative study on (1) sedimentation rates and bioturbation depths, (2) redox zonation of the sediments and element fluxes as well as (3) rates and pathways of biogeochemical reactions at six sites in the eastern CCZ. The sites are located in four European contract areas and in the APEI3. Our results demonstrate that the natural spatial variability of depositional and (bio)geochemical conditions in this deep-sea sedimentary environment is much larger than previously thought. We found that the OPD varies between 1 and 4.5 m, while the sediments at two sites are oxic throughout the sampled interval (7.5 m depth). Below the OPD, manganese and nitrate reduction occur concurrently in the suboxic zone with pore-water Mn2+ concentrations of up to 25 µM. The thickness of the suboxic zone extends over depth intervals of less than 3 m to more than 8 m. Our data and the applied transport-reaction model suggest that the extension of the oxic and suboxic zones is ultimately determined by the (1) low flux of particulate organic carbon (POC) of 1–2 mg Corg m−2 d−1 to the seafloor, (2) low sedimentation rates between 0.2 and 1.15 cm kyr−1 and (3) oxidation of pore-water Mn2+ at depth. The diagenetic model reveals that aerobic respiration is the main biogeochemical process driving OM degradation. Due to very low POC fluxes of 1 mg Corg m−2 d−1 to the seafloor at the site investigated in the protected APEI3 area, respiration rates are twofold lower than at the other study sites. Thus, the APEI3 site does not represent the (bio)geochemical conditions that prevail in the other investigated sites located in the European contract areas. Lateral variations in surface water productivity are generally reflected in the POC fluxes to the seafloor across the various areas but deviate from this trend at two of the study sites. We suggest that the observed spatial variations in depositional and (bio)geochemical conditions result from differences in the degree of degradation of OM in the water column and heterogeneous sedimentation patterns caused by the interaction of bottom water currents with seafloor topography.

Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Gas phase dynamics

Groundwater contamination from ethanol (e.g., alternative fuels) can support vigorous biodegradation, with many possible reactions producing dissolved gases. The objective of this study was to improve the understanding of the development and evolution of trapped gas phase changes occurring within an ethanol plume undergoing biodegradation. The experiment performed involved highly detailed spatial and temporal monitoring of gas phase saturations using Time Domain Reflectometry probes embedded in a 2-dimensional (175 cm high × 525 cm long) synthetic aquifer (homogeneous sand tank with horizontal groundwater flow). Ethanol injection immediately promoted gas-producing reactions, including: fermentation, denitrification, sulphate-reduction and iron(III)-reduction, with methanogenesis developing between 69 and 109 days. Substantial in situ increases in trapped gas were observed over ~330 days, with maximum gas saturations reaching 27% of the pore volume. Despite sustained gas production, this maximum was never exceeded, likely due to the onset of gas phase mobilization (i.e., ebullition) upon reaching a buoyancy-capillarity threshold. Reductions in the quasi-saturated hydraulic conductivity, resulting from the gas phase accumulation, were restricted by ebullition to a factor of ≤2; but still appeared to alter the groundwater flow field. Overall, trapped gas saturations exhibited high spatial and temporal variability, including declines within the plume and increases outside of the plume. Influential factors included vertically-shifting ethanol inputs and resultant secondary redox reactions, microbial controls on redox zonation, ebullition, and altered groundwater flows. These observations have implications for the transport of gases and volatile compounds within plumes and above the water table at sites with groundwater contamination from ethanol or other highly degradable organics.

Iron cycling and stable Fe isotope fractionation in Antarctic shelf sediments, King George Island

Iron (Fe) fluxes from reducing sediments and subglacial environments are potential sources of bioavailable Fe into the Southern Ocean. Stable Fe isotopes (δ56Fe) are considered a proxy for Fe sources and reaction pathways, but respective data are scarce and Fe cycling in complex natural environments is not understood sufficiently to constrain respective δ56Fe “endmembers” for different types of sediments, environmental conditions, and biogeochemical processes.We present δ56Fe data from pore waters and sequentially extracted sedimentary Fe phases of two contrasting sites in Potter Cove (King George Island, Antarctic Peninsula), a bay that is affected by fast glacier retreat. Sediments close to the glacier front contain more easily reducible Fe oxides and pyrite and show a broader ferruginous zone, compared to sediments close to the ice-free coast, where surficial oxic meltwater streams discharge into the bay. Pyrite in sediments close to the glacier front predominantly derives from eroded bedrock. For the high amount of easily reducible Fe oxides proximal to the glacier we suggest mainly subglacial sources, where Fe liberation from comminuted material beneath the glacier is coupled to biogeochemical weathering processes (likely pyrite oxidation or dissimilatory iron reduction, DIR). Our strongest argument for a subglacial source of the highly reactive Fe pool in sediments close to the glacier front is its predominantly negative δ56Fe signature that remains constant over the whole ferruginous zone. This implies in-situ DIR does not significantly alter the stable Fe isotope composition of the accumulated Fe oxides. The nonetheless overall light δ56Fe signature of easily reducible Fe oxides suggests pre-depositional microbial cycling as it occurs in potentially anoxic subglacial environments. The strongest 56Fe-depletion in pore water and most reactive Fe oxides was observed in sediments influenced by oxic meltwater discharge. The respective site showed a condensed redox zonation and a pore water δ56Fe profile typical for in-situ Fe cycling.We demonstrate that the potential of pore water δ56Fe as a proxy for benthic Fe fluxes is not straight-forward due to its large variability in marine shelf sediments at small spatial scales (−2.4‰ at the site proximal to oxic meltwater discharge vs. −0.9‰ at the site proximal to the marine glacier terminus, both at 2 cm sediment depth). The controlling factors are multifold and include the amount and reactivity of reducible Fe oxides and organic matter, the isotopic composition of the primary and secondary ferric substrates, sedimentation rates, and physical reworking (bioturbation, ice scraping). The application of δ56Fe geochemistry may prove valuable in investigating biogeochemical weathering and Fe cycling in subglacial environments. This requires, however (similarly to the use of δ56Fe for the quantification of benthic fluxes), that the spatial and temporal variability of the isotopic endmember is known and accounted for. Since geochemical data from subglacial environments are very limited, further studies are needed in order to sufficiently assess Fe cycling and fractionation at glacier beds and the composition of discharges from those areas.

Redox zonation and organic matter oxidation in palaeogroundwater of glacial origin from the Baltic Artesian Basin

Ordovician-Cambrian aquifer system (O-Cm) in the northern part of the Baltic Artesian Basin (BAB), Estonia, is part of a unique groundwater reservoir where groundwater originating from glacial meltwater recharge from the Scandinavian Ice Sheet is preserved. The distribution of redox zones in the anoxic O-Cm aquifer system is unusual. Strongly reducing conditions are found near the modern recharge area characterized by low concentrations of sulphate (<5 mg·L−1) and the presence of CH4 (up to 3.26 vol%). The concentrations of SO42− increase and concentrations of CH4 decrease farther down the groundwater flow path. Sulphate in fresh glacial palaeogroundwater originates probably from pyrite oxidation while brackish waters have gained their sulphate through mixing with relict saline formation waters residing in the deeper parts of the aquifer system. Stable isotopic composition of sulphate, especially relations between δ18OSO4-δ18Owater (∆18OSO4-H2O from +20.5 to +31.1‰) and δ34SSO4-δ34SH2S (∆34SSO4-H2S value of +47.9‰) support a widespread occurrence of bacterial sulphate reduction in fresh glacial palaeogroundwater. We propose, that the observed unusual redox zonation is a manifestation of two different flow systems in the O-Cm aquifer system: 1) the topographically driven flow system which drives the infiltration of waters through the overlying carbonate formation in the modern recharge area; 2) the relict flow system farther down the groundwater flow path which developed as a response to large hydraulic gradients imposed by the Scandinavian Ice Sheet in Pleistocene. Thus, the strongly reducing conditions surrounding the modern recharge area may show the extent to which post-glacial recharge has influenced the aquifer system. O-Cm aquifer system is an example of an aquifer that has not reached a near-equilibrium state with respect to present day flow conditions and still exhibits hydrogeochemical patterns established under the influence of a continental ice sheet in Pleistocene.

Redox zonation for different groundwater flow paths during bank filtration: a case study at Liao River, Shenyang, northeastern China

The spatial and temporal distribution of redox zones in an aquifer is important when designing groundwater supply systems. Redox zonation can have direct or indirect control of the biological and chemical reactions and mobility of pollutants. In this study, redox conditions are characterized by interpreting the hydrogeological conditions and water chemistry in groundwater during bank infiltration at a site in Shenyang, northeast China. The relevant redox processes and zonal differences in a shallow flow path and deeper flow path at the field scale were revealed by monitoring the redox parameters and chemistry of groundwater near the Liao River. The results show obvious horizontal and vertical components of redox zones during bank filtration. Variations in the horizontal extent of the redox zone were controlled by the different permeabilities of the riverbed sediments and aquifer with depth. Horizontally, the redox zone was situated within 17 m of the riverbank for the shallow flow path and within 200 m for the deep flow path. The vertical extent of the redox zone was affected by precipitation and seasonal river floods and extended to 10 m below the surface. During bank filtration, iron and manganese oxides or hydroxides were reductively dissolved, and arsenic that was adsorbed onto the medium surface or coprecipitated is released into the groundwater. This leads to increased arsenic content in groundwater, which poses a serious threat to water supply security.

Sediment Flux of Particulate Organic Phosphorus in the Open Black Sea

The interannual variation of the monthly average (weighted average) concentrations of particulate organic phosphorus (PPOM) in the photosynthetic layer, oxycline, redox zone, and H2S zone in the open Black Sea is estimated based on long-term observation data. The suspension sedimentation rates from the studied layers are assessed using model calculations and published data. The annual variation of PPOM sediment fluxes from the photosynthetic layer, oxycline, redox zone, and upper H2S zone to the anaerobic zone of the sea and the correspondingly annual average values are estimated for the first time. A regular decrease in the PPOM annual average flux with depth in the upper active layer is demonstrated. A correlation between the annual average values of PPOM sediment flux from the photosynthetic layer and ascending phosphate flux to this layer is shown, which suggests their balance in the open sea. The results are discussed in terms of the phosphorus biogeochemical cycle and the concept of new and regenerative primary production in the open Black Sea.

Meromixis and Seasonal Dynamics of Vertical Structure of Lake Uchum (South Siberia)

The seasonal dynamics of the vertical structure of small saline Lake Uchum, located in the steppe arid zone of the south of Siberia (Krasnoyarsk krai), has been studied in detail for the first time. This lake is a meromictic water body. We have revealed a heterogeneous vertical distribution of plankton organisms and a dense population of purple sulfuric bacteria in the redox zone. The taxonomic composition and seasonal dynamics of phyto- and zooplankton are described. Presumably, the meromixis of Lake Uchum is due to the inflow of fresh water to the surface of the saline water body during the rise of its level in the early 20th century, similarly to lakes Shira and Shunet located nearby. The processes of salt displacement into the solution during the formation of ice, as well as the precipitation of salts in the winter, also contribute to the maintenance of permanent stratification. The information on the current state of the lake can be useful for reconstructing the climate by bottom sediments, as well as for creating a model of water quality and investigating the therapeutic properties of lake mud.

Microbial communities associated with uranium in-situ recovery mining process are related to acid mine drainage assemblages

A large fraction (47%) of the world's uranium is mined by a technique called “In Situ Recovery” (ISR). This mining technique involves the injection of a leaching fluid (acidic or alkaline) into a uranium-bearing aquifer and the pumping of the resulting solution through cation exchange columns for the recovery of dissolved uranium. The present study reports the in-depth alterations brought to autochthonous microbial communities during acidic ISR activities. Water samples were collected from a uranium roll-front deposit that is part of an ISR mine in operation (Tortkuduk, Kazakhstan). Water samples were obtained at a depth of ca 500 m below ground level from several zones of the Uyuk aquifer following the natural redox zonation inherited from the roll front deposit, including the native mineralized orebody and both upstream and downstream adjacent locations. Samples were collected equally from both the entrance and the exit of the uranium concentration plant. Next-generation sequencing data showed that the redox gradient shaped the community structures, within the anaerobic, reduced, and oligotrophic habitats of the native aquifer zones. Acid injection induced drastic changes in the structures of these communities, with a large decrease in both cell numbers and diversity. Communities present in the acidified (pH values < 2) mining areas exhibited similarities to those present in acid mine drainage, with the dominance of Sulfobacillus sp., Leptospirillum sp. and Acidithiobacillus sp., as well as the archaean Ferroplasma sp. Communities located up- and downstream of the mineralized zone under ISR and affected by acidic fluids were blended with additional facultative anaerobic and acidophilic microorganisms. These mixed biomes may be suitable communities for the natural attenuation of ISR mining-affected subsurface through the reduction of metals and sulfate. Assessing the effect of acidification on the microbial community is critical to evaluating the potential for natural attenuation or active bioremediation strategies.

Melting phase relations in the Fe-S and Fe-S-O systems at core conditions in small terrestrial bodies

We report an experimental investigation of phase equilibria in the Fe-S and Fe-S-O systems. Experiments were performed at high temperatures (1400–1850 °C) and high pressures (14 and 20 GPa) using a multi-anvil apparatus. The results of this study are used to understand the effect of sulfur and oxygen on core dynamics in small terrestrial bodies. We observe that the formation of solid FeO grains occurs at the Fe-S liquid – Fe solid interface at high temperature ( > 1400 °C at 20 GPa). Oxygen fugacities calculated for each O-bearing sample show that redox conditions vary from ΔIW = −0.65 to 0. Considering the relative density of each phase and existing evolutionary models of terrestrial cores, we apply our experimental results to the cores of Mars and Ganymede. We suggest that the presence of FeO in small terrestrial bodies tends to contribute to outer-core compositional stratification. Depending on the redox and thermal history of the planet, FeO may also help form a transitional redox zone at the core-mantle boundary.

Composition and Activity of Microbial Communities along the Redox Gradient of an Alkaline, Hypersaline, Lake.

We compared the composition of microbial communities obtained by sequencing 16S rRNA gene amplicons with taxonomy derived from metatranscriptomes from the same samples. Samples were collected from alkaline, hypersaline Mono Lake, California, USA at five depths that captured the major redox zones of the lake during the onset of meromixis. The prokaryotic community was dominated by bacteria from the phyla Proteobacteria, Firmicutes, and Bacteroidetes, while the picoeukaryotic chlorophyte Picocystis dominated the eukaryotes. Most (80%) of the abundant (>1% relative abundance) OTUs recovered as amplicons of 16S rRNA genes have been reported in previous surveys, indicating that Mono Lake's microbial community has remained stable over 12 years that have included periods of regular, annual overturn interspersed by episodes of prolonged meromixis that result in extremely reducing conditions in bottom water. Metatranscriptomic sequences binned predominately to the Gammaproteobacteria genera Thioalkalivibrio (4–13%) and Thioalkalimicrobium (0–14%); and to the Firmicutes genera Dethiobacter (0–5%) and Clostridium (1–4%), which were also abundant in the 16S rRNA gene amplicon libraries. This study provides insight into the taxonomic affiliations of transcriptionally active communities of the lake's water column under different redox conditions.

Water Column Distribution of Mercury Species in Permanently Stratified Aqueous Environments

Biogeochemical structures of three permanently stratified waterbodies were studied: a sea water basin (the Black Sea), an estuary (Hunnbunn fjord), and a freshwater lake (Nordbytjernet), with focus on the distributions of methylmercury (MeHg) and total mercury (THg). THg concentrations were similar in the sea water basin (0.2–1.8 ng/L) and the freshwater lake (0.8–1.2 ng/L), but significantly higher in the estuary (0.6–9.4 ng/L). An increase in the MeHg concentration and MeHg/THg ratio were found in the redox zone in all three basins, indicating bacterial production of MeHg in the aqueous phase. In the lake and estuary, the maximum MeHg concentration and MeHg/THg ratio were found in samples located closest to the bottom sediments, likely due to the formation of MeHg in surface sediments and subsequent diffusion to the overlying waters.

Anaerobic biodegradation of dissolved ethanol in a pilot-scale sand aquifer: Variability in plume (redox) biogeochemistry

The use of ethanol in alternative fuels has led to contamination of groundwater with high concentrations of this easily biodegradable organic compound. Previous laboratory and field studies have shown vigorous biodegradation of ethanol plumes, with prevalence of reducing conditions and methanogenesis. The objective of this study was to further our understanding of the dynamic biogeochemistry processes, especially dissolved gas production, that may occur in developing and aging plume cores at sites with ethanol or other organic contamination of groundwater. The experiment performed involved highly-detailed spatial and temporal monitoring of ethanol biodegradation in a 2-dimensional (175cm high×525cm long) sand aquifer tank for 330days, with a vertical shift in plume position and increased nutrient inputs occurring at ~Day 100. Rapid onset of fermentation, denitrification, sulphate-reduction and iron(III)-reduction occurred following dissolved ethanol addition, with the eventual widespread development of methanogenesis. The detailed observations also demonstrate a redox zonation that supports the plume fringe concept, secondary reactions resulting from a changing/moving plume, and time lags for the various biodegradation processes. Additional highlights include: i) the highest dissolved H2 concentrations yet reported for groundwater, possibly linked to vigorous fermentation in the absence of common terminal electron-acceptors (i.e., dissolved oxygen, nitrate, and sulphate, and iron(III)-minerals) and methanogenesis; ii) evidence of phosphorus nutrient limitation, which stalled ethanol biodegradation and perhaps delayed the onset of methanogenesis; and iii) the occurrence of dissimilatory nitrate reduction to ammonium, which has not been reported for ethanol biodegradation to date.

Predicted microbial secretomes and their target substrates in marine sediment.

Scientific drilling has identified a biosphere in marine sediments 1 , which contain many uncultivated microbial groups known only by their DNA sequences 2-4 . Recycling of organic matter in sediments is an important component of biogeochemical cycles because marine sediments are critical forlong-term carbon storage 5 . Turnover of carbon is hypothesized to be driven by the secretion of enzymes by microbial organisms 5-7 , which act to break down macromolecules into constitutive monomers that can be transported into cells. As such, the nature of the microbial secretome often influences the function of a community 6 . However, the microbial groups involved in this process and the biochemistry theyencode is poorly understood. Here, we show that expressed genes from 5 to 159 meters below the seafloor 8 (mbsf) encode numerous candidate peptidases and carbohydrate-active enzymes ('CAZymes') 9 targeted for secretion. The majority (90-99%) were assigned to Bacteria, of which 12% shared the highest sequence similarity with candidate phyla 10,11 . The remaining putatively secreted proteins shared highest sequence similarity with archaeal and fungal enzymes, which peak in two redox transition zones 12 . In the shallower redox zone at 30 mbsf, 20% of the transcripts encoding putative secreted peptidases were assigned to lineages 7,13,14 of uncultivated Archaea. The target compounds of the predicted secreted proteome show a preference for necromass in the form of microbial cell envelopes as well as plankton and algal detritus. The predicted fungal secreted proteome encodes CAZymes not present in the predicted bacterial or archaeal secreted proteomes, indicating that fungi putatively play a minimal but specialized role in subseafloor carbohydrate recycling.

Hells Bells – unique speleothems from the Yucatán Peninsula, Mexico, generated under highly specific subaquatic conditions

We here report on a type of meter-sized pendant speleothem growing under water in the submerged El Zapote sinkhole (cenote) west of Puerto Morelos on the Mexican Yucatán Peninsula. These conical, mantle-shaped downward expanding and diverging calcareous structures, here termed as Hells Bells, are yet unreported in the scientific literature. They are characterized by bell- or trumpet shaped longitudinal and circular, elliptical or horse-shoe-like horizontal cross-sections. Hells Bells grow downward, based on the downward divergence of the structures and the horizontally laminated internal texture of both blade-shaped spar calcite and microspar laminae. Age dating confirms that Hells Bells are young (<4500yr) and formed in a subaquatic environment. They grow under lightless conditions in a stratified water body, which is characterized by a fresh water body overlying a salt water body with a stagnant transition zone (halocline) of several meters. We hypothesize that the growth of these structures is mediated by specific physical and biogeochemical conditions above and in the halocline. Stagnant hydraulic conditions led to extensive diffusion profiles of several nutrients including calcium originating from the salt water body. Dissolved organic carbon from the fresh water is microbially oxidized in the upper part of the halocline, where a distinct redox zonation was identified from oxic to anoxic conditions. Degradation processes combined with slightly alkaline pH values as well as the diffusive transport of calcium into this zone may induce an increase in calcite oversaturation. Phylogenetic analysis of the community on the surface of the Hells Bells suggests the presence of microorganisms involved in the nitrogen-cycle, from which some potentially have the capability to increase the pH by autotrophic growth and denitrifying activity, thus supporting calcite precipitation. The growth of Hells Bells is strictly dependent on the elevation of the halocline. This offers a wide potential for the use of Hells Bells as archives of paleo-hydrological conditions during the Holocene, e.g. the variation of thickness of the fresh water lens on the Yucatán Peninsula.