Biogeochemistry of iron in an acidic lake

In this paper, the fate of iron in Lake Cristallina, an acidic lake in the Alps of Switzerland, is discussed. A simple conceptual model is developed in order to explain the observed diel variation in dissolved iron(II) concentration. Biotite weathering provides reduced iron that is oxidized and subsequently precipitated in the lake. The amorphous Fe(III)hydroxide (FeOOH xH₂O), found in the sediments of Lake Cristallina, is an Fe(II) oxidation product. This oxygenation reaction is most probably catalyzed by bacteria surfaces, as indicated by the relatively high estimated oxidation rate compared to the oxidation rate of the homogeneous oxidation of inorganic Fe(II) species at the ambient pH of Lake Cristallina (pH 5.4 at 4 °C) and by the scanning electron micrograph pictures. Under the influence of light, these amorphous iron(III)hydroxide phases are reductively dissolved. The net concentration of Fe(II) reflects the balance of the reductive dissolution and the oxidation/precipitation reactions and tends to parallel the light intensity, leading to a diurnal variation in the Fe(II) concentration. The rate of the photochemical reductive dissolution of Lake Cristallina iron(III)hydroxides is greatly enhanced in situ and in the laboratory by addition of oxalate to the lake water.     

Lithological controls on biological activity and groundwater chemistry in Quaternary sediments

Depth profiles of solute chemistry and sulfate isotopic compositions are presented for groundwater and pore water in a sequence of Quaternary glacial outwash sediments. Sand units show evidence for hydraulic connection to the surface and thus modern sources of solutes. Finer‐grained sediments show a general pattern of increasing solute concentrations with depth, with sulfate derived from ancient rainwater and pyrite oxidation in the soil/drift. In these sediments sulfate has undergone bacterial sulfate reduction (BSR) to produce biogenic sulfide. In clay sediments, with d₁₀ ≤ 1·6 µm, high concentrations of sulfate and acetate now co‐exist, implying that BSR is inhibited. The correlation with smaller sediment grain size indicates that this is due to pore size exclusion of the sulfate reducing bacteria. Mechanical restriction of microbial function thus provides a fundamental limitation on microbial respiration in buried clay‐rich sediments, which acts as a control on the chemical evolution of their pore waters. Copyright © 2009 John Wiley & Sons, Ltd.     

Microbial iron reduction during passive in situ remediation of an acidic mine pit lake mesocosm

Ferric iron reduction was studied in a pilot-scale enclosure experiment for passive biological remediation of an acidic mine pit lake in Lusatia, Germany. The metabolic properties of prokaryotes involved in Fe(III) reduction may be important for the outcome of biological remediation, as chemolithotrophic Fe(III) reduction can counteract the desired pH increase, but heterotrophic Fe(III) reduction will provide the necessary Fe(II) for precipitation of sulfide minerals following sulfate reduction. Therefore, vertical profiles of sediment parameters related to iron and sulfur cycling were determined in conjunction with viable counts of different ferric iron-reducing micro-organisms using selective media. Findings were compared to an untreated reference site. The addition of organic matter stimulated ferric iron reduction and sulfate reduction in the enclosure and led to elevated pH and accumulations of ferrous iron and reduced sulfur compounds. Numbers of neutrophilic heterotrophic Fe(III) reducers increased during treatment, those of acidophilic heterotrophic Fe(III) reducers remained similar, and those of acidophilic chemolithotrophic Fe(III) reducers decreased. Zones of ferric iron-reducing activity corresponded well with microbial depth profiles; however, viable counts of neutrophilic or acid-tolerant Fe(III) reducers must have been underestimated based on the corresponding observed activity levels. Ferric iron reduction by chemolithotrophic acidophiles seemed to be of minor importance, so a lowering of pH values due to Fe(III) reducing activity is unlikely.     

How does landfill leachate affect the chemical processes in a lake system downgradient from a landfill site?

A field study on the geochemical properties of a chemically-stressed limnic environment was performed in Lake Silbersee, which receives leachate water of high inorganic loading from an upgradient landfill site. The highly concentrated sulfate ion in groundwater, when entering the pore water system of the lake, gives rise to an intensive microbial sulfate reduction. A diagenetic approach was used to explain the existence of a marine-like aqueous system within a geologically slightly acidic aquifer, consisting of a well-buffered lake water and an alkalinity producing, excess sulphide containing sediment pore water system.     

Glacial and periglacial floodplain sediments regulate hydrologic transfer of reactive iron to a high arctic fjord

The transport of reactive iron (i.e. colloidal and dissolved) by a glacier‐fed stream system draining a high relief periglacial landscape in the high Arctic archipelago of Svalbard is described. A negative, non‐linear relationship between discharge and iron concentration is found, indicative of increased iron acquisition along baseflow pathways. Because the glaciers are cold‐based and there are no intra‐ or sub‐permafrost groundwater springs, baseflow is principally supplied by the active layer and the colluvial and alluvial sediments in the lower valley. Collectively, these environments increase the flux of iron in the stream by 40% over a floodplain length of just 8 km, resulting in 6 kg Fe km^?2a^?1 of reactive iron export for a 20% glacierized watershed. We show that pyrite oxidation in shallow‐groundwater flowpaths of the floodplain is the most important source of reactive iron, although it is far less influential in the upper parts of the catchment where other sources are significant (including ironstone and secondary oxide coatings). Microbial catalysis of the pyrite oxidation occurs in the floodplain, enabling rapid, hyporheic water exchange to enhance the iron fluxes at high discharge and cause the non‐linear relationship between discharge and reactive iron concentrations. Furthermore, because the pyrite oxidation is tightly coupled to carbonate and silicate mineral weathering, other nutrients such as base cations and silica are also released to the stream system. Our work therefore shows that high Arctic floodplains should be regarded as critically important regulators of terrestrial nutrient fluxes to coastal ecosystems from glacial and periglacial sources. Copyright © 2015 John Wiley & Sons, Ltd.     

Optical properties and light penetration in a deep,naturally acidic,iron rich lake: Lago Caviahue (Patagonia,Argentina)

The optical properties and light climate in the deep and extremely acid Lake Caviahue have been studied in order to better understand its characteristics and the possible influence upon the phytoplankton community. The absorption coefficients for the dissolved fraction were maximal in the ultraviolet (UV) region and the water absorption spectra showed a shoulder around 300 nm, which was attributed to the concentration of Fe(III). No radiation was detected in the water column below 360 nm. The depth of the 1% incident radiation was dependent of wavelength, showing its maximum of 13.3 m at 565 nm, compared to 1.7 m and 4.8 m at 400 nm and 700 nm, respectively. Phytoplankton biomass was low and showed an almost constant profile with depth despite the relative darkness of the water column. Optical climate of Lake Caviahue is not typical of high elevation lakes but is more similar to low elevation shallow lakes of the Andean region. The chemical composition of the water, mainly Fe oxidation state and concentration, is the responsible for the high attenuation of the UV radiation (UVR). Living organisms are protected of UVR because Lake Caviahue waters are a shield against UV-B.     

Evidence for extreme variations in the permeability of laterite from a detailed analysis of well behaviour in Nigeria

Laterite soils are widespread in tropical Africa and have a large impact on the hydrology of the areas they cover. The permeability of laterite helps determine the partitioning of runoff and interflow and regulates groundwater recharge to underlying bedrock. Groundwater within laterite also forms a widespread source of drinking water, typically from unimproved hang‐dug‐wells. Despite its importance, there is little published information on laterite aquifer properties. In this study, data from a 6 m deep well in Nigeria have been analysed to characterise the hydraulic conductivity of the laterite from repeated pumping tests. Transmissivity measurements from 40 tests spread out across a hydrological year varied from 0.1 to 1000 m²/d. Further interpretation of the data demonstrate a strong non‐linear decrease in horizontal hydraulic conductivity with depth, characterised by an upper horizon of extreme permeability (400 m/d), and a much lower permeability profile beneath (<0.1 m/d). These data are substantiated with observations from other wells throughout the area. This non‐linear permeability structure has several implications: the upper laterite can facilitate rapid lateral throughflow in the wet season, enabling contaminants to be transported significant distances (up to 1 km); natural groundwater levels are restricted to a narrow range for much of the year; and, in the dry season, the lower permeability of the deeper laterite restricts the amount of water which can be abstracted from shallow wells, leading to well failure. The work highlights the need for a wider study to better understand laterite soils and the role they play in regional hydrology. © 2013 Natural Environment Research Council. Hydrological Processes published by John Wiley & Sons Ltd.     

The role of sediments in the phosphorus cycle in Lake Lugano. II. Seasonal and spatial variability of microbiological processes at the sediment-water interface

P, Fe, Mn, and S species were analyzed in water samples from the sediment-water interface collected at four seasonally different times during the course of a year at two sampling sites in the southern basin of Lake Lugano (Lago di Lugano). The results reveal the strong influence of the biogeochemical processes in the sediment on the chemical composition of the lake water above. Consumption of oxygen and nitrate under oxic to microoxic conditions in the water column as well as sequential release of reduced manganese and iron under anoxic conditions was observed as a direct or indirect consequence of microbially mediated degradation of organic matter. The seasonal pattern observed for the release and the retainment of dissolved reduced iron and manganese correlates well with the one for dissolved phosphate. Iron, manganese and phosphorus cycling are coupled tightly in these sediments. Both sediment types act as sinks for hydrogen sulfide and sulfate. An inner-sedimentary sulfur cycle is proposed to couple iron, manganese and phosphorus cycling with the degradation of organic matter. Nutrient cycling at the sediment-water interface might thus be driven by a microbially regulated electron pumping mechanism. The results contribute to a better understanding of the role of sediment processes in the lake's internal phosphorus cycle and its seasonal dynamics.     

Evidence for toxic cyanobacteria in sediments and the water-sediment interface of a tropical drinking water reservoir

Cyanobacterial blooms in drinking water reservoirs constitute a health risk for humans and animals, especially in tropical zones where climate conditions may favour their prevalence throughout the year. The presence, viability, and toxicity of cyanobacteria were determined in the euphotic zone, in the water-sediment interface, and in the upper sediment fraction of the Riogrande II reservoir (Antioquia, Colombia), which provides drinking water for 1.4 million people. Cyanobacterial identification and quantification were performed in environmental samples of the euphotic zone and of the sediment-water interface. In addition, the effects of environmental parameters on occurrences of cyanobacteria were assessed and two microcystin synthetase (mcy) genes were extracted from water, interface, and sediment samples and quantified using qPCR. The viability of the cells in cultures from these different matrices was determined using chlorophyll-a measurements. Chlorophyll-a concentrations representing the biomass of cyanobacteria were higher at the interface than in the euphotic zone at all sampling sites. The potentially toxic genera Dolichospermum and Microcystis predominated in the euphotic zone and the interface, respectively. Moreover, the copy numbers of mcy genes was higher in cyanobacteria sampled at the interface and the upper sediment layers than in cyanobacteria sampled in the euphotic zone, which were correlated with the order Chroococcales. No impact of variation in environmental conditions on cyanobacterial abundance was observed. Viability of cyanobacterial cultures sampled from the interface and the upper sediment fraction showed the ability of cyanobacteria from several orders to proliferate under lab conditions. These results show that the surface sediment layer from Riogrande II serves as a sink for potentially toxic cyanobacteria which have the potential to recolonize and bloom in the water column.     

Seasonal dynamics of microbial sulfate reduction in temperate intertidal surface sediments: controls by temperature and organic matter

The role of microbial sulfate reduction on organic matter oxidation was studied quantitatively in temperate intertidal surface sediments of the German Wadden Sea (southern North Sea) on a seasonal base in the years 1998–2007. The sampling sites represent the range of sediments found in the back-barrier tidal area of Spiekeroog Island: sands, mixed and muddy flats. The correspondingly different contents in organic matter, metals, and porosities lead to significant differences in the activity of sulfate-reducing bacteria with volumetric sulfate reduction rates (SRR) in the top 15 cm of up to 1.4 μmol cm^?3 day^?1. Depth-integrated areal SRR ranged between 0.9 and 106 mmol m^?2 day^?1, with the highest values found in the mudflat sediments and lower rates measured in sands at the same time, demonstrating the impact of both temperature and organic matter load. According to a modeling approach for a 154-km² large tidal area, about 39, 122, and 285 tons of sulfate are reduced per day, during winter, spring/autumn, and summer, respectively. Hence, the importance of areal benthic organic matter mineralization by microbial sulfate reduction increases during spring/autumn and summer by factors of about 2 and 7, respectively, when compared to winter time. The combined results correspond to an estimated benthic organic carbon mineralization rate via sulfate reduction of 78 g C m^?2 year^?1.     

Effects of reservoir stratification and watershed hydrology on manganese and iron in a dam‐regulated river

The presence of metals, including manganese (Mn) and iron (Fe), adversely impacts water quality. In seasonally stratified reservoirs, Mn and Fe can accumulate in the water column due to reducing conditions in sediments and be released to downstream rivers through dam discharge. In addition to reservoir stratification influences, the release of metals downstream is influenced by hydrologic conditions in the river. We examined the seasonal and spatial variability of Mn and Fe concentrations in a eutrophic, hydropower reservoir and the downstream river over a two‐year period. Overall, we found that reservoir stratification was a strong predictor of tailrace Mn and Fe concentrations but that tailrace Fe concentrations were also influenced by dam discharge. Downgradient of the tailrace, river discharge and suspended sediment were the dominant predictors of both Mn and Fe concentrations. Using our data, we develop a conceptual model of seasonal and hydrologic drivers of metal concentrations. The model can be modified for other systems aiding drinking water utilities and other water users in forecasting under what seasonal and hydrologic conditions that Mn and Fe concentrations in river systems are likely to be elevated.     

A kinetic approach for simulating redox‐controlled fringe and core biodegradation processes in groundwater: model development and application to a landfill site in Piedmont,Italy

A three‐dimensional model for predicting redox controlled, multi‐species reactive transport processes in groundwater systems is presented. The model equations were fully integrated within a MODFLOW‐family reactive transport code, RT3D. The model can simulate organic compound biodegradation coupled to different terminal electron acceptor processes. A computational approach, which uses the spatial and temporal distribution of the rates of different redox reactions, is proposed to map redox zones. The method allows one to quantify and visualize the biological degradation reactions occurring in three distinct patterns involving fringe, pseudo‐core and core processes. The capabilities of the numerical model are demonstrated using two hypothetical examples: a batch problem and a simplified two‐dimensional reactive transport problem. The model is then applied to an unconfined aquifer underlying a leaking landfill located near the city of Turin, in Piedmont (Italy). At this site, high organic load from the landfill leachate activates different biogeochemical processes, including aerobic degradation, denitrification, manganese reduction, iron reduction, sulfate reduction and methanogenesis. The model was able to describe and quantify these complex biogeochemical processes. The proposed model offers a rational framework for simulating coupled reactive transport processes occurring beneath a landfill site. Copyright © 2008 John Wiley & Sons, Ltd.     

Groundwater pollution containing ammonium,iron and manganese in a riverbank filtration system: Effects of dynamic geochemical conditions and microbial responses

Bench-scale experiments were conducted to investigate the effect of hydraulic loadings and influent concentration on the migration and biotransformation behaviour of three groundwater pollutants: ammonium (NH₄⁺), iron (Fe²⁺) and manganese (Mn²⁺). Columns packed with aquifer media collected from a riverbank filtration (RBF) site in Harbin City, NE China were introduced synthetic groundwater (SGW) or real groundwater (RGW) were at two different constant flow rates and initial contaminant concentrations to determine the impact of system conditions on the fate of the target pollutants biotransformation. The results showed that the biotransformation rate of Fe²⁺ Mn²⁺ and NH₄⁺ decreased by 8%, 39% and 15% under high flow rate (50 L d⁻¹) compared to low flow rate (25 L d⁻¹), which was consistent with the residence-time effect. While the biotransformation rate of Fe²⁺ Mn²⁺ and NH₄⁺ decreased by 7%, 14% and 9% under high influent concentration comparing with original groundwater. The 16S rRNA analysis of the aquifer media at different depths after experiments completion demonstrated that the relative abundance of major functional microbes iron-oxidizing bacteria and manganese-oxidizing bacteria under higher flow rate and higher influent concentration decreased 13%, 14% and 25%, 24%, respectively, whereas the ammonium-oxidizing bacteria and nitrite-oxidizing bacteria exhibited minimal change, compared to the lower flow rate. Above all results indicated that both high flow rate and high concentration inhibit the biotransformation of NH₄⁺, Fe²⁺ and Mn²⁺. The biotransformation of Fe²⁺ and Mn²⁺ occurs primarily in the 0–40 cm and 20–60 cm depth intervals, respectively, whereas the NH₄⁺ biotransformation appears to occur relatively uniformly throughout the whole 110 cm column. The biotransformation kinetics of NH₄⁺ in RGW and SGW, Mn²⁺ in RGW at different depths accords with the first order kinetics model, while Fe²⁺ in RGW and SGW, Mn²⁺ in SGW presented more complicated biotransformation process. The results should improve understanding of the transport and fate of common groundwater pollutants in RBF and other groundwater recharge environments.     

Development of a three‐dimensional watershed modelling system for water cycle in the middle part of the Heihe rivershed,in the west of China

A three‐dimensional numerical modelling system is developed to study transformation processes of water resources in alluvial fan and river basin along the middle reaches of the Heihe River Basin, Northwest China, an arid and semi‐arid region. Integrating land utilization, remote sensing and geographic information systems, we have developed a numerical modelling system that can be used to quantify the effects of land use and anthropogenic activities on the groundwater system as well as to investigate the interaction between surface water and groundwater. Various hydraulic measurements are used to identify and calibrate the hydraulic boundary conditions and spatial distributions of hydraulic parameters. In the modelling study, various water exchanges and human effects on the watershed system are considered. These include water exchange between surface water and groundwater, groundwater pumping, lateral water recharges from mountain areas, land utilization, and infiltration and evaporation in the irrigation and non‐irrigation areas. The modelling system provides a quantitative method to describe spatial and temporal distributions and transformations between various water resources, and it has application to other watersheds in arid and semi‐arid areas. Copyright © 2011 John Wiley & Sons, Ltd.     

Cretaceous desert cycles,wind direction and hydrologic cycle variations in Ordos Basin: Evidence for Cretaceous climatic unequability

Whether climate under greenhouse condition in geological history, especially in Cretaceous, was eq-uable or not has been acutely debated for a long time. Early studies[1—8] show that the subtropical zones then expanded northwards and southwards to the latitudes about 65S and 65N, while the temperate zones oc-cupied the latitudes of 65—90S and 65—90N. Con-sequently, the two poles were ice-free, equator-to-pole surface temperature gradient was obviously reduced, amplitude of climatic change…     

REE and (э)Nd of clay fractions in sediments from the eastern Pacific Ocean: Evidence for clay sources

Clay fractions in the non-calcareous surface sediments from the eastern Pacific were analyzed for clay minerals, REE and 143Nd/144Nd. Montmorillonite/illite ratio (M/I ratio), total REE contents ((REE), LREE/HREE ratio and cerium anomaly (бCe) may effectively indicate the genesis of clay minerals. Clay fractions with M/I ratio >1, бCe (0.85, (REE (400 μg/g, LREE/HREE ratio (4, and REE patterns similar to those of pelagic sediments are terrigenous and autogenetic mixed clay fractions and contain more autogenetic montmorillonite. Clay fractions with M/I ratio <1, бCe=0.86 to 1.5, ΣREE=200 to 350 μg/g, LREE/HREE ratio (6 and REE distribution patterns similar to that of China loess are identified as terrigenous clay fraction. The 143Nd/144Nd ratios or (э)Nd values of clay fractions inherit the features of terrigenous sources of clay minerals. Clay fractions are divided into 4 types according to (э)Nd values. Terrigenous clay minerals of type I with the (э)Nd values of -8 to -6 originate mainly from North American fluvial deposits. Those of type II with the (э)Nd values of -9 to -7 are mainly from the East Asia and North American fluvial deposits. Those of type III with (э)Nd values of -6 to -3 could come from the central and eastern Pacific volcanic islands. Those of type IV with (э)Nd values of -13 to -12 may be from East Asia eolian. The terrigenous and autogenetic mixed clay fractions show patchy distributions, indicating that there are volcanic or hot-spot activities in the eastern Pacific plate, while the terrigenous clay fractions cover a large part of the study area, proving that the terrigenous clay minerals are dominant in the eastern Pacific.     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

A comparison of element outputs in solution,suspended sediments and bedload for a small upland catchment

The individual outputs of several elements in solution, suspended solids and bedload were estimated for a stream draining a small upland catchment in mid-Wales. The data indicate the overall importance of transport in solution, although the solid phase can make a significant contribution to the export of potassium, iron and silicon from the site.