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.     

Diel cycles of hydrogen peroxide in marine bathing waters in Southern California, USA: In situ surf zone measurements

Hydrogen peroxide is photochemically produced in natural waters. It has been implicated in the oxidative-induced mortality of fecal indicator bacteria (FIB), a microbial water quality measure. To assess levels and cycling of peroxide in beach waters monitored for FIB, diel studies were carried out in surf zone waters in July 2009 at Crystal Cove State Beach, Southern California, USA. Maximum concentrations of 160–200 nM were obtained within 1 h of solar noon. Levels dropped at night to 20–40 nM, consistent with photochemical production from sunlight. Day-time production and night-time dark loss rates averaged 16 ± 3 nM h⁻¹ and 12 ± 4 nM h⁻¹ respectively. Apparent quantum yields averaged 0.07 ± 0.02. Production was largely dominated by sunlight, with some dependence on chromophoric dissolved organic matter (CDOM) levels in waters with high absorption coefficients. Peroxide levels measured here are sufficient to cause oxidative-stress-induced mortality of bacteria, affect FIB diel cycling and impact microbial water quality in marine bathing waters.     

Iron in the southeastern Bering Sea: Elevated leachable particulate Fe in shelf bottom waters as an important source for surface waters

Surface transects and vertical profiles of total and leachable particulate Fe, Mn, Al and P, along with dissolved and soluble Fe were obtained during August 2003 in the southeastern Bering Sea. High concentrations of leachable particulate Fe were observed in the bottom waters over the Bering Sea shelf with an unusually high percentage of the suspended particulate Fe being leachable. Leachable particulate Fe averaged 81% of total particulate Fe, and existed at elevated concentrations that averaged 23 times greater than dissolved Fe in the isolated cool pool waters over the mid shelf where substantial influence of sedimentary denitrification was apparent. The elevated leachable particulate Fe is suggested to be a result of sedimentary Fe reduction in surficial sediments, diffusion of Fe(II) from the sediments to the bottom waters, and subsequent oxidation and precipitation of reduced Fe in the overlying bottom waters. Eddies and meanders of the Bering Slope Current can mix this Fe-rich water into the Green Belt at the outer shelf-break front. Elevated levels of leachable particulate Fe were observed in surface waters near the Pribilof Islands where enhanced vertical mixing exists. Storm events and/or cooling during fall/winter with the resultant destruction of the thermally stratified two-layer system can also mix the subsurface water into surface waters where the elevated leachable particulate Fe is a substantial source of biologically available Fe.     

Iron oxide formation in artificial ground waters

Artificial ground water containing 40 mg/l Ca and varying concentrations of Fe(II), Fe(III) and Si were rapidly oxidized with air. The ferrihydrite forming is similar to those found in natural Finish ground waters.     

Temporal variability of selected dissolved elements in the lower Orinoco River,Venezuela

Monthly analyses of pH, conductance, alkalinity, total suspended solids, dissolved major cations (Na, K, Ca and Mg), and selected dissolved trace elements (Fe, Al, Mn, Cu, Zn and Cr) were conducted on waters of the lower Orinoco River from February 2004 to May 2006. The data show strong seasonal variability. Major cations had maximum concentrations at low water, and were correlated with pH, conductance and alkalinity because of the tributaries coming from the Andean zones, where the weathering of evaporites and carbonate shales controls water chemistry. K concentrations did not show any relation with evaporite weathering, probably because large amounts of K come from the Guayana Shield rivers as a consequence of feldspar weathering. The concentrations of dissolved Fe, Mn and Cu were highest during the high water stage. Concentrations of the elements K, Cr, Zn and Cu are correlated with each other but not with dissolved Fe and Al, which probably are complexed with humic and fulvic substances. Mn concentrations did not show relationships with other variables. Inter‐annual variability of dissolved elements is explained by temporal changes in precipitation. Copyright © 2008 John Wiley & Sons, Ltd.     

A laboratory study of the biogeochemical cycling of Fe,Mn, Zn and Cu across the sediment-water interface of a productive lake

Laboratory incubation experiments were carried out on sediment cores collected from Esthwaite Water, U.K., during April 1987, when the sediments displayed a characteristic surface (1.5 to 2 cm) oxide floc. The experiments were undertaken at 10°C, in the dark, under variable redox and pH conditions for periods of ~ 720 h (30 d). In some cases, realistic amounts of decomposing lake algae were added to simulate the deposition of an algal bloom. Pore waters and overlying waters were obtained from the incubated sediment cores at various time intervals and the samples analysed for pH and dissolved Fe, Mn, Zn and Cu by AAS. The results demonstrated that trace metal concentrations at the sediment-water interface can show rapid, pulsed responses to episodic events associated with controlling factors such as algal deposition and mixing conditions. The variations in dissolved Fe and Mn concentrations could generally be explained by their well known redox behaviour. Appreciable loss of Mn from solution under conditions of well-developed anoxia was consistent with adsorption of Mn²⁺ by FeS. Cu and Zn were both rapidly (24 h) released into solution during incubation of sediment cores prior to the development of anoxia in the overlying waters. Their most likely sources were the reductive remobilization of Mn oxides and the decomposition of organic matter. The addition of decomposing algae to a series of cores resulted in even higher interfacial dissolved concentrations of Cu and Zn, probably through acting as a supplementary source of the metals and through increased oxide dissolution. Switching from anoxic to oxic conditions also rapidly increased dissolved Cu and Zn concentrations, possibly due to their release during the oxidation of metal sulphides. The enhanced releases of dissolved Cu and Zn were generally short-lived with removal being attributed to the formation of sulphides during anoxia and to adsorption by Fe and Mn oxides under oxic conditions.     

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

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.     

The estuarine chemistry and isotope systematics of U in the Amazon and Fly Rivers

Natural concentrations of ²³⁸U and δ²³⁴U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land–sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates.On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0–16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (1 m) zones of Fe(III)—and, to a lesser degree, Mn(IV)—reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved ²³⁸U profile co-varied closely with Mn(II). Isotopic variations as evidenced in δ²³⁴U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the δ²³⁴U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched δ²³⁴U values represent a riverine surface complexation product that is actively involved in Mn–Fe diagenetic cycles and surface complexation reactions.In the Fly River estuary, ²³⁸U appears to exhibit a reasonably conservative distribution as a function of salinity. The absence of observed U removal does not necessarily imply non-reactivity, but instead may record an integration of concurrent U removal and release processes. There is not a linear correlation between δ²³⁴U vs. 1/²³⁸U that would imply simple two component mixing. It is likely that resuspension of bottom sediments, prolonged residence times in the lower reaches of the Fly River, and energetic particle–colloid interactions contribute to the observed estuarine U distribution. The supply of uranium discharged from humid, tropical river systems to the sea appears to be foremost influenced by particle/water interactions that are ultimately governed by the particular physiographic and hydrologic characteristics of an estuary.     

Study of Heavy Metal Compound Transformations in Surface Waters

Results of studying Fe(III) hydrolysis and sorption of heavy metal compounds by organic matter of bottom sediments are discussed. The rate of Fe(III) hydrolysis is found to be largely determined by the concentration of dissolved organic substances. Values of kinetic parameters are obtained for heavy metal compounds sorption under static and dynamic conditions. Calculating the solubility of Fe, Cu, Cd, Zn, and Pb sulfides allowed the assessment of the amount of metals lost by bottom sediments due to the formation of metal complexes with dissolved organic substances contained in natural waters.     

Modeling and Validating Long‐Term Dynamics of Diel Dissolved Oxygen with Particular Reference to pH in a Temperate Shallow Lake (Turkey)

Long‐term monitoring of changes in dissolved oxygen (DO) and pH is of great importance to quantifying aquatic ecosystem metabolism, particularly for lakes under the changing global environment. During 173 days, diel DO cycles were measured in situ along with the main driving variables of pH, wind speed (WS), and net solar radiation (Rn) in a temperate shallow lake. Best‐fit multiple non‐linear regression (MNLR) models of diel DO time series were built and validated on a monthly basis, with R² values ranging from 42.4% in September to 95.4% in November for validation. The strong relationship between diel DO and pH (r = 0.6) appeared to be related to the patterns of ecosystem productivity and respiration, and sensitivity of decomposing bacteria to changes in pH. pH‐driven lake metabolism appears to have significant implications for diel and seasonal lake metabolism in a changing global environment.     

Optical properties of chromophoric dissolved organic matter (CDOM) in surface and pore waters adjacent to an oil well in a southern California salt marsh

Chromophoric dissolved organic matter (CDOM) optical properties were measured in surface and pore waters as a function of depth and distance from an oil well in a southern California salt marsh. Higher fluorescence and absorbances in pore vs. surface waters suggest soil pore water is a reservoir of CDOM in the marsh. Protein-like fluorophores in pore waters at distinct depths corresponded to variations in sulfate depletion and Fe(II) concentrations from anaerobic microbial activity. These variations were supported by fluorescence indexes and are consistent with differences in optical molecular weight and aromaticity indicators. Fluorescence indices were consistent with autochthonous material of aquatic origin in surface waters, with more terrestrial, humified allochthonous material in deeper pore waters. CDOM optical properties were consistent with significantly enhanced microbial activity in regions closest to the oil well, along with a three-dimensional excitation/emission matrix fluorescence spectrum peak attributable to oil, suggesting anaerobic microbial degradation of oil.     

The Apure River: geochemistry of major and selected trace elements in an Orinoco River tributary coming from the Andes,Venezuela

The analysis of physicochemical variables and selected dissolved elements was performed on the Apure River waters for 15 months. The variables pH, alkalinity, dissolved O₂, conductivity and Na, Ca, Mg and Cd concentrations showed maximum values during low water, whereas K, Si, Fe, Al, Mn, Zn, Cu, Cr and dissolved organic carbon (DOC) showed maximum concentrations during rising and high water. Five important factors were found to control the amount and temporal variability of the dissolved elements: lithology, hydrology, vegetation–floodplain processes, redox conditions and organic complexation. Weathering of silicates, carbonates and evaporites in the Andes provides most of the proportion of Na, Ca, Mg and HCO₃^? to waters. The temporal variability of these ions is controlled by a dilution process. Although Si can be taken up by the biomass, Si and K can be leached from the floodplain by weathering of clays. Microbial decay of the submerged plants in the floodplain during the inundation periods provides DOC and K to river waters and changes the redox conditions in water. The changing redox conditions control the solubility of Mn, Zn and Fe. Dissolved Mn is a function of pH‐dependent redox process, whereas Zn solubility is controlled by scavenging of Zn during the oxidation of Mn²⁺ to MnO₂. Positive relationships between Al, Fe, Cu, Cr and DOC suggest that these elements are complexed by organic colloids generated in the floodplain. Moreover, the binding capacity of Fe with DOC increases under reducing conditions. Although Cd seems to be provided by weathering in the Andes, several processes can affect the mobility of Cd during transport. Copyright © 2010 John Wiley & Sons, Ltd.     

Vertical distribution of the dominant planktonic crustaceans in a mesotrophic reservoir, Xujiahe reservoir (central China)

The day and night vertical distributions of the dominant planktonic crustaceans in Xujiahe Reservoir were investigated on July 7, 1998. Sampling was carried out at Station D in the upstream region, Doupuohe, and Stations LI and LII in the downstream region, Lujiaodao. At Station D and Station LI, Leptodora kindti showed diel vertical migrations. In Daphnia galeata and Diaphanosoma dubia a limited reverse diel vertical migration was found at Station D, and large individuals tended to stay in lower layers during the day. Neutrodiaptomus incongruens seemed to avoid the water column of 0–6 m by day, but a detectable proportion of the population moved upwards at night. Mesocyclops thermocyclopoides showed a clearly defined diel vertical migration behavior at all three stations. The vertical distribution of Thermocyclops crassus was similar at different stations: in daylight hours it was found almost exclusively in the water column below 6 m and during the night a significant proportion of the population shifted upwards.     

Space-time variations of river water chemistry in RF southern Far East

Concentrations and seasonal variations of water chemistry, including dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in rivers of Primorskii Krai are determined. It is shown that, unlike the macrocomposition, the effect of hydrological regime on the concentration of dissolved metal forms is controversial and depends on anthropogenic load, watershed landscapes, and pH variations. Elevated concentrations of dissolved metal forms are recorded in the beginning of spring flood and during low-water period. Beyond the limits of local impact of wastewater, the concentrations of dissolved forms of Cu, Zn, Ni, Pb, and Cd in river waters of the region insignificantly differ from the clearest rivers of the World.     

Evidence for Enhanced Mineral Dissolution in Organic Acid-Rich Shallow Ground Water

Total concentrations of formate, acetate, and isobutyrate varied from less than 5 to greater than 9,000 μmol/l over distances of < 3 m in ground water from a shallow hydrocarbon contaminated aquifer. Laboratory incubations of aquifer material indicate that organic acid concentrations were dependent on the amount of hydrocarbon loading in the sediment and the relative rates of microbial organic acid production and consumption. In heavily contaminated sediments, production greatly exceeded consumption and organic acid concentrations increased. In lightly contaminated sediments rates were essentially equal and organic acid concentrations remained low. Concentrations of dissolved calcium, magnesium, and iron generally were one to two orders of magnitude higher in organic acid-rich ground water than in ground water having low organic acid concentrations. Carbonate and Fe(III)-oxyhydroxide minerals were the likely sources of these elements. Similarly, concentrations of dissolved silica, derived from quartz and k-feldspar, were higher in organic acid-rich ground water than in other waters. The positive relation (r = 0.60, p < .05, n = 16) between concentrations of silica and organic acids suggests that the microbially mediated buildup of organic acids in ground water enhanced quartz/k-feldspar dissolution in the aquifer, although it was not the only factor influencing their dissolution. A model that included organic acid microequivalents normalized by cation microequivalents significantly strengthened the correlation (r = 0.79, p < .001, n = 16) between dissolved silica and organic acid concentrations, indicating that competition between silica and cations for complexation sites on organic acids also influenced quartz/k-feldspar dissolution. Physical evidence for enhanced mineral dissolution in organic acid-rich waters included scanning electron microscopy images of highly corroded quartz and k-feldspar grains from portions of the aquifer containing organic acid-rich ground water. Microporosity generated in hydrocarbon contaminated sediments may adversely affect remediation efforts that depend on the efficient injection of electron acceptors into an aquifer or on the recovery of solutes from an aquifer.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration

Pyrite is a common sulfide mineral, particularly abundant in mining waste. It is a focus of mine envi-ronmental concern because the oxidation of exposed pyrite may lead to acid drainage and poisonous mate-rials (like As and heavy metals) release. In the United States, approximately $1000000 per day is spent in alleviating acid mine drainage[1], while the Canadian mining community has environmental liabilities that exceed $2 billion for disposal, management, and rec-lamation of mine waste[2]. …