The chemistry of suspended matter in Esthwaite Water,a biologically productive lake with seasonally anoxic hypolimnion

Ten detailed vertical water column profiles were taken between April and November, 1979, in Esthwaite Water (English Lake district), a lake with high biological productivity and a seasonally anoxic hypolimnion. Measurements of the major-element particle composition (organic C, P, S, Si, Al, Ti, K, Mg, Ca, Fe, Mn, and Ba) and hydrochemical constituents (temperature, pH, dissolved oxygen, total suspended load, dissolved Fe, Mn, P, and Ba) were carried out. These have revealed new information about the mechanisms and kinetics of biogeochemical cycles in a lake.Pronounced seasonal cycles exist in which large excess concentrations (those unsupported by detrital components) of particulate organic C, Fe, Mn, P, S, Mg, K, Ba, and Ca are being generated and lost in situ in the water column (15m deep). In the epilimnion these elements (excepting Fe and Mn) are incorporated into the organic components of growing phytoplankton during the spring and summer. Simultaneously, in the hypolimnion there is a build-up and then a decrease in the excess concentrations of particulate C, P, S, Mg, K, Ba and Ca; this cycle is due to the indirect involvement of these elements with the iron redox cycle. As the hypolimnion becomes anoxic, dissolved ferrous Fe is released from the sediments and large concentrations of excess particulate iron (III) oxides accumulate; these oxides act as adsorbing substrates for the above mentioned elements. As conditions become more reducing, these same elements are solubilized as the iron (III) oxide particles are reduced to dissolved ferrous iron.Adsorption equations are derived from the field data which relate the concentration of excess particulate Fe to those of POC, P, S, Ca, Mg, Ba, and K. At the last stages of anoxia (before the lake overturns) large populations of bacteria and the formation of iron sulfide particles control the concentrations of excess particulate C, S, P, Mg, K, and Ca.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

Iron isotope systematics in estuaries: The case of North River, Massachusetts (USA)

Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ⁵⁶Fe values (with an average of 0.43 ± 0.04‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ⁵⁶Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ⁵⁶Fe values vary from −0.09‰ at no flocculation to ∼0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ⁵⁶Fe composition of rivers can also be characterized by more positive δ⁵⁶Fe values (up to 0.3‰) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.     

Iron isotope fractionation during biogeochemical cycle: Information from suspended particulate matter (SPM) in Aha Lake and its tributaries,Guizhou, China

Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ⁵⁶Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ⁵⁶Fe value: the δ⁵⁶Fe values of SPM in summer were lower than in winter. The seasonal variation in δ⁵⁶Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ⁵⁶Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ⁵⁶Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ⁵⁶Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ⁵⁶Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.     

Fast transformation of iron oxyhydroxides by the catalytic action of aqueous Fe(II)

Iron oxides may undergo structural transformations when entering an anoxic environment. These transformations were investigated using the isotopic exchange between aqueous Fe(II) and iron oxides in experiments with ⁵⁵Fe-labelled iron oxides. ⁵⁵Fe was incorporated congruently into a ferrihydrite, two lepidocrocites (#1 and #2), synthesised at 10°C and 25°C, respectively, a goethite and a hematite. The iron oxides were then submerged in Fe²⁺ solutions (0-1.0 mM) with a pH of 6.5. In the presence of aqueous Fe²⁺, an immediate and very rapid release of ⁵⁵Fe was observed from ferrihydrite, the two lepidocrocites and goethite, whereas in the absence of Fe²⁺ no release was observed. ⁵⁵Fe was not released from hematite, even at the higher Fe²⁺ concentration. The release rate is mainly controlled by characteristics of the iron oxides, whereas the concentration of Fe²⁺ only has minor influence. Ferrihydrite and 5-nm-sized lepidocrocite crystals attained complete isotopic equilibration with aqueous Fe(II) within days. Within this timeframe ferrihydrite transformed completely into new and more stable phases such as lepidocrocite and goethite. Lepidocrocite #2 and goethite, having larger particles, did not reach isotopic equilibrium within the timeframe of the experiment; however, the continuous slow release of ⁵⁵Fe suggests that isotopic equilibrium will ultimately be attained.Our results imply a recrystallization of solid Fe(III) phases induced by the catalytic action of aqueous Fe(II). Accordingly, iron oxides should properly be considered as dynamic phases that change composition when exposed to variable redox conditions. These results necessitate a reevaluation of current models for the release of trace metals under reducing conditions, the sequestration of heavy metals by iron oxides, and the significance of stable iron isotope signatures.     

The diagenetic geochemistry and contamination assessment of iron,cadmium, and lead in the sediments from the Shuangtaizi estuary,China

Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m^?2 a^?1), followed by Cd (0.54 mg m^?2 a^?1) and Pb (0.42 mg m^?2 a^?1). Low Fe²⁺ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe²⁺ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS₂). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb²⁺ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd²⁺ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.     

Revealing forms of iron in river-borne material from major tropical rivers of the Amazon Basin (Brazil)

The present study deals with the direct determination of colloidal forms of iron in river-borne solids from main rivers of the Amazon Basin. The contribution of different forms of colloidal iron have been assessed using ultrafiltration associated with various techniques including electron paramagnetic resonance spectroscopy (EPR), high resolution transmission electron microscopy (HRTEM), and micro proton-induced X ray emission analysis (μPIXE). EPR shows the presence of Fe³⁺ bound to organic matter (Fe³⁺-OM) and colloidal iron oxides. Quantitative estimate of Fe³⁺-OM content in colloidal matter ranges from 0.1 to 1.6 weight % of dried solids and decreases as the pH of the river increases in the range 4 to 6.8. The modeling of the field data with the Equilibrium Calculation of Speciation and Transport (ECOSAT) code demonstrates that this trend is indicative of a geochemical control resulting from the solubility equilibrium of Fe oxyhydroxide phase and Fe binding to organic matter. Combining EPR and μPIXE data quantitatively confirms the presence of colloidal iron phase (min. 35 to 65% of iron content), assuming no divalent Fe is present. In the Rio Negro, HRTEM specifies the nature of colloidal iron phase mainly as ferrihydrite particles of circa 20 to 50 Å associated with organic matter. The geochemical forms of colloidal iron differentiate the pedoclimatic regions drained by the different rivers, corresponding to different major weathering/erosion processes. Modeling allows the calculation of the speciation of iron as mineral, organic and dissolved phases in the studied rivers.     

The adsorption of aquatic humic substances by two oxides of manganese

A study was made of the adsorption of humic substances (HS) by Mn₃O₄ and by oxide B, a preparation with the β-MnOOH diffraction pattern but having a manganese oxidation state of 3.4. The interactions follow trends found for other oxides. Thus in 0.01 mol dm^?3 NaCl adsorption decreases with increasing pH, while it is enhanced by Ca²⁺. The HS adsorb more strongly to the oxide with the higher zero point of charge (Mn₃O₄), while the effect of Ca²⁺ is greater for oxide B.Microelectrophoretic measurements show that the oxide particles take on the electrokinetic characteristics of the adsorbed HS. However it was found that the magnitude of the mobility depends on the underlying oxide surface and on the source of the HS. The electrokinetic properties of the two oxides dispersed in surface water samples of Esthwaite Water, Cumbria, England, can be accounted for by the adsorbed HS together with coadsorbed Ca²⁺.     

Oxidation products of Mn(II) in lake waters

Oxygenation of Mn(II)-rich water samples taken from two English lakes (Esthwaite Water, Cumbria, and Rostherne Mere, Cheshire) during the summer months caused the precipitation of Mn-oxide, the process being catalysed by particulate matter. The Mnoxide formed resembles vernadite (δ-MnO₂) with regard to: (1) Mn oxidation state (> 3.6 in all but one case); and (2) its fine morphology (crumpled thin sheets) as determined by electron microscopy. The precipitates are, however, rather amorphous to X-rays, giving only very weak reflections which cannot be assigned unequivocally. Electron probe microanalysis shows the presence of a number of other elements in the Mn-containing phase. The most abundant is Ca (Ca/Mn weight ratio $\text{? 0.1}$), others are Mg, Si, P, S, Cl, K, Ba and Fe. The precipitates contain much organic matter (20–30 wt.%) but little appears to be associated directly with the Mn phase. Only small amounts (～ 1 wt.%) of humic substances are present. Some but not all of the specimens examined had the gross morphology of Metallogenium, a Mn-depositing bacterium.Naturally occurring Mn-oxides present in Esthwaite Water during the summer resemble, the products of oxygenation in their fine morphology and contents of other elements. Mn-oxides present during the winter are somewhat different morphologically. In one summer sample of particulate matter from Esthwaite Water no Mn-oxide could be found by electron microscopic examination, but Mn was found concentrated in bacteria. This observation, the rapid rates of oxidation and the high Mn oxidation states, suggest that bacteria might play a rôle in catalysing the oxidation of Mn(II).     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg²⁺ and CH₃Hg⁺ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg²⁺ is strongly dependent on complexation to dissolved organic matter, the solubility of CH₃Hg⁺ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH₃Hg⁺. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.     

Release of arsenic associated with the reduction and transformation of iron oxides

The behaviour of trace amounts of arsenate coprecipitated with ferrihydrite, lepidocrocite and goethite was studied during reductive dissolution and phase transformation of the iron oxides using [⁵⁵Fe]- and [⁷³As]-labelled iron oxides. The As/Fe molar ratio ranged from 0 to 0.005 for ferrihydrite and lepidocrocite and from 0 to 0.001 for goethite. For ferrihydrite and lepidocrocite, all the arsenate remained associated with the surface, whereas for goethite only 30% of the arsenate was desorbable. The rate of reductive dissolution in 10 mM ascorbic acid was unaffected by the presence of arsenate for any of the iron oxides and the arsenate was not reduced to arsenite by ascorbic acid. During reductive dissolution of the iron oxides, arsenate was released incongruently with Fe²⁺ for all the iron oxides. For ferrihydrite and goethite, the arsenate remained adsorbed to the surface and was not released until the surface area became too small to adsorb all the arsenate. In contrast, arsenate preferentially desorbs from the surface of lepidocrocite. During Fe²⁺ catalysed transformation of ferrihydrite and lepidocrocite, arsenate became bound more strongly to the product phases. X-ray diffractograms showed that ferrihydrite was transformed into lepidocrocite, goethite and magnetite whereas lepidocrocite either remained untransformed or was transformed into magnetite. The rate of recrystallization of ferrihydrite was not affected by the presence of arsenate. The results presented here imply that during reductive dissolution of iron oxides in natural sediments there will be no simple correlation between the release of arsenate and Fe²⁺. Recrystallization of the more reactive iron oxides into more crystalline phases, induced by the appearance of Fe²⁺ in anoxic aquifers, may be an important trapping mechanism for arsenic.     

Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB⁺, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB⁺ at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.     

Quantitative mineralogical and chemical assessment of the Nkout iron ore deposit,Southern Cameroon

The Nkout deposit is part of an emerging iron ore province in West and Central Africa. The deposit is an oxide facies iron formation comprising fresh magnetite banded iron formation (BIF) at depth, which weathers and oxidises towards the surface forming caps of high grade hematite/martite–goethite ores. The mineral species, compositions, mineral associations, and liberation have been studied using automated mineralogy (QEMSCAN^®) combined with whole rock geochemistry, mineral chemistry and mineralogical techniques. Drill cores (saprolitic, lateritic, BIF), grab and outcrop samples were studied and divided into 4 main groups based on whole rock Fe content and a weathering index. The groups are; enriched material (EM), weathered magnetite itabirite (WMI), transitional magnetite itabirite (TMI) and magnetite itabirite (MI). The main iron minerals are the iron oxides (magnetite, hematite, and goethite) and chamosite. The iron oxides are closely associated in the high grade cap and liberation of them individually is poor. Liberation increases when they are grouped together as iron oxides. Chamosite significantly lowers the liberation of the iron oxides. Automated mineralogy by QEMSCAN^® (or other similar techniques) can distinguish between Fe oxides if set up and calibrated carefully using the backscattered electron signal. Electron beam techniques have the advantage over other quantitative mineralogy techniques of being able to determine mineral chemical variants of ore and gangue minerals, although reflected light optical microscopy remains the most sensitive method of distinguishing closely related iron oxide minerals. Both optical and electron beam automated mineralogical methods have distinct advantages over quantitative XRD in that they can determine mineral associations, liberation, amorphous phases and trace phases.     

Analysis of cation distribution in the octahedral sheet of dioctahedral 2:1 phyllosilicates by using inverse Monte Carlo methods

An inverse Monte Carlo (MC) method was developed to determine the distribution of octahedral cations (Al³⁺, Fe³⁺, and Mg²⁺) in bentonite illite–smectite (I–S) samples (dioctahedral 2:1 phyllosilicates) using FT–IR and ²⁷Al MAS NMR spectroscopies. FT–IR allows determination of the nature and proportion of different cation pairs bound to OH groups measuring the intensities of OH-bending bands. ²⁷Al MAS NMR data provide information about cation configuration because ²⁷Al MAS NMR intensity depends on Fe distribution. MC calculations based on FT–IR data alone show Fe segregation by short-range ordering (Fe clusters within 9 to 15?Å from a given Fe atom). Fe segregation increases with illite proportion. MC calculations based on IR and ²⁷Al NMR simultaneously yield similar configurations in which Fe clusters are smaller. The latter calculations fail to build appropriate cation distributions for those samples with higher number of illite layers and significant Fe content, which is indicative of long-range Fe ordering that cannot be detected by FT–IR and ²⁷Al MAS NMR. The proportion of Mg–Mg pairs is negligible in all samples, and calculations, in which the number of Mg atoms, as second neighbours, is minimised, create appropriate configurations.     

The formation of graphite upon the interaction of subducted carbonates and sulfur with metal-bearing rocks of the lithospheric mantle

Experimental studies of the Fe⁰–(Mg, Ca)CO₃–S system were carried out during 18–20 h at 6.3 GPa, 900–1400°C. It is shown that the major processes resulting in the formation of free carbon include reduction of carbonates upon redox interaction with Fe⁰ (or Fe₃C), extraction of carbon from iron carbide upon interaction with a sulfur melt/fluid, and reduction of the carbonate melt by Fe–S and Fe?S–C melts. Reconstruction of the processes of graphite formation indicates that carbonates and iron carbide may be potential sources of carbon under the conditions of subduction, and participation of the sulfur melt/fluid may result in the formation of mantle sulfides.     

Ferromanganese carbonate metasediments of the Sob area,Polar Urals: Bedding conditions,composition, and genesis

The paper presents the results of study of ferromanganese carbonate rocks in the Sob area (Polar Urals), which is located between the Rai-Iz massif and the Seida–Labytnangi Railway branch. These rocks represent low-metamorphosed sedimentary rocks confined to the Devonian carbonaceous siliceous and clayey–siliceous shales. In terms of ratio of the major minerals, ferromanganese rocks can be divided into three varieties composed of the following minerals: (1) siderite, rhodochrosite, chamosite, quartz, ± kutnahorite, ± calcite, ± magnetite, ± pyrite, ± clinochlore, ± stilpnomelane; (2) spessartite, rhodochrosite, and quartz, ± hematite, ± chamosite; (3) rhodochrosite, spessartite, pyroxmanite, quartz ± tephroite, ± fridelite, ± clinochlore, ± pyrophanite, ± pyrite. In all varieties, the major concentrators of Mn and Fe are carbonates (rhodochrosite, siderite, kutnahorite, Mn-calcite) and chlorite group minerals (clinochlore, chamosite). The chemical composition of rocks is dominated by Si, Fe, Mn, carbon dioxide, and water (L.O.I.): total SiO₂ + Fe₂O ₃ ^tot + MnO + L.O.I. = 85.6?98.4 wt %. The content of Fe and Mn varies from 9.3 to 55.6 wt % (Fe₂O ₃ ^tot + MnO). The Mn/Fe ratio varies from 0.2 to 55.3. In terms of the aluminum module Al_M = Al/(Al + Mn + Fe), the major portion of studied samples corresponds to metalliferous sediments. The δ¹³C_carb range (–30.4 to–11.9‰ PDB) corresponds to authigenic carbonates formed with carbon dioxide released during the microbial oxidation of organic matter in sediments at the dia- and/or catagenetic stage. Ferromanganese sediments were likely deposited in relatively closed seafloor zones (basin-traps) characterized by periodic stagnation. Fe and Mn could be delivered from various sources: input by diverse hydrothermal solutions, silt waters in the course of diagenesis, river discharges, and others. The diagenetic delivery of metals seems to be most plausible. Mn was concentrated during the stagnation of bottom water in basin-traps. Interruption of stagnation promoted the precipitation of Mn. The presence of organic matter fostered a reductive pattern of postsedimentary transformations of metalliferous sediments. Fe and Mn were accumulated initially in the oxide form. During the diagenesis, manganese and iron oxides reacted with organic matter to make up carbonates. Relative to manganese carbonates, iron carbonates were formed under more reductive settings and higher concentrations of carbon dioxide in the interstitial solution. Crystallization of manganese and iron silicates began already at early stages of lithogenesis and ended during the regional metamorphism of metalliferous sediments.     

Geochemistry,water balance,and stable isotopes of a “clean” pit lake at an abandoned tungsten mine,Montana, USA

The Calvert Mine is a small tungsten-rich (scheelite) skarn deposit in a remote, mountainous region of southwest Montana, USA. The open-pit mine closed in the 1970s and subsequently flooded to form a pit lake that is roughly conical in shape, 30 m deep and 120 m in diameter, with no surface inlet or outlet. The lake is holomictic with a groundwater flow-through hydrology and an estimated residence time of 2.5–5 y. Water isotopes show that the lake is at an approximate steady state with respect to water balance and has experienced 30% evaporation. The lake has a near-neutral pH, exceptional clarity, and extremely low concentrations of nutrients, sulfate, and most metals, including tungsten. Manganese concentrations are slightly elevated and increase with depth towards the sediment–water interface. Despite seasonally anoxic conditions in the deep water, dissolved Fe concentrations are orders of magnitude lower than Mn, suggesting that insufficient organic carbon is present in the sediment of this oligotrophic lake to drive bacterial Fe reduction. Based on stable isotope fingerprinting, diffuse seepage that enters a nearby headwater stream at the base of a large waste-rock pile can be directly linked to the partially evaporated pit lake. However, this seepage has neutral pH and low metal concentrations, and poses no threats to the environment. Stable isotopes of dissolved inorganic carbon (DIC) and dissolved oxygen (DO) are used to track the relative importance of photosynthesis and respiration with depth. In summer, a zone of high productivity exists near the base of the chemocline, releasing DO that is isotopically light. Respiration exceeds photosynthesis below the Secchi depth, which causes DO concentrations to approach zero towards the bottom of the lake. In winter, thick ice and snow cover prohibits photosynthesis. However, because of the low nutrient content, most of the volume of the lake remains oxic through the winter. Overall, the Calvert Lake is a good example of a pit lake formed from metal mining that has excellent water quality, which is a result of its favorable geology (paucity of sulfide minerals) and hydrology (flow-through lake with short residence time in a temperate climate).