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1.
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.  相似文献   

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3.
A critical evaluation of literature values for the solubility products, K sp NBS = [Fe2+][HS–] Fe2+ HS– (H NBS + )–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe2S2 species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)2 and (Fe (HS)3)– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.  相似文献   

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5.
Traditional ocean modeling treats fields resolved on the model grid according to the classical dynamics of continua. Variability on smaller scales is included through sundry eddy viscosities, mixing coefficients and other schemes. In this paper we develop an alternative approach based on statistical dynamics. First, we recognize that we treat probabilities of flows, not the flows themselves. Modeled dependent variables are the moments (expectations) of the probabilities of possible flows. Second, we address the challenge to obtain the equations of motion for the moments of probable flows rather than the (traditional) equations for explicit flows. For linear terms and on larger resolved scales, the statistical equations agree with classical dynamics where those of traditional modeling works well. Differences arise where traditional modeling would relegate unresolved motion to eddy viscosity, etc.. Instead, changes of entropy (<-log P> over the probability distribution of possible flows) with respect to the modeled moments act as forcings upon those moments. In this way we obtain a consistent framework for specifying the terms which, traditionally, represent subgridscale effects. Although these statistical equations are close to the classical equations in many ways, important differences are also evident; here, two phenomena are described where the results differ. We consider eddies interacting with bottom topography. It is seen that traditional eddy viscosity and/or topographic drag, which would reduce large scale flows toward rest, are wrong. The second law of thermodynamics is violated; the arrow of time is running backwards! From statistical dynamics, approximate corrections are obtained, yielding a practical improvement to the fidelity of ocean models. Another phenomenon occurs at much smaller scales in the turbulent mixing of heat and salt. Even when both heat and salt are stably stratifying, their rates of turbulent transfer should differ. This suggests a further model improvement.  相似文献   

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7.
Geochemical studies on cold meteoric waters, post-1980 hot spring waters, fumarole emissions from the dacite dome, and volcanic rocks at Mount St. Helens (MSH) from 1985 to 1989 show that magmatic volatiles are involved in the formation of a new hydrothermal system. Hot spring waters are enriched in 18O by as much as 2 and display enrichments in D relative to cold waters. A well-defined isotopic trend is displayed by the isotopic composition of a>400°C fumarole condensate collected from the central crater in 1980 (-33 D, +6 18O), of condensate samples collected on the dome, and of cold meteoric and hot spring waters. The trend indicates that mixing occurs between local meteoric water and magmatic water degassing from the dacite dome. Between 30 and 70% magmatic water is present in the dome fumarole discharges and 10% magnatic water has been added to the waters of the hydrothermal system. Relations between Cl, SO4 and HCO3 indicate that the hot spring waters are immature volcanic waters formed by reaction of rocks with waters generated by absorption of acidic volcanic fluids. In addition, the B/Cl ratios of the spring waters are similar to the B/Cl ratios of the fumarole condensates (0.02), values of 13C in the HCO3 of the hot springs (-9.5 to-13.5) are similar to the magmatic value at MSH (-10.5), and the 3He/4He ratio, relative to air, in a hot spring water is 5.7, suggesting a magmatic origin for this component.managed by Martin Marietta Energy Systems, Inc., under contract DE-AC05-84OR21400 with the US Department of Energy  相似文献   

8.
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.  相似文献   

9.
铁(氢)氧化物介导的溶解性有机质(DOM)和无机磷(DIP)的固定在水生态系统中普遍存在,对碳、磷元素的生物地球化学循环有重要的影响. 铁(氢)氧化物主要通过吸附和共沉淀两种过程固定DOM和DIP,且铁(氢)氧化物、DOM和DIP三者存在复杂的相互作用. 本文主要从铁(氢)氧化物对DOM和DIP的固定,铁(氢)氧化物、DOM和DIP之间的相互影响等方面综述了相关研究进展,梳理了铁(氢)氧化物、DOM和DIP在吸附和共沉淀过程中的相互作用机制与影响因素. DOM的存在会通过占据铁(氢)氧化物表面吸附点位、络合、抑制铁水解沉淀等途径影响铁(氢)氧化物对DIP的固定; 且不同机制与DOM的不同性质如分子大小、芳香组分、羧基官能团含量等有关. 而DIP的存在会改变铁(氢)氧化物对DOM的固定分馏过程,改变溶液中DOM的组分和性质. 在明晰三者相互作用基础上,探讨了铁(氢)氧化物介导的DOM和DIP的固定过程对湖泊内源磷释放和碳埋藏的可能影响,并对未来的研究方向进行了展望.  相似文献   

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11.
Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.  相似文献   

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13.
A new phenomenon was found at the polar edge of the auroral oval in the postmidnight-morning sectors: field-aligned (FA) high-energy upward electron beams in the energy range 20–40 keV at altitudes about 3 RE, accompanied by bidirectional electron FA beams of keV energy. The beam intensity often reaches more than 0.5 · 103 electrons/s · sr · keV · cm2, and the beams are observed for a relatively long time (3 102–103 s), when the satellite at the apogee moves slowly in the ILAT-MLT frame. A qualitative scenario of the acceleration mechanism is proposed, according to which the satellite is within a region of bidirectional acceleration where a stochastic FA acceleration is accomplished by waves with fluctuating FA electric field components in both directions.  相似文献   

14.
High-time resolution CUTLASS observations and ground-based magnetometers have been employed to study the occurrence of vortical flow structures propagating through the high-latitude ionosphere during magnetospheric substorms. Fast-moving flow vortices (800 m s–1) associated with Hall currents flowing around upward directed field-aligned currents are frequently observed propagating at high speed (1 km s–1) azimuthally away from the region of the ionosphere associated with the location of the substorm expansion phase onset. Furthermore, a statistical analysis drawn from over 1000 h of high-time resolution, nightside radar data has enabled the characterisation of the bulk properties of these vortical flow systems. Their occurrence with respect to substorm phase has been investigated and a possible generation mechanism has been suggested.  相似文献   

15.
The recent boom in shale gas development in the Marcellus Shale has increased interest in the methods to distinguish between naturally occurring methane in groundwater and stray methane associated with drilling and production operations. This study evaluates the relationship between natural methane occurrence and three principal environmental factors (groundwater redox state, water type, and topography) using two pre‐drill datasets of 132 samples from western Pennsylvania, Ohio, and West Virginia and 1417 samples from northeastern Pennsylvania. Higher natural methane concentrations in residential wells are strongly associated with reducing conditions characterized by low nitrate and low sulfate ([NO3?] < 0.5 mg/L; [SO42?] < 2.5 mg/L). However, no significant relationship exists between methane and iron [Fe(II)], which is traditionally considered an indicator of conditions that have progressed through iron reduction. As shown in previous studies, water type is significantly correlated with natural methane concentrations, where sodium (Na) ‐rich waters exhibit significantly higher (p<0.001) natural methane concentrations than calcium (Ca)‐rich waters. For water wells exhibiting Na‐rich waters and/or low nitrate and low sulfate conditions, valley locations are associated with higher methane concentrations than upland topography. Consequently, we identify three factors (“Low NO3? & SO42?” redox condition, Na‐rich water type, and valley location), which, in combination, offer strong predictive power regarding the natural occurrence of high methane concentrations. Samples exhibiting these three factors have a median methane concentration of 10,000 µg/L. These heuristic relationships may facilitate the design of pre‐drill monitoring programs and the subsequent evaluation of post‐drill monitoring results to help distinguish between naturally occurring methane and methane originating from anthropogenic sources or migration pathways.  相似文献   

16.
In natural waters arsenic concentrations up to a few milligrams per litre were measured. The natural content of arsenic found in soils varies between 0.01 mg/kg and a few hundred milligrams per kilogram. Anthropogenic sources of arsenic in the environment are the smelting of ores, the burning of coal, and the use of arsenic compounds in many products and production processes in the past. A lot of arsenic compounds are toxic and cause acute and chronic poisoning. In aqueous environment the inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) are the most abundant species. The mobility of these species is influenced by the pH value, the redox potential, and the presence of adsorbents such as oxides and hydroxides of Fe(III), Al(III), Mn(III/IV), humic substances, and clay minerals.  相似文献   

17.
High time resolution data from the CUTLASS Finland radar during the interval 01:30–03:30 UT on 11 May, 1998, are employed to characterise the ionospheric electric field due to a series of omega bands extending 5° in latitude at a resolution of 45 km in the meridional direction and 50 km in the azimuthal direction. E-region observations from the STARE Norway VHF radar operating at a resolution of 15 km over a comparable region are also incorporated. These data are combined with ground magnetometer observations from several stations. This allows the study of the ionospheric equivalent current signatures and height integrated ionospheric conductances associated with omega bands as they propagate through the field-of-view of the CUTLASS and STARE radars. The high-time resolution and multi-point nature of the observations leads to a refinement of the previous models of omega band structure. The omega bands observed during this interval have scale sizes 500 km and an eastward propagation velocity 0.75 km s–1. They occur in the morning sector (05 MLT), simultaneously with the onset/intensification of a substorm to the west during the recovery phase of a previous substorm in the Scandinavian sector. A possible mechanism for omega band formation and their relationship to the substorm phase is discussed.  相似文献   

18.
Initial coagulation rates of colloidal hematite (-Fe2O3) particles (diameter less than 0.1 µm) were measured experimentally in well-defined laboratory systems at constant temperature. The relative stability ratio,W, was obtained at various ionic strengths in NaCl medium and at pH values in the range from 3 to 12. ExperimentalW values ranged from 1 to 104 in various systems. The results delineate the roles ofspecific andgeneralized coagulation mechanisms for iron oxides. Among the specifically-interacting species (G ads 0 >G coul 0 ) studied were phosphate, monomeric organic acids of various structures, and polymeric organic acids. The critical coagulation-restabilization concentrations of specifically-interacting anions (from 10–7 to 10–4 molar) can be compared with the general effects of non-specific electrolyte coagulants (10–3 to 10–1 molar). The laboratory results are interpreted with the help of a Surface Complex Formation/Diffuse Layer Model (SCF/DLM) which describes variations of interfacial charge and potential resulting from variations of coagulating species in solution. Comparison of these laboratory experiments with observations on iron behavior in estuarine and lake waters aids in understanding iron removal mechanisms and coagulation time scales in natural systems.  相似文献   

19.
Iron geochemistry of the sediments and interstitial waters of the Roaring River alluvial fan in the Rocky Mountain National Park, Colorado was studied using a chemical equilibria approach. Large concentrations of colloidal Fe in the filterable Fe of the interstitial waters results in considerable overestimation of Fe2 + activity. The overestimation of Fe(II) seriously hampered the usefulness of chemical equilibria approach in the study of Fe geochemistry. Buried soil organic matter and a high water table within the alluvial fan has produced a highly reduced environment which results in elevated colloidal and filterable iron concentrations in the interstitial waters. The source of the iron is probably iron oxides within the buried soil and primary iron-bearing minerals in the sediments. When the iron-rich solutions reach the surface, the water rapidly oxidizes and amorphous ferric hydroxides precipitate. Between 190 to 370 mmol of iron per kg of surficial material were precipitated at the surface within two months. Noticeable decreases in the total amount of C and extractable iron (20 per cent and 30 per cent respectively) in the buried soil were observed during the study period (1985-1987) which implies a significant reduction in iron dissolution and subsequent deposition across the alluvial fan.  相似文献   

20.
Regular surveys of bottom water chemistry (SiO2, O2, Fe, Mn) have been carried from 1978 to 1986 in the deepest 30 m of Lake Léman (max. depth 309 m) including interface waters sampled with a Jenkins Mortimer corer. When compared to normal chemical gradients near bottom, i.e. O2 decrease and SiO2 increase, three types of anomalies (lens, interface, and behaviour) have been observed on O2 and SiO2, the most sensitive chemical species. These anomalies were found throughout the year, in several stations of the deepest part of the lake and even along the slope of the lake basin. Major anomalies (O2 + 3 to 10 mg ·l–1; SiO2 -1 to 2 mg·l–1) were generally found at the sediment water interface and may extend 10–20 m above the sediment and last 10 weeks. Others marked lens anomalies could be observed for 3 to 4 months. Several mechanisms are probably responsible for this injection of surface waters along the lake slope (accumulation of turbid water on lake banks after severe windstorms; river density currents due to temperature and/or turbidity difference with lake waters). These water-inputs do not represent important volumes ( 1% total lake volume) but, when occuring at the interface, they ensure a sufficient oxygen level to prevent diffusion of phosphate and ammonia from pore waters when winter lake overturns do not reach bottom layers (from 1972 to 1980). Complete overturns, as observed in 1980/81, are connected with major interface anomalies (bottom O2 moves up from 2 to 10 mg·l–1) occuring before surface mixing reaches the deepest layers.  相似文献   

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