Fe/P concentration ratio in Mozhaisk reservoir deposits as an indicator of phosphate sorption

A relationship is established between within-year variations in Fe_tot/P_tot ratio in pore solution and the concentration of organic P compounds in solid phase. The passage of the FeOOH-P system in the silts of the Mozhaisk Reservoir from the aerobic conditions to aerobic is generally accompanied by dissolution of FeOOH and desorption of phosphates. The change from anaerobic conditions to aerobic during the spring and autumn seasons exhibits hysteresis in oxidation of Fe compounds in silts, such that variations in Fe/P ratio in the solid phase of silt do not agree with those in the pore solution.     

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely be controlled by isotope fractionation between the free and complexed iron. We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fe-desferrioxamine B (at pH 2). The two differently complexed Fe(III) pools were separated by addition of Na₂CO₃, which led to immediate precipitation of the inorganic Fe without causing significant dissociation of Fe-desferrioxamine complexes. Experiments using enriched ⁵⁷Fe tracer showed that isotopic equilibration between the ⁵⁷Fe-labelled inorganic species and the isotopically “normal” siderophore-bound Fe was rapid during the first few seconds and then became slower. Consequently, the data fitted poorly to first and second order reaction equations. However, with a two-stage reaction, the data fit perfectly with a first order equation for the slower stage, indicating that approximately 40% re-equilibration may take place during the separation of the two pools. To further test if the induced precipitation leads to experimental artefacts, the fractionation during precipitation of inorganic Fe was determined. Assuming a Rayleigh-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of ⁵⁶Fe_{solution-solid} = 1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within experimental uncertainty, yielding an average fractionation factor, Δ⁵⁶Fe_DFOB-inorg of 0.60 ± 0.15‰. The results indicate that equilibrium Fe isotope fractionation induced by strongly coordinating organic ligands may fractionate Fe isotopes in nature. The fractionation is likely to be important in oxic, Fe(III)-bearing environments, such as soils and rivers, and may, for example, largely control the Fe isotope composition of marine Fe–Mn crusts.     

Iron compound occurrence forms in freshwater deposits: Analytical review

Data on the occurrence forms and concentrations of crystalline, amorphous, and organic Fe in the solid phase of silts in lakes and reservoirs, as well as data on concentrations of Fe forms in the pore solution of deposits are analyzed. The major mechanisms of Fe compound transformations are briefly considered.     

Quantitative Separation of As(III) and As(V) from a Synthetic Water Solution Using Ion Exchange Columns in the Presence of Fe and Mn Ions

The quantitative separation of As(III) from a water sample containing As(III) and As(V) in the presence of Fe and Mn in an ion exchange resin (AG1 X8) column for the speciation of arsenic is described. Individual and combined effects of Fe and Mn on the separation of As(III) from the solution have been studied separately. In absence of Fe and Mn, the ratio between the As(T) concentration in the eluent and the As(III) concentration in the original sample has been found to be 0.9717 under optimum process conditions. The presence of Fe(II) in the water sample increased the As(T) concentration in the eluent whereas Mn(II) decreased it. Combined effects of Fe and Mn on the percentage increment in the eluent arsenic concentration have been expressed by additive and interactive models. The interactive model has been developed by a statistical software with a 95 % confidence level. In most of the cases the error on the determination of the As(III) concentration had a minimum when using the interactive model.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

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.     

Mathematical modeling of marine environment pollution processes by petroleum hydrocarbons and their degradation in Caspian Sea ecosystem

The available observational data on the pollution of tributaries and areas of the Caspian Sea by petroleum hydrocarbons and products are examined. The possible petroleum input from sources in the sea is assessed using up-to-date data of satellite observations of sea surface pollution by oil films. The hydroecological CNPSi-model is applied to studying water pollution processes by petroleum hydrocarbons in ten areas chosen in the Caspian Sea and the subsequent biodegradation of those pollutants. The model calculations of the within-year dynamics of petroleum hydrocarbon concentrations use mean annual observational data on within-year variations in water mediium characteristics (water temperature, light intensity, and transparency), as well as the morphometric parameters of sea areas (the area, mean depth, and water volumes). The characteristics of water exchange between the areas were evaluated using a hydrodynamic model. The model calculations were used to characterize the within-year variations in petroleum hydrocarbon concentrations, the biomasses of petroleum-oxidizing bacteria, the characteristics of their oxidation activity and bioproduction, and the internal fluxes of petroleum hydrocarbons (their input from various sources, horizontal and vertical transport, and biotransformation) in different sea areas. Calculation results were used to compile annual balances for the processes of input and consumption of petroleum hydrocarbons in the chosen and aggregated sea areas.     

Peculiarities of annual variations in the concentration of iron compounds in the water-bottom sediments system of the Mozhaisk Reservoir

Annual variations in concentrations of Fe forms in the bottom water (0–70 cm from the bottom, by layers), pore water, and in solid phase of silts (25 cm, by layers) of the Krasnovidovo Pool channel area of the Mozhaisk Reservoir are studied. A drastic increase in the concentration and ratio of Fe_susp/Fe_dis in the water layer 0–20 cm from the bottom is detected. Fe(II) dominates in dissolved and suspended forms. The concentrations of Fe(III) reaching 2–3 mg/l were for the fist time revealed in the pore water of silts (Eh ～ ?120 mV). The factors responsible for this phenomenon are discussed. Fe flux from sediments is tentatively assessed as 0.2–0.6 mg Fe m²/day.     

Determination of thermodynamic properties of (Fe,Mg)-pyroxenes at 1000 K by the emf method

Emf measurements were made on the cell Pt|Fe,(Fe,Mg)_xSi₂O₆,SiO₂|(ZrO₂)_0.85(CaO)_0.15|Fe,FeO|Pt at 1000 K. Using the present data, the standard free energy of formation of ferrosilite (compound FeSiO₃), from the component oxides FeO and SiO₂, is calculated to be −6.35 ± 0.80 kJ/mol. The activity-composition relation for pyroxene solid solution shows that it has a positive deviation from ideality at 1000 K. The present results are compared with the results of other workers.ΔG_mix andΔG^ex are calculated and plotted againstN_FeSiO3.     

The crystal structure of (Fe_4Cr_4Ni)_9C_4

The Luobusha podiform chromite deposit occursin the Luobusha ophiolite exposed at the In-dus-Yarlung Zangbo suture[1]. The wall rocks of chro-mitites are harzburgites. Many mantle minerals werefound in chromitites and harzburgites. Among of them,there are 120 grains of diamond[2], many elementalmetals (mainly Au, Cu, Fe, Ni, Cr, Al, W, Zn, Pb, Sn,Os, Ir, Ru, C, etc.) and their intermetallic compounds.Besides diamond and graphite, the element C isalso combined with Fe, Cr, Ni, Ti and …     

Correlating the concentration of mobile manganese with redox- and acid–base properties in sediment column of the Mozhaisk Reservoir in the period of its formation (1970-1975)

Data of 1970-1971 and 1974-1975 for six layers of the Mozhaisk Reservoir were used to analyze the within-year relationships between Mn concentration and silt Eh and pH. The character of these relationships is explained. For the first time, a critical Eh zone, where Mn concentration abruptly changes, was identified. The redox processes involving Mn were shown to gradually stabilize over time.     

Simulation of the impacts of diagenesis or low-grade metamorphism on neutrophilic microaerobic Fe(II)-oxidizing biofilm

The microaerobic iron-oxidizing bacteria in circumneutral environment produce extracellular polymeric substances(EPS)with unique morphologic features,such as stalks or sheaths,which can be regarded as geobiological signatures.The Archean and early Palaeoproterozoic oceans were anoxic with high soluble Fe(II)that were suggested to have been oxidized through the metabolism of Fe(II)-oxidizing bacteria.The precursor of the ultrafine hematite in banded iron formation(BIF),e.g.,ferrihydrite,was suggested to be the mineral record of microbial Fe(II)-oxidation at that time.However,both the biological materials and primary iron minerals were prone to being altered by diagenetic or low-grade metamorphic processes.This makes it difficult to interpret the genesis of Precambrian BIFs.Here,we report experimental simulation on the effects of diagenesis or low-grade metamorphism on neutrophilic microaerobic Fe(II)-oxidizing bacteria and their biomass.Stalks,sheaths,and iron oxide spheroidal aggregates are partially preserved after the 100 MPa/300°C treatments,which indicates the mixed organic matters and iron oxides could survive the diagenetic or low-grade metamorphic processes.Some organic-mineral mixing structures carry information on microbial processes,though they appear similar to pseudomorphs of fossilized bacteria.     

Residence times in river basins as determined by analysis of long-term tritium records

The US Geological Survey has maintained a network of stations to collect samples for the measurement of tritium concentrations in precipitation and streamflow since the early 1960s. Tritium data from outflow waters of river basins draining 4500–75000 km² are used to determine average residence times of water within the basins. The basins studied are the Colorado River above Cisco, Utah; the Kissimmee River above Lake Okeechobee, Florida; the Mississippi River above Anoka, Minnesota; the Neuse River above Streets Ferry Bridge near Vanceboro, North Carolina; the Potomac River above Point of Rocks, Maryland; the Sacramento River above Sacramento, California; the Susquehanna River above Harrisburg, Pennsylvania. The basins are modeled with the assumption that the outflow in the river comes from two sources—prompt (within-year) runoff from precipitation, and flow from the long-term reservoirs of the basin. Tritium concentration in the outflow water of the basin is dependent on three factors: (1) tritium concentration in runoff from the long-term reservoir, which depends on the residence time for the reservoir and historical tritium concentrations in precipitation; (2) tritium concentrations in precipitation (the within-year runoff component); (3) relative contributions of flow from the long-term and within-year components. Predicted tritium concentrations for the outflow water in the river basins were calculated for different residence times and for different relative contributions from the two reservoirs. A box model was used to calculate tritium concentrations in the long-term reservoir. Calculated values of outflow tritium concentrations for the basin were regressed against the measured data to obtain a slope as close as possible to 1. These regressions assumed an intercept of zero and were carried out for different values of residence time and reservoir contribution to maximize the fit of modeled versus actual data for all the above rivers. The final slopes of the fitted regression lines ranged from 0.95 to 1.01 (correlation coefficient > 0.96) for the basins studied. Values for the residence time of waters within the basins and average relative contributions of the within-year and long-term reservoirs to outflow were obtained. Values for river basin residence times ranged from 2 years for the Kissimmee River basin to 20 years for the Potomac River basin. The residence times indicate the time scale in which the basin responds to anthropogenic inputs. The modeled tritium concentrations for the basins also furnish input data for urban and agricultural settings where these river waters are used.     

Regularities in the formation of groundwater infiltration recharge

The effect of meteorological, landscape, geological-pedological, and hydrogeological factors on the formation of total water balance and infiltration recharge of groundwater. The results of analysis of calculated mean annual and within-year values of water balance elements on land surface and in the vadose zone were used to identify some regularities, governing the resulting input of moisture to groundwater table at different depth of its occurrence (infiltration).     

Effect of regional climate variations and economic activity on changes in the hydrological regime of watersheds and small-river runoff

Regularities of long-term within-year and between-zone variations in climate characteristics (air temperature and precipitation) were identified, and estimates were obtained for the response time of the factors of hydrothermal state of watersheds at the beginning of snow-melting (maximal snow storage, freezing depth, and soil moisture content), spring surface slope runoff, annual and spring river runoff of small rivers in different natural zones of Russian Plain.     

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.     

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.     

Modeling of the Removal of Arsenic Species from Simulated Groundwater Containing As,Fe, and Mn: A Neural Network Based Approach

The present paper deals with the modeling of the removal of total arsenic As(T), trivalent arsenic As(III), and pentavalent arsenic As(V) from synthetic solutions containing total arsenic (0.167–2.0 mg/L), Fe (0.9–2.7 mg/L), and Mn (0.2–0.6 mg/L) in a batch reactor using Fe impregnated granular activated charcoal (GAC‐Fe). Mass ratio of As(III) and As(V) in the solution was 1:1. Multi‐layer neural network (MLNN) has been used and full factorial design technique has been applied for the selection of input data set. The developed models are able to predict the adsorption of arsenic species with an error limit of ?0.3 to +1.7%. Combination of MLNN with design of experiment has been able to generalize the MLNN with less number of experimental points.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.