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At least 361 records · Page 20Linked to original sources

Landscape genomics of Sphaeralcea ambigua in the Mojave Desert: a multivariate, spatially-explicit approach to guide ecological restoration

Local adaptation influences plant species’ responses to climate change and their performance in ecological restoration. Fine-scale physiological or phenological adaptations that direct demographic processes may drive intraspecific variability when baseline environmental conditions change. Landscape genomics characterize adaptive differentiation by identifying environmental drivers of adaptive genetic variability and mapping the associated landscape patterns. We applied such an approach to Sphaeralcea ambigua , an important restoration plant in the arid southwestern United States, by analyzing variation at 153 amplified fragment length polymorphism loci in the context of environmental gradients separating 47 Mojave Desert populations. We identified 37 potentially adaptive loci through a combination of genome scan approaches. We then used a generalized dissimilarity model (GDM) to relate variability in potentially adaptive loci with spatial gradients in temperature, precipitation, and topography. We identified non-linear thresholds in loci frequencies driven by summer maximum temperature and water stress, along with continuous variation corresponding to temperature seasonality. Two GDM-based approaches for mapping predicted patterns of local adaptation are compared. Additionally, we assess uncertainty in spatial interpolations through a novel spatial bootstrapping approach. Our study presents robust, accessible methods for deriving spatially-explicit models of adaptive genetic variability in non-model species that will inform climate change modelling and ecological restoration.

California, Nevada

Radionuclides, trace elements, and radium residence in phosphogypsum of Jordan

Voluminous stockpiles of phosphogypsum (PG) generated during the wet process production of phosphoric acid are stored at many sites around the world and pose problems for their safe storage, disposal, or utilization. A major concern is the elevated concentration of long-lived 226Ra (half-life = 1,600 years) inherited from the processed phosphate rock. Knowledge of the abundance and mode-of-occurrence of radium (Ra) in PG is critical for accurate prediction of Ra leachability and radon (Rn) emanation, and for prediction of radiation-exposure pathways to workers and to the public. The mean (??SD) of 226Ra concentrations in ten samples of Jordan PG is 601 ?? 98 Bq/kg, which falls near the midrange of values reported for PG samples collected worldwide. Jordan PG generally shows no analytically significant enrichment (< 10%) of 226Ra in the finer (< 53 ??m) grain size fraction. Phosphogypsum samples collected from two industrial sites with different sources of phosphate rock feedstock show consistent differences in concentration of 226Ra and rare earth elements, and also consistent trends of enrichment in these elements with increasing age of PG. Water-insoluble residues from Jordan PG constitute <10% of PG mass but contain 30-65% of the 226Ra. 226Ra correlates closely with Ba in the water-insoluble residues. Uniformly tiny (< 10 ??m) grains of barite (barium sulfate) observed with scanning electron microscopy have crystal morphologies that indicate their formation during the wet process. Barite is a well-documented and efficient scavenger of Ra from solution and is also very insoluble in water and mineral acids. Radium-bearing barite in PG influences the environmental mobility of radium and the radiation-exposure pathways near PG stockpiles. ?? 2010 US Government.

Environmental Geochemistry and Health

Atmospheric particulate matter in proximity to mountaintop coal mines: Sources and potential environmental and human health impacts

Mountaintop removal mining (MTM) is a widely used approach to surface coal mining in the US Appalachian region whereby large volumes of coal overburden are excavated using explosives, removed, and transferred to nearby drainages below MTM operations. To investigate the air quality impact of MTM, the geochemical characteristics of atmospheric particulate matter (PM) from five surface mining sites in south central West Virginia, USA, and five in-state study control sites having only underground coal mining or no coal mining whatsoever were determined and compared. Epidemiologic studies show increased rates of cancer, respiratory disease, cardiovascular disease, and overall mortality in Appalachian surface mining areas compared to Appalachian non-mining areas. In the present study, 24-h coarse (>2.5 &micro;m) and fine (&le;2.5 &micro;m) PM samples were collected from two surface mining sites in June 2011 showed pronounced enrichment in elements having a crustal affinity (Ga, Al, Ge, Rb, La, Ce) contributed by local sources, relative to controls. Follow-up sampling in August 2011 lacked this enrichment, suggesting that PM input from local sources is intermittent. Using passive samplers, dry deposition total PM elemental fluxes calculated for three surface mining sites over multi-day intervals between May and August 2012 were 5.8 &plusmn; 1.5 times higher for crustal elements than at controls. Scanning microscopy of 2,249 particles showed that primary aluminosilicate PM was prevalent at surface mining sites compared to secondary PM at controls. Additional testing is needed to establish any link between input of lithogenic PM and disease rates in the study area.

West Virginia

Relative effectiveness of a radionuclide (210Pb), surface elevation table (SET), and LiDAR at monitoring mangrove forest surface elevation change

Sea-level rise (SLR) is one of the greatest future threats to mangrove forests. Mangroves have kept up with or paced past SLR by maintaining their forest floor elevation relative to sea level through root growth, sedimentation, and peat development. Monitoring surface elevation change (SEC) or accretion rates allows us to understand mangrove response to SLR and prioritizes resilient ecosystems for conservation or vulnerable ecosystems for restoration. We compared three methods to measure SEC and accretion in mangrove forests: 210 Pb, surface elevation tables (SETs), and a terrestrial light detection and ranging system (compact biomass LiDAR—CBL). Lead-210 accretion rates were not significantly different than SET SEC rates and differences between the two methods (− 2 to 2 mm/year) were within the error of our measurements. Lead-210 only measures accretion in the upper meter of sediment and cannot capture deeper subsurface processes (e.g., subsidence, compaction) that SETs can. The lack of differences suggests the following: (1) surface processes in the active root zone are influencing forest floor elevation more than subsurface processes, (2) subsurface processes were not large enough to effect elevation, or (3) the SETs were not installed deep enough to capture subsurface processes. CBL SEC rates did not differ significantly from SET SEC rates. The larger spatial scale of the CBL scans resulted in significantly different SEC rates from some of the plots. This was due to the CBL measuring areas missed by the SET. The greater number of points measured by CBL (~ 30,000 vs 36) increased precision and lowered standard error. The traditional SET/rSET method is currently 3–10 × cheaper than the 210 Pb or CBL method, respectively, and can accurately track changes in forest floor elevation. Costs of the use of LiDAR are likely to decrease in the future with the advent of newer and more cost-effective technology.

Estuaries and Coasts

Sediment record of mining legacy and water quality from a drinking-water reservoir, Aztec, New Mexico, USA

The record of mining legacy and water quality was investigated in sediments collected in 2018 from four trenches in the Aztec, New Mexico, drinking-water reservoir #1. Bulk chemical analysis of sediments with depth in the reservoir revealed variable trace-element (uranium, vanadium, arsenic, copper, sulfur, silver, lead, and zinc) concentrations, which appear to coincide with historical mining and milling operations. Cesium-137 age dating, which identified the location of the 1963 radioactive fallout maximum, combined with the known age of the bottom and top of the sediment trenches, was used to estimate a polynomial sedimentation rate (average rate = 1.7 cm/yr). The clay size fraction (< 0.004 mm) was the dominant grain-size fraction of the sediments. Abundant fine-grained phyllosilicate (clay) minerals, predominantly montmorillonite and kaolinite, may explain sorption properties of trace elements. Scanning electron microscopy evaluation of sediments from two trenches showed copper and zinc associated with sulfur, and arsenic associated with iron and aluminum oxides. Results from laboratory batch experiments indicated that uranium, vanadium, and arsenic were released when sediments were reacted with a 150 mg/L sodium bicarbonate solution whereas copper was released when sediments were reacted with 2 mMol/L acetic acid. Observed concentrations from the two leach tests were below regulatory thresholds for delivery of solids to a landfill and were below drinking-water standards. Diatom relative abundance indicates that the water quality in the reservoir was not impaired by high metal concentrations.

Colorado, New Mexico

Distinguishing shocked from tectonically deformed quartz by the use of the SEM and chemical etching

Multiple sets of crystallographically-oriented planar deformation features (PDFs) are generated by high-strain-rate shock waves at pressures of > 12 GPa in naturally shocked quartz samples. On surfaces, PDFs appear as narrow (50-500 nm) lamellae filled with amorphosed quartz (diaplectic glass) which can be etched with hydrofluoric acid or with hydrothermal alkaline solutions. In contrast, slow-strain-rate tectonic deformation pressure produces wider, semi-linear and widely spaced arrays of dislocation loops that are not glass filled. Etching samples with HF before examination in a scanning electron microscope (SEM) allows for unambiguous visual distinction between glass-filled PDFs and glass-free tectonic deformation arrays in quartz. This etching also reveals the internal 'pillaring' often characteristic of shock-induced PDFs. This technique is useful for easily distinguishing between shock and tectonic deformation in quartz, but does not replace optical techniques for characterizing the shock features.

Earth and Planetary Science Letters

Distribution of trace elements in coal from the Powhatan No. 6 mine, Ohio

Size and density separates of low-temperature-ashed coal from the Powhatan No. 6 mine, Ohio, have been used to determine the mode of occurrence of 28 minor and trace elements in coal. The size distribution of the major minerals has been determined, and correlations of trace elements with major minerals have been made. The role of minor minerals in the mode of occurrence of trace elements is also discussed. Instrumental-neutron-activation analysis was used to determine elemental concentrations, and X-ray diffraction and scanning electron microscopy were used for mineral identification.

Ohio

Phase relations in the system NaCl-KCl-H2O. Part I: Differential thermal analysis of the NaCl-KCl liquidas at 1 atmosphere and 500, 1000, 1500, and 2000 bars

A simple differential thermal analysis (DTA) technique has been developed to study phase relations of various chemical systems at elevated pressures and temperatures. The DTA system has been calibrated against known melting temperatures in the system NaCl-KCl. Isobaric sections of the liquidus in the system NaCl-KCl have been determined at pressures of 1 atmosphere and 500, 1000, 1500, and 2000 bars. Using the least-squares method, the following equation was used to fit the experimental data: T(&#xB0;C)= &#x2211; i=0 6 a i X i KCl "> T(°C)=∑i=06a i X i KCl where T is the liquidus temperature, X KCl is mole fraction of KCl, and a i (listed below) are the derived empirical constants. P (bars) a o "> ao a 1 "> a1 a 2 "> a2 a 3 "> a3 a 4 "> a4 a 5 "> a5 a 6 "> a6 1 atm. 800.1 −334.2 781.6 −6490.3 17553.1 −17638.4 6098.3 500 813.5 −354.9 743.3 −6011.7 16406.4 −16516.3 5702.8 1000 824.5 −406.7 1446.8 −8818.4 21253.5 −20343.7 6839.4 1500 838.6 −418.7 1434.7 −8819.0 21557.9 −20908.4 7123.1 2000 848.5 −381.5 1246.9 −8605.0 21785.8 −21449.1 7375.8 The liquidus temperatures estimated from these equations are within ±3°C of experimental values. The measured liquidus temperatures at 1 atmosphere agree with the best available data to within 5°C. The melting temperatures for pure end members at higher pressures agree with the values calculated from the Simon equation (Clark, 1959) to within 3°C. No previous melting data are available for the intermediate compositions at elevated pressures. Using the data in both heating and cooling scans, the minimum melting temperature at 1 atmosphere in the system was located at 658° ± 3° C where the sample has an equimolar composition.

Geochimica et Cosmochimica Acta

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO 3 ) from 5 to 1000 K. These measurements yield S 298 0 = 108.9 J /( mol · K ). Calculations from published experimental data on the reduction of ilmenite yield Δ 298 0 ( I 1) = −1153.9 kJ /( mol · K ). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of &#x192;O 2 ">ƒ ƒO2 are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookite ss and hematite-ilmenite ss . Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling.

Geochimica et Cosmochimica Acta

Degradation of carbohydrates and lignins in buried woods

Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13 C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15–25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13 C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p- hydroxyl "> p-hydroxyl lignin structural units > syringyl and lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.

Geochimica et Cosmochimica Acta

Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system NaFeAlSiOF

The heat capacity of cryolite (Na 3 AlF 6 ) has been measured from 7 to 1000 K by low-temperature adiabatic and high-temperature differential scanning calorimetry. Low-temperature data were obtained on material from the same hand specimen in the calorimetric laboratories of the University of Michigan and U.S. Geological Survey. The results obtained are in good agreement, and yield average values for the entropy of cryolite of: S 0 298 = 238.5 J / mol K "> S 0 298 = 238.5J/mol K S 0 T &#x2212; S 0 298 = 145.114 ln T+ 193.009&#x2217;10 &#x2212;3 T&#x2212; 10.366&#x2217; 10 5 T 2 &#x2212; 872.89 J / mol K (273&#x2212;836.5 K ) "> S 0 T −S 0 298 = 145.114lnT+ 193.009∗10 −3 T−10.366∗ 10 5 T 2 − 872.89J/mol K(273−836.5K) &#x394; S Trans = 9.9 J / mol K "> ΔS Trans = 9.9J/mol K S 0 T &#x2212; S 0 298 =198.414 ln T+73.203&#x2217; 10 &#x2212;3 T&#x2212;63.814&#x2217; 10 5 T 2 &#x2212;1113.11 J / mol K (836.5&#x2212;1153 K ) "> S 0 T −S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗10 5 T 2 −1113.11J/mol K(836.5−1153K) with the transition temperature between α- and β-cryolite taken at 836.5 K. These data have been combined with data in the literature to calculate phase equilibria for the system Na Fe Al Si O F. The resultant phase diagrams allow constraints to be placed on the f O 2 , f F 2 , a SiO 2 and T conditions of formation for assemblages in alkalic rocks. A sample application suggests that log f O 2 is approximately −19.2, log f F 2 is −31.9 to −33.2, and a SiO 2 is −1.06 at assumed P T "> PT conditions of 1000 K, 1 bar for the villiaumite-bearing Ilimaussaq intrusion in southwestern Greenland.

Geochimica et Cosmochimica Acta

The decarbonation and heat capacity of ZnCO3

The decarbonation curve for ZnCO 3 has been determined in the pressure range 3–20 kbar by using a combination of cold-seal vessels and piston-cylinder apparatus with NaCl assemblies. Heat capacities for both synthetic and natural ZnCO 3 samples were measured by differential scanning calorimetry at temperatures ranging from 340 to 497 K. The results of these experiments indicate that the enthalpy of formation for smithsonite, ΔH f (1,298.15), is approximately −817. kJ/mol. which is about 4 kJ more negative than most tabulated values.

Geochimica et Cosmochimica Acta

Heat capacities of synthetic hedenbergite, ferrobustamite and CaFeSi2O6 glass

Heat capacities have been measured for synthetic hedenbergite (9–647 K), ferrobustamite (5–746 K) and CaFeSi 2 O 6 glass (6–380 K) by low-temperature adiabatic and differential scanning calorimetry. The heat capacity of each of these structural forms of CaFeSiO 6 exhibits anomalous behavior at low temperatures. The X-peak in the hedenbergite heat-capacity curve at 34.5 K is due to antiferromagnetic ordering of the Fe 2+ ions. Ferrobustamite has a bump in its heat-capacity curve at temperatures less than 20 K, which could be due to weak cooperative magnetic ordering or to a Schottky anomaly. Surprisingly, a broad peak with a maximum at 68 K is present in the heat-capacity curve of the glass. If this maximum, which occurs at a higher temperature than in hedenbergite is caused by magnetic ordering, it could indicate that the range of distortions of the iron sites in the glass is quite small and that coupling between iron atoms is stronger in the glass than in the edge-shared octahedral chains of hedenbergite. The standard entropy change, S o 298.15 − S o 0 , is 174.2 ± 0.3, 180.5 ± 0.3 and 185.7 ± 0.4 J/mol·K for hedenbergite, ferrobustamite and CaFeSi 2 O 6 glass, respectively. Ferrobustamite is partially disordered in Ca-Fe distribution at high temperatures, but the dependence of the configuratonal entropy on temperature cannot be evaluated due to a lack of information. At high temperatures (298–1600 K), the heat capacity of hedenbergite may be represented by the equation C o p (J/mol·K) = 3 l 0.46 + 0.01257 T -2039.93 T &#x2212;1 2 &#x2212; 1.84604&#xD7; l0 6 T &#x2212;2 "> −12− 1.84604× 10 6 T −2 and the heat capacity of ferrobustamite may be represented by C o p (J/mol&#xB7;K) = 403.83&#x2212;0.04444T+ 1.597&#xD7; 10 &#x2212;5 T 2 &#x2212;3757.3T &#x2212;1 2 "> C o p (J/mol·K)= 403.83−0.04444T+ 1.597× 10 −5 T 2 −3757.3T −12 .

Geochimica et Cosmochimica Acta

Heat capacity and thermodynamic properties of andradite garnet, Ca 3 Fe 2 Si 3 O 12 , between 10 and 1000 K and revised values for ΔfGom (298.15 K) of hedenbergite and wollastonite

The heat capacity of synthetic andradite garnet (Ca 3 Fe 2 Si 3 O 12 ) was measured between 9.6 and 365.5 K by cryogenic adiabatic calorimetry and from 340 to 990 K by differential scanning calorimetry. At 298.15 K C o p , m and S o m are 351.9 &plusmn; 0.7 and 316.4 &plusmn; 2.0 J/(mol&middot;K), respectively. Andradite has a &lambda;-peak in C o p , m with a maximum at 11.7 &plusmn; 0.2 K which is presumably associated with the antiferromagnetic ordering of the magnetic moments of the Fe 3+ ions. The Gibbs free energy of formation, &Delta; f G o m (298.15 K) of andradite is &minus;5414.8 &plusmn; 5.5 kJ/mol and was obtained by combining our entropy and heat capacity data with the known breakdown of andradite to pseudowollastonite and hematite at &asymp; 1410 to 1438 K. From a reexamination of the calcite + quartz = wollastonite equilibrium data we obtained &Delta; f H o m (298.15 K) = &minus; 1634.5 &plusmn; 1.8 kJ/mol for wollastonite. Between 300 and 1000 K the molar heat capacity of andradite can be represented by the equation C o p , m = 809.24 - 7.025 &times; 10&minus;2 T &minus; 7.403 &times; 10 3 T &minus;0.5 &minus; 6.789 &times; 10 5 T &minus;2. We have also used our thermochemical data for andradite to estimate the Gibbs free energy of formation of hedenbergite (CaFeSi 2 O 6 ) for which we obtained &Delta; f G o m (298.15 K ) = &minus;2674.3 &plusmn; 5.8 kJ/mol.

Geochimica et Cosmochimica Acta

Melting and thermodynamic properties of pyrope (Mg3Al2Si3O12)

The heat capacity of Mg 3 Al 2 Si 3 O 12 glass has been measured from 10 to 1000 K by adiabatic and differential scanning calorimetry. The heat capacity of crystalline pyrope has been determined from drop-calorimetry measurements between 820 and 1300 K. From these and previously published results a consistent set of thermodynamic data is presented for pyrope and Mg 3 Al 2 Si 3 O 12 glass and liquid for the interval 0–2000 K. The enthalpy of fusion at 1570 &#xB1; 30 "> 1570 ± 30 K, the metastable congruent 1-bar melting point, is 241 &#xB1; 12 kJ/mol "> 241 ± 12kJ/mol .

Geochimica et Cosmochimica Acta

Surface alteration and physical properties of glass from the Cretaceous-Tertiary boundary

The scalloped surface feature on Cretaceous-Tertiary boundary glass is often explained as being due to terrestrial aqueous leaching. Leaching of man-made glass results in a reduction in density of the glass. Also, Fe, because of its relative insolubility, is concentrated by the leaching process. Thus, the Haitian glass specimens which have been heavily altered should have a thin rim of less dense glass in which the Fe is concentrated compared to the core glass. The higher Fe concentration in the rim glass should cause it to have an enhanced Curie constant and a lower density compared to the unaltered glass. The magnetic Curie constant, density, and scanning electron microscopic studies were made on altered specimens of Haitian glass and also on specimens showing a minimum of alteration. The results show that the less altered samples have the highest density and the lowest Curie constant. The data substantiate the terrestrial hypothesis.

Geochimica et Cosmochimica Acta

Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400°C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from −6.25 moles alkali m −2 s −1 at 400°C to − 11.7 moles alkali m −2 s −1 at 200°C. The variation in these rates with temperature is given by the equation log k&#x2217; = &#x2212;8.17(1000/T(K)) + 5.54 (r 2 = 0.987) "> k∗ = −8.17(1000/T(K)) + 5.54 (r 2 = 0.987) which yields an activation energy of 37.4 ± 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ± 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100°C. Computed hydrogen diffusion coefficients range from −15.7 to −17.3 cm 2 s −1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause alteration of their radiometric ages. Furthermore, the rapid rate of hydrogen diffusion observed at 100–150°C suggests that fine-grained alunites are susceptible to rapid D-H re-equilibration even at surficial conditions.

Geochimica et Cosmochimica Acta

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1–7 at 25°C. For an aqueous transition metal m , such reactions are 3 [ Fe 2 + Fe 2 3 + ] O 4 (magnetite) + 2 / n m z &#x2192; 4 [ Fe 2 3 + ] O 3 (magnetite) + Fe 2 + + 2 / n m z &#x2212; n "> 3[Fe2+Fe23+]O4(magnetite)+2/nmz→4[Fe23+]O3(magnetite)+Fe2++2/nmz−n and 3 [ Fe 2 + Ti ] O 3 (ilmenite) + 2 / n m z &#x2192; Fe 2 3 + Ti 3 O 9 (pseudorutile) + Fe 2 + + 2 / n m z &#x2212; n , "> 3[Fe2+Ti]O3(ilmenite)+2/nmz→Fe23+Ti3O9(pseudorutile)+Fe2++2/nmz−n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] → [Fe(III)] is −0.34 to −0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe 2+ (−0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 × 10 −10 mol m −2 s −1 . Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe 2+ is oxidized homogeneously in solution to Fe 3+ . X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

Geochimica et Cosmochimica Acta