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USGS2007

Prediction of resource volumes at untested locations using simple local prediction models

This paper shows how local spatial nonparametric prediction models can be applied to estimate volumes of recoverable gas resources at individual undrilled sites, at multiple sites on a regional scale, and to compute confidence bounds for regional volumes based on the distribution of those estimates. An approach that combines cross-validation, the jackknife, and bootstrap procedures is used to accomplish this task. Simulation experiments show that cross-validation can be applied beneficially to select an appropriate prediction model. The cross-validation procedure worked well for a wide range of different states of nature and levels of information. Jackknife procedures are used to compute individual prediction estimation errors at undrilled locations. The jackknife replicates also are used with a bootstrap resampling procedure to compute confidence bounds for the total volume. The method was applied to data (partitioned into a training set and target set) from the Devonian Antrim Shale continuous-type gas play in the Michigan Basin in Otsego County, Michigan. The analysis showed that the model estimate of total recoverable volumes at prediction sites is within 4 percent of the total observed volume. The model predictions also provide frequency distributions of the cell volumes at the production unit scale. Such distributions are the basis for subsequent economic analyses. ?? Springer Science+Business Media, LLC 2007.

Natural Resources Research↗

USGS2017

Disease protection and allelopathic interactions of seed-transmitted endophytic pseudomonads of invasive reed grass ( Phragmites australis )

Background and aims Non-native Phragmites australis (haplotype M) is an invasive grass that decreases biodiversity and produces dense stands. We hypothesized that seeds of Phragmites carry microbes that improve seedling growth, defend against pathogens and maximize capacity of seedlings to compete with other plants. Methods We isolated bacteria from seeds of Phragmites , then evaluated representatives for their capacities to become intracellular in root cells, and their effects on: 1.) germination rates and seedling growth, 2.) susceptibility to damping-off disease, and 3.) mortality and growth of competitor plant seedlings (dandelion ( Taraxacum officionale F. H. Wigg) and curly dock ( Rumex crispus L.)). Results Ten strains (of 23 total) were identified and characterized; seven were identified as Pseudomonas spp. Strains Sandy LB4 ( Pseudomonas fluorescens ) and West 9 ( Pseudomonas sp.) entered root meristems and became intracellular. These bacteria improved seed germination in Phragmites and increased seedling root branching in Poa annua . They increased plant growth and protected plants from damping off disease. Sandy LB4 increased mortality and reduced growth rates in seedlings of dandelion and curly dock. Conclusions Phragmites plants associate with endophytes to increase growth and disease resistance, and release bacteria into the soil to create an environment that is favorable to their seedlings and less favorable to competitor plants.

Plant and Soil↗

USGS2018

Species-specific nitrogenase activity in lichen-dominated biological soil crusts from the Colorado Plateau, USA

Background and aim Biological soil crusts (biocrusts) play numerous crucial roles in drylands, which comprise over 40% of Earth’s terrestrial surface. Among these key contributions is the fixation of atmospheric nitrogen. Yet, relatively little is known about the N 2 fixation capabilities of different lichen species that are found in late successional biocrust communities across drylands globally. Methods In order to improve our species-specific understanding of biocrust lichen N 2 fixation, we collected biocrusts dominated by four common species of lichens – Collema spp., Gyalolechia desertorum , Psora decipiens , and Squamarina lentigera – that represent a range of lichen families and morphological types. Nitrogenase activity of the biocrust community dominated by these lichens was evaluated using the acetylene reduction assay. Additionally, biocrust community composition was assessed using the point-intercept method along transects at varied distances from exposed bedrock. Results As expected, Collema spp.-dominated biocrusts had the highest rates of nitrogenase activity, with rates up to seven times larger than those of the other three target species. Nitrogen concentrations and carbon:nitrogen ratios of lichen tissue differed among lichen species. However, when the composite biocrust profile was assessed (i.e., biocrust tissue, microbial cells, and mineral soil to a 2 cm depth) these among-species differences in total nitrogen disappeared. Community composition changed according to distance from exposed bedrock, with a higher diversity of lichens closer to the bedrock. Conclusion Multiple drivers, including climate and land use change, affect biocrust community composition and species-specific functional information, even within a group such as late successional biocrusts, could help in forecasting the potential effects of global change on N 2 fixation, and consequently, soil fertility in drylands.

Colorado Plateau↗

USGS2010

Measuring sediment accretion in early tidal marsh restoration

Sediment accretion is a critical indicator of initial progress in tidal marsh restoration. However, it is often difficult to measure early deposition rates, because the bottom surface is usually obscured under turbid, tidally-influenced waters. To accurately measure early sediment deposition in marshes, we developed an echosounder system consisting of a specialized acoustic profiler, differential global positioning system unit, and laptop computer mounted on a shallow-draft boat. We conducted a bathymetry at the Tubbs Setback tidal restoration site on San Pablo Bay, California, along north–south transects at 25-m intervals. Horizontal position was recorded within 1 m each second and water depth to 1 cm every 0.05 s. Bottom elevations were adjusted for tidal height with surveyed tide gages. We created detailed bathymetric maps (grid cell size: 12.5 m x 12.5 m) by interpolation with inverse distance weighting. During the third year after restoration, sediment accretion averaged 57.1 ± 1.1 cm and the estimated sediment gain was 132,900 m3. The mean difference between the elevations from the bathymetry system and the 9 sediment pins was 2.0 ± 1.0 cm. The mean difference of the intersection points of east–west and north–south survey transects was 2.1 ± 0.2 cm, which provided a measure of repeatability with changing water levels. Our echosounder system provided accurate and repeatable measurements of sediment accretion of a recently restored tidal wetland, and this system proved to be a viable tool for determining sediment deposition in marshes and assessing early restoration progress.

California↗

USGS2014

Phytoplankton growth balanced by clam and zooplankton grazing and net transport into the low-salinity zone of the San Francisco Estuary

We estimated the influence of planktonic and benthic grazing on phytoplankton in the strongly tidal, river-dominated northern San Francisco Estuary using data from an intensive study of the low salinity foodweb in 2006–2008 supplemented with long-term monitoring data. A drop in chlorophyll concentration in 1987 had previously been linked to grazing by the introduced clam Potamocorbula amurensis, but numerous changes in the estuary may be linked to the continued low chlorophyll. We asked whether phytoplankton continued to be suppressed by grazing and what proportion of the grazing was by benthic bivalves. A mass balance of phytoplankton biomass included estimates of primary production and grazing by microzooplankton, mesozooplankton, and clams. Grazing persistently exceeded net phytoplankton growth especially for larger cells, and grazing by microzooplankton often exceeded that by clams. A subsidy of phytoplankton from other regions roughly balanced the excess of grazing over growth. Thus, the influence of bivalve grazing on phytoplankton biomass can be understood only in the context of limits on phytoplankton growth, total grazing, and transport.

California↗

USGS2010

Isolation of microsatellite loci from the lesser long-nosed bat (Leptonycteris yerbuenae)

Leptonycteris yerbabuenae is a nectarivore (subfamily: Glossophaginae, family: Phyllostomidae), is found from southern Arizona/southwestern New Mexico to southern Mexico including the Baja California peninsula (Ceballos et al.1997; Cockrum 1991). Leptonycteris yerbabuenae is listed as endangered in the United States (Shull 1988) and threatened in Mexico (SEMARNAT 2002). They migrate up to 1,800 km between wintering and breeding grounds (Fleming and Eby 2001). Females mate in the winter in southern Mexico, and migrate to maternity roosts in northern Mexico/southern Arizona to give birth in late spring-early summer (Ceballos et al.1997; Cockrum 1991). Wilkinson and Fleming (1996) have suggested two separate migration corridors where bats occupy southeastern Arizona and southwestern Arizona arrive and leave through separate corridors. We isolated 12 microsatellites loci to estimate gene flow between southwestern and southeastern Arizona roosts, as well as Sonora, Baja California, and Jalisco, Mexico. Genomic DNA was extracted using the DNeasy Blood & Tissue Kit (Qiagen). Approximately 5 μg of genomic DNA was digested with RsaI (NEB) and fragments were ligated to double-stranded SuperSNX-24 linkers to construct an enriched genomic DNA library using a modified version of Glenn and Schable (2005). Linker-ligated fragments ranging from 300–1400 bp were recovered using the polymerase chain reaction (PCR) with a SuperSNX-24 forward primer and Platinum high-fidelity Taq DNA polymerase (Invitrogen), and were hybridized to 5′-biotinylated microsatellite oligonucleotide probes (GT) 15 , (CT) 15 , (GATA) 10 and (GACA) 8 . Hybridized fragments were captured on streptavidin-coated paramagnetic beads (Dynal) and then recovered by PCR. These fragments were ligated into the vector PCR4-TOPO (Invitrogen), and transformed into TOP10 chemically competent E. coli cells (Invitrogen) following the manufacturer’s protocol.

Conservation Genetics Resources↗

USGS1970

Cummingtonite: A reversible, nonquenchable transition from P21/m to C2/m symmetry

Cummingtonite from the Gouverneur, New York, talc district (Sample No. U.S.N.M. 115046) with the composition, (Ca 0.36 Na 0.06 Mn 0.96 Mg 0.57 ) Mg 5 Si 8 O 22 (OH) 2 , unit cell parametersa = 9.550 ± 0.001, b = 18.007 ± 0.003, c = 5.298 ± 0.001Å, β = 102°39′ ± 1′, and space groupP2 1 /m, has been used in a high-temperature, single-crystal, X-ray diffraction study. When diffraction patterns are taken of the crystals heated in a sealed silica capillary to 45°C or higher, these reflections disappear, indicating a transition toC2/m symmetry. The transition appears to be analogous to theP2 1 /ctoC2/c transition between 700° and 800°C discovered recently in (Mg 0.30 Fe 0.70 ) SiO 3 clinopyroxene. In addition to the cummingtonite transition, we have also found a transition in pigeonite at higher temperatures. The transition occurs in this pigeonite (Gunflint Iron Formation, Minnesota, (Ca 0.04 Fe 0.78 Mg 0.18 )SiO 3 ) at about 670°C. This is a significantly lower temperature than was found for the Ca-poor clinopyroxene.

Earth and Planetary Science Letters↗

USGS1978

The crystal structure and thermal history of orthopyroxene from lunar anorthosite 15415

A single crystal of untwinned orthopyroxene from lunar anorthosite sample 15415, with composition (Mg 1.14 Fe 0.80 Mn 0.02 Ca 0.04 )(Si 1.97 Al 0.03 )O 6 , has a unit cell in space group Pbca with a = 18.310(15)Å, b = 8.904(10)Å, c = 5.214(7)Å, containing 2 formula units. A set of 742 counter-measured intensity data made with MoK α radiation has been used to refine the crystal structure in isotropic thermal mode to R = 0.116. Anisotropic refinement led to R = 0.092, but thermal parameters are distorted by non-random errors resulting from poor crystal texture. The resulting structure is in close agreement with that obtained by Ghose [9] for a hypersthene from Greenland. A parameter q , which gives ( Mg q Fe 1−q ) for cation site M (1) and (Mg 1.14− q Fe q −0.18 Ca 0.04 ) for site M (2), was included in the least-squares analysis, yielding q = 0.90(1). This orthopyroxene has the high degree of cation order expected of pyroxenes subjected to Apollonian metamorphism at lower than 500–600°C. No evidence exists for a subsequent thermal event of sufficient intensity to disorder the pyroxene. On the basis of previous laboratory studies of argon-release patterns of lunar plagioclase and order-disorder kinetics of terrestrial pyroxenes, we attribute the reported isotopic age (3.9–4.1 AE) to cessation of metamorphism, perhaps caused by impact excavation.

Earth and Planetary Science Letters↗

USGS1983

Effects of dietary cadmium on mallard ducklings

Mallard (Anas platyrhynchos) ducklings were fed cadmium in the diet at 0, 5, 10, or 20 ppm from 1 day of age until 12 weeks of age. At 4-week intervals six males and six females from each dietary group were randomly selected, bled by jugular venipuncture, and necropsied. Significant decreases in packed cell volume (PCV) and hemoglobin (Hb) concentration and a significant increase in serum glutamic pyruvic transaminase (GPT) were found at 8 weeks of age in ducklings fed 20 ppm cadmium. Mild to severe kidney lesions were evident in ducklings fed 20 ppm cadmium for 12 weeks. No other blood chemistry measurement, hematological parameter, or tissue histopathological measurement indicated a reaction to cadmium ingestion. Body weight, liver weight, and the ratio of the femur weight to length were not affected by dietary cadmium. Femur cadmium concentration In all ducklings 12 weeks of age declined from the values detected at 4 and 8 weeks of age. Liver cadmium concentrations were significantly higher in relation to the increased dietary levels and in relation to the length of time the ducklings were fed the cadmium diets. At 12 weeks of age the cadmium concentration in liver tissue was twice that in the diet.

Environmental Research↗

USGS1966

Electron microscope study of Sarcocystis sp

Sarcocystis sp. obtained from wild populations of grackles, Quiscalus quiscula (Linn.), were examined to clarify the effect of the parasite on the host. Electron micrographs are presented to show areas of muscle destruction adjacent to the parasite which appear to be mechanically produced by the parasite. The microtubules within the villus-like projections of the cyst suggest that their possible function is absorptive and/or conductive with regard to the production of a toxin or the conveyance of nutritive material to the developing cells. The proposed function of submembranous filaments and their relation to the conoid is discussed. Similarities in the ultrastructure to Toxoplasma and other protozoa tend to negate the relegation of Sarcocystis to the fungi and further emphasize its protozoan nature.

Experimental Parasitology↗

USGS1957

Systematic variation of rare-earth elements in cerium-earth minerals

In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (∑), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ∑ for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ∑ for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ∑ is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ∑ greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements—efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ∑ in one crystal and a slightly smaller value of ∑ in the outer part of the other crystal compared to the inner part. The ∑ of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ∑ of monazites in the intruded host rock. These results indicate that the fractionation of the rare-earth elements is not a simple unidirectional process. When a cerium-earth mineral undergoes replacement, its rare-earth elements may be fractionated into two parts, one forming a new mineral with ∑ that is smaller, and the other a second new mineral with ∑ that is larger than that of the original mineral. The complete analysis of a cerium-earth mineral to determine its ∑ is time consuming. The discovery of a direct relationship between ∑ and the Ce/(Nd + Y) atomic ratio in cerium earth minerals allows a rapid determination of ∑ from spectrograms obtained in a previously described method for determining thorium in these minerals.

Geochimica et Cosmochimica Acta↗

USGS1968

Dissociation constants of KSO 4 - from 10°-50°C

A cell without liquid junction was used to obtain dissociation constants for the reaction: KSO 4 − = K + + SO 4 2− . At 10°, 25°, 38° and 50°C, values for K diss KSO 4 − are, respectively, 0.19 5 , 0.14 2 , 0.11 7 , and 0.09 5 . At 25°C, , and values for the KSO 4 − ion are −245.96 and −274.02 kcal mole −1 , and S ° is +42.3 cal mole −1 deg −1 .

Geochimica et Cosmochimica Acta↗

USGS1973

Simultaneous flow of water and solutes through geological membranes-I. Experimental investigation

The relative retardation by geological membranes of cations and anions generally present in subsurface waters was investigated using a high pressure and high temperature ‘filtration cell’. The solutions were forced through different clays and a disaggregated shale subjected to compaction pressures up to 9500 psi and to temperatures from 20 to 70°C. The overall efficiences measured increased with increase of exchange capacity of the material used and with decrease in concentration of the input solution. The efficiency of a given membrane increased with increasing compaction pressure but decreased slightly at higher temperatures for solutions of the same ionic concentration. The results further show that geological membranes are specific for different dissolved species. The retardation sequences varied depending on the material used and on experimental conditions. The sequences for monovalent and divalent cations at laboratory temperatures were generally as follows: Li < Na < NH 3 < K < Rb < Cs Mg < Ca < Sr < Ba. The sequences for anions at room temperature were variable, but at 70°C, the sequence was: HCO 3 < I < B < SO 4 < Cl < Br. Monovalent cations contrary to some field data were generally retarded with respect to divalent cations. The differences in the filtration ratios among the divalent cations were smaller than those between the monovalent cations. The passage rate of B, HCO 3 , I and NH 3 was greatly increased at 70°C.

Geochimica et Cosmochimica Acta↗

USGS1985

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↗

USGS1985

Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

Significant amounts of SO 4 2− , Na + , and OH − are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO 4 2− . Aragonites and most biogenic low Mg-calcites contain significant amounts of Na + , but very low concentrations of SO 4 2− . The SO 4 2− content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na + and SO 4 2− increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO 4 2− beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO 4 2− is the same as that of aragonite. Na + appears to have very little effect on the solubility product of calcites. The amounts of Na + and SO 4 2− incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ( D "> D ) of SO 4 2− in calcite at 25.0°C and 0.50 molal NaCl is described by the equation D = k 0 + k 1 R "> D = k 0 + k 1 R where k 0 "> k 0 and k 1 "> k 1 are constants equal to 6.16 × 10 −6 "> 6.16 × 10 −6 and 3.941 × 10 −6 "> 3.941 × 10 −6 , respectively, and R "> R is the rate of crystal growth of calcite in mg·min −1 ·g −1 of seed. The data on Na + are consistent with the hypothesis that a significant amount of Na + occupies interstitial positions in the calcite structure. The distribution of Na + follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na + distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na + contents of calcites are not very accurate indicators of environmental salinities.

Geochimica et Cosmochimica Acta↗

USGS1988

Bacterial ethane formation from reduced, ethylated sulfur compounds in anoxic sediments

Trace levels of ethane were produced biologically in anoxic sediment slurries from five chemically different aquatic environments. Gases from these locations displayed biogenic characteristics, having 12 C-enriched values of δ 13 CH 4 (−62 to −86%.), δ 13 C 2 H 6 (−35 to −55%.) and high ratios (720 to 140,000) of CH 4 [C 2 H 6 + C 3 H 8 ] "> CH4[C2H6+ C3H8] . Endogenous production of ethane by slurries was inhibited by autoclaving or by addition of the inhibitor of methanogenic bacteria, 2-bromoethanesulfonic acid (BES). Ethane formation was stimulated markedly by ethanethiol (ESH), and, to a lesser extent, by diethylsulfide (DES). Formation of methane and ethane in ESH- or DES-amended slurries was blocked by BES. Experiments showed that ethionine (or an analogous compound) could be a precursor of ESH. Ethylamine or ethanol additions to slurries caused only a minor stimulation of ethane formation. Similarly, propanethiol additions resulted in only a minor enhancement of propane formation. Cell suspensions of a methyltrophic methanogen produced traces of ethane when incubated in the presence of DES, although the organism did not grow on this compound. These results indicate that methanogenic bacteria produce ethane from the traces of ethylated sulfur compounds present in recent sediments. Preliminary estimates of stable carbon isotope fractionation associated with sediment methane formation from dimethylsulfide was about 40%., while ethane formation from DES and ESH was only 4. 6 and 6.5%., respectively.

Geochimica et Cosmochimica Acta↗

USGS1994

Electrochemistry and dissolution kinetics of magnetite and ilmenite

Natural samples of magnetite and ilmenite were experimentally weathered in pH 1–7 anoxic solutions at temperatures of 2–65 °C. Reaction of magnetite is described as [ Fe 2+ Fe 2 3+ ] O 4(magnetite) + 2 H + → γ [ Fe 2 3+ ] O 3(maghemite) + Fe 2+ + H 2 O . Dynamic polarization experiments using magnetite electrodes confirmed that this reaction is controlled by two electrochemical half cells, 3[ Fe 2+ Fe 2 3+ ] O 4 (magnetite) → 4 γ [ Fe 2 3+ ] O 3 (maghemite) + Fe 2+ + 2 e − and [ Fe 2+ Fe 2 3+ ] O 4(magnetite) + 8 H + + 2 e − → 3 Fe 2+ + 4 H 2 O , which result in solid state Fe 3+ reduction, formation of an oxidized layer and release of Fe(II) to solution. XPS data revealed that iron is present in the ferric state in the surfaces of reacted magnetite and ilmenite and that the Ti Fe "> TiFe ratio increased with reaction pH for ilmenite. Short-term (<36 h) release rates of Fe(II) were linear with time. Between pH 1 and 7, rates varied between 0.3 and 13 × 10 −14 mol · cm −2 · s −1 for magnetite and 0.05 and 12.3 × 10 −14 mol · cm −2 · s −1 for ilmenite. These rates are two orders of magnitude slower than electrochemical rates determined by Tafel and polarization resistance measurements. Discrepancies are due to both differences in geometric and BET surface area estimates and in the oxidation state of the mineral surface. In long-term closed-system experiments (<120 days), Fe(II) release slowed with time due to the passivation of the surfaces by increasing thicknesses of oxide surface layers. A shrinking core model, coupling surface reaction and diffusion transport, predicted that at neutral pH, the mean residence time for sand-size grains of magnetite and ilmenite will exceed 10 7 years. This agrees with long-term stability of these oxides in the geologic record.

Geochimica et Cosmochimica Acta↗

USGS1996

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 → 4 [ Fe 2 3 + ] O 3 (magnetite) + Fe 2 + + 2 / n m z − 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 → Fe 2 3 + Ti 3 O 9 (pseudorutile) + Fe 2 + + 2 / n m z − 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↗