Sediments with basaltic provenance, such as those at the Hanford nuclear reservation, Washington, U.S.A, are rich in Fe-bearing minerals of mixed valence. These minerals are redox reactive with aqueous O2 or Fe(II), and have the potential to react with important environmental contaminants including Tc. Here, we isolate, identify and characterize natural Fe(II)/Fe(III)-bearing microparticles from Hanford sediments, develop synthetic analogues and investigate their batch redox reactivity with aqueous Tc(VII). Natural Fe-rich mineral samples were isolated by magnetic separation from sediments collected at several locations on Hanford's central plateau. This magnetic mineral fraction was found to represent up to 1 wt% of the total sediment, and be composed of 90% magnetite with minor ilmenite and hematite, as determined by X-ray diffraction. The magnetite contained variable amounts of transition metal impurities consistent with alio-and isovalent metal substitutions for Fe. X-ray microprobe analysis showed that Ti was the most significant impurity, and that these grains could be described with the titanomagnetite formula Fe3 xTixO4, which falls between endmember magnetite (x = 0) and ulvöspinel (x = 1). The dominant composition was determined to be x = 0.15 by chemical analysis and electron probe microanalysis in the bulk, and by Ledge X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the surface. Site-level characterization of the titanomagnetites by X-ray magnetic circular dichrosim showed that despite native oxidation, octahedral Fe(II) was detectable within 5 nm of the mineral surface. By testing the effect of contact with oxic Hanford and Ringold groundwaters to reduced Ringold groundwater, it was found that the concentration of this near-surface structural Fe(II) was strongly dependent on aqueous redox condition. This highlights the potential for restoring reducing equivalents and thus reduction capacity to oxidized Fe-mineral surfaces through redox cycling in the natural environment. Reaction of these magnetically-separated natural phases from Hanford sediments with a-1 Tc(VII) showed that they were able to reduce Tc(VII) to Tc(IV) with concurrent oxidation of Fe(II) to Fe(III) at the mineral surface, as were synthetic x = 0.15 microparticle and nanoparticle analogue phases. When differences in the particle surface area to solution volume ratio were taken into consideration, measured Tc(VII) reduction rates for Fe3 xTixO4 (x = 0.15) natural material, synthetic bulk powder and nanoparticles scaled systematically, suggesting possible utility for comprehensive batch and flow reactivity studies.
Total-count contoured aeroradiometric maps for the Coastal Plain of Virginia were used in an effort to locate economic heavy-mineral placer deposits. The principle behind this approach is that heavymineral suites commonly contain radioactive minerals that, if the concentration of heavy minerals is exposed at or within inches of the surface, enable the deposit to be located by use of airborne instruments because of its radiometric contrast with the host sediment. Detailed and regional geologic maps, soil maps, land-use and landcover maps, information on fertilizer use, and ground-spectrometer data were used to study aeroradiometric anomalies for efficient exploration. Aeroradiometric anomalies in the Coastal Plain of Virginia have three general causes. First, the most intense anomalies are associated with cultural features, such as roads made of granitic material. Second, most anomalies of high to intermediate intensity are associated with land used for agricultural purposes and evidently are caused by applications of radioactive fertilizer. Third, anomalies of intermediate to low intensity are associated with heavy-mineral deposits. Results of this study show that aeroradiometric anomalies associated with heavy-mineral accumulations in the Coastal Plain of Virginia have ground radiometric spectra in which thorium is the strongest component and uranium and potassium are lesser components. Heavy-mineral accumulations found in this study by use of the aeroradiometric data are not considered to be of economic importance, mostly because of the low percentage of economic minerals in the heavy-mineral suites and also because of other factors such as the very fine grained nature of the host sediments and competing land use.
This study models geochemical and adjunct geologic data to define provinces that are favorable for radioactive-mineral exploration. A multi-element bed-sediment geochemical survey of streams was carried out in the headwaters region of the Ganga River in northern India. Overall median values for uranium and thorium (3.6 and 13.8 ppm; maxima of 4.8 and 19.0 ppm and minima of 3.1 and 12.3 ppm respectively) exceed average upper crustal abundances (2.8 and 10.7 ppm) for these radioactive elements. Anomalously high values reach up to 8.3 and 30.1 ppm in thrust zone rocks, and 11.4 and 22.5 ppm in porphyroids. At their maxima, these abundances are nearly four-and three-fold (respectively) enriched in comparison to average crustal abundances for these rock types. Deformed, metamorphosed and sheared rocks are characteristic of the main central thrust zone (MCTZ). These intensively mylonitized rocks override and juxtapose porphyritic (PH) and proterozoic metasedimentary rock sequences (PMS) to the south. Granitoid rocks, the major protoliths for mylonites, as well as metamorphosed rocks in the MCT zone are naturally enriched in radioelements; high values associated with sheared and mylonitized zones are coincident with reports of radioelement mineralization and with anomalous radon concentrations in soils. The radioelement abundance as well as REE abundance shows a northward enrichment trend consistent with increasing grade of metamorphism indicating deformation-induced remobilization of these elements. U and Th illustrate good correlation with REEs but not with Zr. This implies that zircon is not a principal carrier of U and Th within the granitoid-dominant thrust zone and that other radioelement-rich secondary minerals are present in considerable amounts. Thus, the relatively flat, less fractionated, HREE trend is also not entirely controlled by zircon. The spatial correlation of geologic boundary zones (faults, sheared zones) with geochemical and with geophysical (Rn) anomalies infers ore mineralization by hydrothermal processes generated during multiple episodes of deformation and thrusting. The geologic setting of the anomalies also suggests that crystalline rocks (MCT Zone) along the nearly 2500 km length of the LesserHimalayan belt, where in the vicinity of thrust and fault zones, have potential for radioelement mineralization. Zones of higher concentrations of radioelements delineated by this study and locations of anomalous radon discharge determined by other investigations may indicate a potential health hazard over the long term. However, the low human population density precludes direct manifestation of health effects attributable to chronic exposure to these radioelements; however, the magnitude of natural concentrations suggests the need for more detailed studies and monitoring.
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