Inputs of dissolved and particulate 226Ra to lakes and implications for 210Pb dating recent sediments

Gamma spectroscopy was used to measure radioisotope (²¹⁰Pb, ²²⁶Ra, ¹³⁷Cs) activities in sediment cores from 20 lakes and a wetland in Florida, USA. Nine profiles display relatively low (<5 dpm g^–1) and constant ²²⁶Ra activities, whereas 12 show high (>5 dpm g^–1) and variable ²²⁶Ra activities. In the latter group, most display up-core increases in activity. Upper sediments from two lakes (Round and Rowell) possess very high (>20 dpm g^–1) ²²⁶Ra activities that exceed total ²¹⁰Pb activities, clearly illustrating disequlibrium between ²²⁶Ra and supported ²¹⁰Pb. Supported ²¹⁰Pb activity is generally thought to come from in situ, ²²⁶Ra-containing detrital mineral particles, and is typically assumed to be in secular equilibrium with ²²⁶Ra activity. Since 1966, Round Lake has been augmented hydrologically with ²²⁶Ra-rich (6.2 dpm L^–1) groundwater pumped from the local deep aquifer. Adsorption of dissolved ²²⁶Ra to recent Round Lake sediments probably accounts for the high measured ²²⁶Ra activities and the pronounced disequilibrium between ²²⁶Ra and supported ²¹⁰Pb in topmost deposits. We suspect that many Florida waterbodies receive some ²²⁶Ra-rich runoff and seepage from groundwater pumped for irrigation, residential use, industrial applications, and mining. This may account for up-core increases in ²²⁶Ra activity measured in sediment cores from some Florida lakes. Significant groundwater pumping began within the last century, and there has been insufficient time for supported ²¹⁰Pb to come into equilibrium with adsorbed ²²⁶Ra in uppermost deposits. Input of ²²⁶Ra-rich groundwater to lakes may occur in any geographic region where local bedrock contains ²³⁸U and its daughters. When dissolved ²²⁶Ra adsorbs to recent sediments, it complicates accurate estimation of supported ²¹⁰Pb activity, and confounds calculation of unsupported ²¹⁰Pb activity that is used in dating models.     

The surface chemistry of multi-oxide silicates

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ∼8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ∼1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ∼3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ∼4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional ‘internal’ adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH_IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO₂ in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.     

Spatial variation of erosion in a small,glaciated basin in the Teton Range,Wyoming, based on detrital apatite (U‐Th)/He thermochronology

Evolution of mountain landscapes is controlled by dynamic interactions between erosional processes that vary in efficiency over altitudinal domains. Evaluation of spatial and temporal variations of individual erosion processes can augment our understanding of factors controlling relief and geomorphic development of alpine settings. This study tests the application of detrital apatite (U‐Th)/He thermochronology (AHe) to evaluate variable erosion in small, geologically complex catchments. Detrital grains from glacial and fluvial sediment in a single basin were dated and compared with a bedrock derived age‐elevation relationship to estimate spatial variation in erosion over different climate conditions in the Teton Range, Wyoming. Controls and pitfalls related to apatite quality and yield were fully evaluated to assess this technique. Probability density functions comparing detrital age distributions identify variations in erosional patterns between glacial and fluvial systems and provide insight into how glacial, fluvial, and hillslope processes interact. Similar age distributions representing erosion patterns during glacial and interglacial times suggest the basin may be approaching steady‐state. This also implies that glaciers are limited and no longer act as buzzsaws or produce relief. However, subtle differences in erosional efficiency do exist. The high frequency of apatite cooling ages from high altitudes represents either rapid denudation of peaks and ridges by mass wasting or an artifact of sample quality. A gap in detrital ages near the mean age, or mid‐altitude, indicates the fluvial system is presently transport limited by overwhelming talus deposits. This study confirms that sediment sources can be traced in small basins with detrital AHe dating. It also demonstrates that careful consideration of mineral yield and quality is required, and uniform erosion assumptions needed to extract basin thermal history from detrital ages are not always valid.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.     

Silicon in iron meteorite metal

Abstract– We report Si concentrations in the metal phases of iron meteorites. Analyses were performed by secondary ion mass spectrometry using a CAMECA 1270 ion probe. The Si concentrations are low (0.09–0.46 μg g^?1), with no apparent difference in concentration between magmatic and nonmagmatic iron meteorites. Coexisting kamacite and Ni‐rich metal phases have similar Si contents. Thermodynamic calculations show that Fe,Ni‐metal in equilibrium with silicate melts at temperatures where metal crystallizes should contain approximately 100 times more Si than found in iron meteorites in this work. The missing Si may either occur as tiny silicate inclusions in metal or it may have diffused as Si‐metal into surrounding silicates at low temperatures. In both cases, extensive low‐temperature diffusion of Si in metal is required. It is therefore concluded that low Si in iron meteorites is a result of subsolidus reactions during slow cooling.