Sources of Sr and implications for weathering of limestone under tallgrass prairie, northeastern Kansas

Grasslands of north-central Kansas are underlain by carbonate aquifers and shale aquitards. Chemical weathering rates in carbonates are poorly known, and, because large areas are underlain by these rocks, solute fluxes are important to estimating global weathering rates. Grasslands exist where the amount of precipitation is extremely variable, both within and between years, so studies in grasslands must account for changes in weathering that accompany changes in precipitation. This study: (1) identifies phases that dominate chemical fluxes at Konza Prairie Biological Station (KPBS) and Long-Term Ecological Research Site, and (2) addresses the impact of variable precipitation on mineral weathering. The study site is a remnant tallgrass prairie in the central USA, representing baseline weathering in a mid-temperate climate grassland.Groundwater chemistry and hydrology in the 1.2 km² watershed used for this study suggest close connections between groundwater and surface water. Water levels fluctuate seasonally. High water levels coincide with periods of precipitation plus low evapotranspiration rather than during precipitation peaks during the growing season. Precipitation is concentrated before recharging aquifers, suggesting an as yet unquantified residence time in the thin soils.Groundwater and surface water are oversaturated with respect to calcite within limitations of available data. Water is more dilute in more permeable aquifers, and water from one aquifer (Morrill) is indistinguishable from surface water. Cations other than Ca co-vary with each other, especially Sr and Mg. Potassium and Si co-vary in all aquifers and surface water, and increases in concentrations of these elements are the best indicators of silicate weathering at this study site. Silicate-weathering indices correlate inversely to aquifer hydraulic conductivity.⁸⁷Sr/⁸⁶Sr in water ranges from 0.70838 to 0.70901, and it decreases with increasing Sr concentration and with increasing silicate-weathering index. Carbonate extracted from aquifer materials, shales, soil, and tufa has Sr ranging from about 240 (soil) to 880 ppm (Paleozoic limestone). ⁸⁷Sr/⁸⁶Sr ranges from 0.70834 ± 0.00006 (limestone) to 0.70904 ± 0.00019 (soil). In all cases, ⁸⁷Sr/⁸⁶Sr of aquifer limestone is lower than ⁸⁷Sr/⁸⁶Sr of groundwater, indicating a phase in addition to aquifer carbonate is contributing solutes to water.Aquifer recharge controls weathering: during periods of reduced recharge, increased residence time increases the total amount of all phases dissolved. Mixing analysis using ⁸⁷Sr/⁸⁶Sr shows that two end members are sufficient to explain sources of dissolved Sr. It is proposed that the less radiogenic end member is a solution derived from dissolving aquifer material; longer residence time increases its contribution. The more radiogenic end member solution probably results from reaction with soil carbonate or eolian dust. This solution dominates solute flux in all but the least permeable aquifer and demonstrates the importance that land-surface and soil-zone reactions have on groundwater chemistry in a carbonate terrain.     

Surface geochemistry at Roosevelt Springs Kgra, Utah

As part of a research program conducted on behalf of the Department of Energy, available data on the Roosevelt Springs KGRA were synthesized to determine the spatial arrangement of the rocks, and the patterns of mass and energy flow within them. The resulting model led to a new interpretation of the geothermal system, and provided “ground truth” for evaluating the application of soil geochemistry to exploration for concealed geothermal fields. Preliminary geochemical studies comparing the surface micro-layer to conventional soil sampling methods indicated both practical and chemical advantages for the surface micro-layer technique.The elements arsenic, antimony and cesium in the surface microlayer samples in particular, gave a strong expression of one of the principal faults in the geothermal field. In contrast the analysis of soil samples from only 20 cm below the surface gave little or no expression of the geothermal field.As a consequence, the surface micro-layer was the chosen sampling medium for the second field program, which entailed the collection of a total of some 300 samples on both a regional and detailed pattern covering about 250 km². These samples were subsequently analyzed by a variety of methods yielding data on 41 elements and ions.Computer contouring revealed that, on a single-element basis, cesium, antimony and arsenic provided the best expression of the KGRA, and indicated other interesting areas of geothermal leakage. Elements such as beryllium and lithium, which are present in highly anomalous concentrations in the opaline sinter deposited by geothermal leakage, do not have an expression in the overlying soils or the surface micro-layer. Computer manipulation of the multi-element data using R-mode factor analysis provided the optimum method of interpretation of the surface micro-layer data. A single factor in which the principal contributors were arsenic, antimony and cesium provided the best indication of the leakage of geothermal solutions within the KGRA. Anomalies in the Escalante Desert to the west of the geothermal field are associated with the trace of a fault zone, and may, therefore, be an activity. Trend surface analysis of the soil mercury data has indicated a regional high in this element in the Mineral Mountains to the east of the KGRA, which may indicate the position of a dry heat source at depth.These data demonstrate that surface micro-layer sampling on a regional scale can serve as a prospecting tool for geothermal resource areas. However, it is possible that the optimum pathfinder elements may vary with the nature of heat source, the geochemistry of the local rocks and the local surficial environment. It is therefore recommended that a multi-element approach should be adopted, with subsequent computer processing of the data.     

Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (∼2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ΔV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction.Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 Å, forming “altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 × 10⁻¹⁴ mol biotite m⁻² s⁻¹. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 μm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone.Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 × 10⁻¹³ mol hornblende m⁻² s⁻¹: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O₂ at the bedrock-saprolite interface.     

SMART-1 after lunar capture: First results and perspectives

SMART-1 is a technology demonstration mission for deep space solar electrical propulsion and technologies for the future. SMART-1 is Europe’s first lunar mission and will contribute to developing an international program of lunar exploration. The spacecraft was launched on 27th September 2003, as an auxiliary passenger to GTO on Ariane 5, to reach the Moon after a 15-month cruise, with lunar capture on 15th November 2004, just a week before the International Lunar Conference in Udaipur. SMART-1 carries seven experiments, including three remote sensing instruments used during the mission’s nominal six months and one year extension in lunar science orbit. These instruments will contribute to key planetary scientific questions, related to theories of lunar origin and evolution, the global and local crustal composition, the search for cold traps at the lunar poles and the mapping of potential lunar resources     

Barium partitioning in coccoliths of Emiliania huxleyi

The coccolithophore Emiliania huxleyi was grown in seawater under different Ba concentrations. The relationship of coccolith Ba/Ca ratio and seawater Ba/Ca ratio was found to be linear. The linear regression yields the apparent Ba exchange coefficient of 0.10. Our data support a recently proposed generic model (Langer G., Gussone N., Nehrke G., Riebesell U., Eisenhauer A., Kuhnert H., Rost B., Trimborn S., and Thoms S. (2006) Coccolith strontium to calcium ratios in Emiliania huxleyi: the dependence on seawater strontium and calcium concentrations. Limnol. Oceanogr.51, 310-320.) developed for explaining apparent exchange coefficients of metabolically inert divalent trace metals, such as Sr, in E. huxleyi. This model represents the first approach combining cell physiological processes and data from inorganic precipitation experiments, which quantitatively explains coccolith apparent Sr and Ba exchange coefficients.     

Phosphorus and iron cycling in deep saprolite,Luquillo Mountains,Puerto Rico

Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut.Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ⁵⁶Fe = 0 to ? 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ⁵⁶Fe = ? 0.26 to ? 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10^? 14 mol m^? 2 s^? 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite.     

Constraints and deception in the isotopic record; the crustal evolution of the west Musgrave Province,central Australia

The Hf and Nd isotopic evolution of the Musgrave Province, central Australia, is used to constrain the timing of crust formation and lithospheric organisation of Proterozoic Australia. The dataset from this region challenges two widely held tenets of Hf and Nd isotope systematics, namely; that crust formation events can only be identified as periods when crystallisation ages correspond to model ages, and that linear Hf evolution arrays away from depleted mantle (along crustal Lu/Hf or Sm/Nd slopes) reflect reworking of the same source.Hf isotopes in Musgrave Province zircon crystals indicate two major crust formation events at c. 1900 Ma and at 1600–1550 Ma. Although no juvenile rocks or crystals are known from c. 1900 Ma, radiogenic addition into the crust at this time is required to account for consistent Nd and Hf evolution patterns, which show no indication of an initially heterogeneous source. Oxygen isotopes in zircon grains confirm that much of the c. 1900 Ma Hf isotopic signal is not compromised by mixtures. Furthermore, the correspondence between mantle extraction and the commencement of reworking of Archean material supports new crust generation at c. 1900 Ma and a coupling between lower and upper crustal processes. The c. 1900 Ma timing of juvenile addition is dissimilar to that in the Albany–Fraser and Arunta Orogens and may reflect continental arc development on the margin of a southern continent.The general Hf isotopic evolution trend of the Musgrave Province apparently reflects reworking from a dominant c. 1900 Ma source with some additional unradiogenic and radiogenic input through time. However, in the 1220–1050 Ma interval this apparent isotopic evolution contrasts with geological observations that indicate input of voluminous mantle-derived material. Intracontinental rifts and other regions with sustained very-high temperature crustal recycling processes generate magmatic provinces with extreme HFSE-enrichment. This can have a profound influence on isotopic evolution trends, suppressing typical juvenile addition patterns. Isotopic mixture modelling indicates that a significant volume of mantle derived material can be accommodated within HFSE enriched magmas without diverging isotopic signatures from apparent reworking trends. In the Musgrave Province, the crust had become so HFSE enriched during the prolonged Musgrave Orogeny (1220–1150 Ma) that it was insensitive to mantle input, which is estimated to have been as much as 85% during this event.