Uranyl Retention on Quartz—New Experimental Data and Blind Prediction Using an Existing Surface Complexation Model

The adsorption behaviour of uranyl onto seven different samples of quartz was studied in batch experiments. Sea-sand (0.1–0.3 mm), Fil-Pro 12/20 (1–2 mm) and five Min-U-Sil samples with smaller particle sizes (5, 10, 15, 30 and 40 μm) were used. The uptake curves show “pH adsorption edges” in the range of pH 4–5. A good agreement of the new data with literature data was found when plotting surface-normalised distribution coefficients versus pH. Differences in the adsorption behaviour for pre-treated and untreated sea-sand samples were detectable resulting in a shift of the pH edge to higher pH values after treatment. A literature surface complexation model was applied for blind predictions of the experimental results. The simulations described the experimental observations quite well for the Min-U-Sil samples. For the two coarser quartz samples, the calculated over-predictions were explained by the larger-than-expected measured specific surface area and measurable amounts of associated minerals, for Fil-Pro 12/20 and sea-sand, respectively. Dissolution of the samples was studied as a function of pH. After 5 days, the measured Si concentrations were all higher than equilibrium quartz solubilities, but lower than those of amorphous silica. With increasing pH, dissolved silica increased. This strongly suggests that formation of dissolved uranyl–silicato complexes have to be considered based on measured silica concentrations.     

A data based mechanistic approach to nonlinear flood routing and adaptive flood level forecasting

Operational flood forecasting requires accurate forecasts with a suitable lead time, in order to be able to issue appropriate warnings and take appropriate emergency actions. Recent improvements in both flood plain characterization and computational capabilities have made the use of distributed flood inundation models more common. However, problems remain with the application of such models. There are still uncertainties associated with the identifiability of parameters; with the computational burden of calculating distributed estimates of predictive uncertainty; and with the adaptive use of such models for operational, real-time flood inundation forecasting. Moreover, the application of distributed models is complex, costly and requires high degrees of skill. This paper presents an alternative to distributed inundation models for real-time flood forecasting that provides fast and accurate, medium to short-term forecasts. The Data Based Mechanistic (DBM) methodology exploits a State Dependent Parameter (SDP) modelling approach to derive a nonlinear dependence between the water levels measured at gauging stations along the river. The transformation of water levels depends on the relative geometry of the channel cross-sections, without the need to apply rating curve transformations to the discharge. The relationship obtained is used to transform water levels as an input to a linear, on-line, real-time and adaptive stochastic DBM model. The approach provides an estimate of the prediction uncertainties, including allowing for heterescadasticity of the multi-step-ahead forecasting errors. The approach is illustrated using an 80 km reach of the River Severn, in the UK.     

Calcium isotope record of Phanerozoic oceans: Implications for chemical evolution of seawater and its causative mechanisms

A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ^44/40Ca_SW) over the Phanerozoic. The compiled δ^44/40Ca_SW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ^44/40Ca_SW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine ⁸⁷Sr/⁸⁶Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO₂, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ^44/40Ca_SW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ^44/40Ca_SW. As to the causes of the short-term oscillations recorded in the secular δ^44/40Ca_SW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.     

Improving BeiDou real-time precise point positioning with numerical weather models

Precise positioning with the current Chinese BeiDou Navigation Satellite System is proven to be of comparable accuracy to the Global Positioning System, which is at centimeter level for the horizontal components and sub-decimeter level for the vertical component. But the BeiDou precise point positioning (PPP) shows its limitation in requiring a relatively long convergence time. In this study, we develop a numerical weather model (NWM) augmented PPP processing algorithm to improve BeiDou precise positioning. Tropospheric delay parameters, i.e., zenith delays, mapping functions, and horizontal delay gradients, derived from short-range forecasts from the Global Forecast System of the National Centers for Environmental Prediction (NCEP) are applied into BeiDou real-time PPP. Observational data from stations that are capable of tracking the BeiDou constellation from the International GNSS Service (IGS) Multi-GNSS Experiments network are processed, with the introduced NWM-augmented PPP and the standard PPP processing. The accuracy of tropospheric delays derived from NCEP is assessed against with the IGS final tropospheric delay products. The positioning results show that an improvement in convergence time up to 60.0 and 66.7% for the east and vertical components, respectively, can be achieved with the NWM-augmented PPP solution compared to the standard PPP solutions, while only slight improvement in the solution convergence can be found for the north component. A positioning accuracy of 5.7 and 5.9 cm for the east component is achieved with the standard PPP that estimates gradients and the one that estimates no gradients, respectively, in comparison to 3.5 cm of the NWM-augmented PPP, showing an improvement of 38.6 and 40.1%. Compared to the accuracy of 3.7 and 4.1 cm for the north component derived from the two standard PPP solutions, the one of the NWM-augmented PPP solution is improved to 2.0 cm, by about 45.9 and 51.2%. The positioning accuracy for the up component improves from 11.4 and 13.2 cm with the two standard PPP solutions to 8.0 cm with the NWM-augmented PPP solution, an improvement of 29.8 and 39.4%, respectively.     

Geochemistry and geochronology of HP mélanges from Tinos and Andros,cycladic blueschist belt,Greece

U–Pb zircon geochronology, Sr–Nd isotope and bulk-rock geochemistry have been applied to meta-igneous and meta-sedimentary rocks from high-pressure metamorphic mélanges exposed on the Cycladic islands of Tinos, Syros and Andros. Ion microprobe (SHRIMP) U–Pb zircon dating of 7 samples representing meta-igneous blocks (Tinos), a blackwall zone (Tinos) and chlorite–talc schists from block-matrix contacts (Syros and Tinos) yielded Cretaceous ages of c. 80 Ma. Many of the criteria commonly used to distinguish between magmatic or metamorphic zircon genesis (internal structure, Th/U ratio, REE characteristics, Ti-in zircon thermometry, enclosed mineral phases) do not provide unambiguous constraints for the mode of formation. However, a magmatic origin for Cretaceous zircon of meta-gabbros and eclogites is considered likely. Supporting evidence for a previously suggested metamorphic origin for c. 80 Ma zircon in eclogite has not been found. Zircon of the same age occurring in chlorite–talc schists is presumably related to non-magmatic processes. Well-defined Cretaceous age groups clustering at c. 79 Ma also occur in the detrital zircon populations of 2 quartz mica schists representing the mélange matrix on Tinos, and suggest a much later time for sediment accumulation than previously assumed. The importance of c. 57 Ma zircon ages remains unclear, but may record either HP metamorphic processes or a post-57 Ma depositional age. The youngest age group in a third quartz mica schist from Tinos, collected outside the main mélange occurrences, clusters at c. 226–238 Ma. In all clastic metasediments from Tinos, most data points plot along the concordia between c. 300 and 900 Ma; single data points indicate concordant ages of c. 2.5 Ga, 2.3 Ga and 1 Ga, respectively. The youngest ²⁰⁶Pb/²³⁸U age group that has been recognized in a felsic paragneiss from Andros indicates an age of 163.1 ± 3.9 Ma, and mostly represents overgrowths around zircon with ages in the range from ～ 272 to ～ 289 Ma. Single data points of other inherited cores provided ²⁰⁶Pb/²³⁸U ages of c. 630 and c. 930 Ma. Meta-gabbros from Tinos show a large compositional variability and were found at 4 locations, each with distinct compositional characteristics, suggesting different crystallization histories, different sources and/or significant post-magmatic disturbance. The geochemistry of mélange blocks and the identical U–Pb zircon ages suggest that the block-matrix associations on Tinos and Syros can be grouped together. On a broader regional scale, there seem to be similarities between some meta-igneous rocks from Tinos and Evvia. Field relationships indicate that the mélanges occurring in southern Andros and northern Tinos can be correlated, but supporting geochemical and/or geochronological evidence for this interpretation could not be established. Previously published Jurassic ages for mafic and felsic mélange blocks from Andros suggest a genetic relationship to the ophiolite occurrences exposed in the larger Balkan region. A similar regional correlation is also considered likely for the Cretaceous meta-gabbros from Tinos and Syros, but cannot be documented with certainty.     

Calcium Isotopes (δ44/40Ca) in MPI-DING Reference Glasses, USGS Rock Powders and Various Rocks: Evidence for Ca Isotope Fractionation in Terrestrial Silicates

We report δ^44/40Ca_{(SRM 915a)} values for eight fused MPI‐DING glasses and the respective original powders, six USGS igneous rock reference materials, the U‐Th disequilibria reference material TML, IAEA‐CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM‐GEOMAR and Saskatchewan Isotope Laboratory) using ⁴³Ca/⁴⁸Ca‐ and ⁴²Ca/⁴³Ca‐double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2‰ at the 95% confidence level. The impact of different preparation methods on the δ^44/40Ca_{(SRM 915a)} values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ^44/40Ca_{(SRM 915a)} values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of δ^44/40Ca_{(SRM 915a)} values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS‐1 (1.49 ± 0.06‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in ⁴⁴Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in ⁴⁴Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.