Mobilization of colloidal ferrihydrite particles in porous media—An inner-sphere complexation approach

Prediction of colloid release and transport as affected by reactive species remains a significant challenge for field applications. In this paper, we report experimental and modeling results of ferrihydrite colloid release under the influence of citrate species. Using a 3-plane surface complexation model, equilibrium constants were obtained for the three proposed inner-sphere complexes by fitting a citrate adsorption isotherm on ferrihydrite at pH 4, and a pH adsorption envelop with 0.64 mM citrate. The constants were used in a reactive transport model for simulating reaction fronts of dissolved species during injection of citrate in ferrihydrite-coated quartz columns. Simulation results show that sorption alone may not adequately describe the breakthrough curves. Inclusions of ferrihydrite dissolution and re-adsorption of Fe(III) improve the prediction of dissolved species transport. Additionally, matrix diffusion may be needed for improved prediction. For the release of colloidal iron oxides it was shown that both oxide dissolution and interfacial repulsion controlled the process during complete breakthrough. However, the peak release of colloids, which occurred during the actual breakthrough of dissolved species, was mainly brought about by electric double layer forces. These particles underwent detachment-deposition-detachment cycles along the flow path, and emerged in the effluent with the major reaction front. To quantitatively predict colloid release, a semi-empirical linear correlation was established, linking the calculated electric potential to experimental colloid release rates. The model may be applied to the prediction and scaling of aquifer remediation studies involved in the injection of organic ligands to mobilize particle bound contaminants.     

The transport of Osmium and Strontium isotopes through a tropical estuary

We have determined the concentration and isotopic composition of Os and Sr in the estuarine waters from the Godavari delta in Peninsular India. Additionally, we have obtained the concentration and isotopic composition of Os and Al concentration in selected suspended particulate matter recovered on 0.45 μm filters. The Na, K, Mg, and Ca concentrations of water samples obtained along salinity gradients from two distributary channels in the delta display a general two component mixing between river- and sea-water. The data also reveal that Al behaves non-conservatively and is affected by interactions with suspended particulates. The ⁸⁷Sr/⁸⁶Sr ratio of the riverine end member is 0.716303 and shows a linear decrease with salinity to seawater value and Sr isotope systematics indicate that its behavior is conservative in the estuary.The ¹⁸⁷Os/¹⁸⁸Os ratio of the Godavari river end-member is 1.24 and within error of the average eroding upper continental crust. The concentration and isotopic composition of Os through the two salinity transects shows that its behavior in the Godavari estuary is complex and non-conservative. By comparing the Al/Os ratios and Os isotopes in the waters with those of the suspended particulate we find that both Os gains and losses occur in the water column. However, in one of the distributaries (Vasishta) the Os concentration of suspended load increases and that of dissolved load decreases with increasing salinity towards the Bay of Bengal end-member. We infer that there is removal of seawater Os at higher salinities. The estimated mean residence time of Os in the oceans is 37 ± 14 (2σ) kyr. A comparison of the Os concentration of the Bay of Bengal and the Indian Ocean waters indicates that the rainout rate of Os in Bay of Bengal is 30% faster than that in the open ocean and suggests that the observed discrepancy between the mean residence time calculated from mass balance considerations and that estimated from the relaxation of the Os isotopic ratio in marine record may not be real as the relaxation time experiments likely estimate the residence time for a basin/sub-basin and not for the entire ocean.     

Adaptive Optics on a 3.6-Meter Telescope. The ADONIS System.

ADONIS is an adaptive optics (AO) user friendly instrument offered to the European astronomical community on the ESO 3.6-m telescope at La Silla. It is an upgraded version of COME-ON-PLUS, the VLT AO prototype, which already produced significative astrophysical results in a wide range of fields, from planetology to extragalactic astrophysics. ADONIS is now allowing the astronomer to use adaptive optics as a common user instrument thanks to the implementation of an open artificial intelligence software that handles the large number of parameters needed to optimise the AO correction. We will describe the ADONIS system, including the two dedicated infrared cameras, summarize its performances and discuss the observing procedures.     

The earth system model of intermediate complexity CLIMBER-3α. Part I: description and performance for present-day conditions

We herein present the CLIMBER-3α Earth System Model of Intermediate Complexity (EMIC), which has evolved from the CLIMBER-2 EMIC. The main difference with respect to CLIMBER-2 is its oceanic component, which has been replaced by a state-of-the-art ocean model, which includes an ocean general circulation model (GCM), a biogeochemistry module, and a state-of-the-art sea-ice model. Thus, CLIMBER-3α includes modules describing the atmosphere, land-surface scheme, terrestrial vegetation, ocean, sea ice, and ocean biogeochemistry. Owing to its relatively simple atmospheric component, it is approximately two orders of magnitude faster than coupled GCMs, allowing the performance of a much larger number of integrations and sensitivity studies as well as longer ones. At the same time its oceanic component confers on it a larger degree of realism compared to those EMICs which include simpler oceanic components. The coupling does not include heat or freshwater flux corrections. The comparison against the climatologies shows that CLIMBER-3α satisfactorily describes the large-scale characteristics of the atmosphere, ocean and sea ice on seasonal timescales. As a result of the tracer advection scheme employed, the ocean component satisfactorily simulates the large-scale oceanic circulation with very little numerical and explicit vertical diffusion. The model is thus suited for the study of the large-scale climate and large-scale ocean dynamics. We herein describe its performance for present-day boundary conditions. In a companion paper (Part II), the sensitivity of the model to variations in the external forcing, as well as the role of certain model parameterisations and internal parameters, will be analysed.     

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

This study investigates the application of sulphur isotope ratios (δ³⁴S) in combination with carbon (δ¹³C) and nitrogen (δ¹⁵N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ³⁴S values were found. The δ³⁴S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ³⁴S values of the fish were clustered and ³⁴S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly ³⁴S-depleted sulphur influenced the soil. The humans show the largest range of δ³⁴S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ³⁴S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R² = 0.71; p < 0.0001) between their δ¹⁵N and δ³⁴S compositions. These δ³⁴S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ³⁴S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.     

Isotopic constraints on the origin of ultramafic and mafic dikes in the Balmuccia peridotite (Ivrea Zone)

The Balmuccia peridotite massif in the central Ivrea Zone constitutes an upper mantle slice which has been tectonically emplaced into the crust. It represents the residue from partial melting of undepleted mantle material and varies in composition from lherzolite to harzburgite and subordinate dunite. Dikes of websterite and gabbroic pods within the peridotite can be subdivided into an older Crdiopside suite and a younger Al-augite suite. Nd isotopic data on whole rocks of these lithotypes in combination with independent observations suggest that the dikes formed during a Hercynian event about 270 Ma ago. The rocks of the Cr-diopside dikes, in particular, display isotopic signatures similar to those of the lherzolite and represent fractionates from partial melts derived from the lherzolite wall rock. The Sm-Nd data of the pyroxenites and gabbros of the Al-augite suite, in contrast, scatter widely and suggest that partial melting of lherzolite was triggered or at least accompanied by introduction of fluids and/or liquid phases. These fluids or liquids carried exotic isotopic components from elsewhere in the crust-mantle complex, and deposited them within the rocks by metasomatic reactions. Two distinct types of metasomatism must have operated not only within the Balmuccia body, but also in the complex of Finero: The first type of metasomatism introduced mantle-derived volatiles and is responsible for formation of amphibole. The other type has a crustal source and led to formation of phlogopite, which occurs mainly within mantle rocks of Finero, but occasionally, within the Balmuccia body also.     

The Jovian atmospheric window at 2.7 μm: A search for H2S

The atmospheric transmission window at 2.7 μm in Jupiter's atmosphere was observed at a spectral resolution of 0.1 cm^?1 from the Kuiper Airborne Observatory. From analysis of the CH₄ abundance (～80m-am) and the H₂O abundance (<0.0125cm-am) it was determined that the penetration depth of solar flux at 2.7 μm is near the base of the NH₃ cloud layer. The upper limit to H₂O at 2.7 μm and other recent results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. The search for H₂S in Jupiter's atmosphere yielded an upper limit of ～0.1cm-am. The corresponding limit to the elemental abundance ratio [S]/[H] was ～1.7 × 10^?8, about 10^?3 times the solar value. Upon modeling the abundance and distribution of H₂S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH₄SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.     

The potential of the ground based arrays of imaging atmospheric Cherenkov telescopes. II. Gamma ray flux sensitivities

We discuss the capability of ‘100 GeV’ class imaging atmospheric Cherenkov telescope (IACT) arrays as future powerful instruments of ground-based gamma-ray astronomy. It is assumed that the array is gathered from individually triggered quadrangular 4-IACT ‘cells’ with a linear size of about 100 m. The multi-cell concept allows coverage of large detection areas economically, and at the same time the effective exploitation of the stereoscopic approach of determination of the shower parameters using information obtained by several IACTs simultaneously. Determination of arrival directions of γ-ray primaries on an event-by-event basis with accuracy δθ ≤ 0.1° combined with high suppression efficiency (at both the hardware and software levels) of the background hadronic showers by a factor of ≈ 10³, and large, up to 1 km² collection areas, can provide minimum detectable energy fluxes of ≥ 100 GeV γ-rays from point sources down to 10⁻¹³ erg/cm² s which is about 3 orders of magnitude lower than the current sensitivities achieved by the satellite-borne detectors at MeV and GeV energies. High sensitivities of multi-IACT arrays would partially compensate the limited efficiency of the technique for all-sky surveys, as well as allow study of moderately extended (≤ 1°) γ-ray sources. IACT arrays with minimum detectable fluence of ≥ 100 GeV γ-rays S_γ < 10⁻⁸ erg/cm² are well suited for effective exploration of highly sporadic nonthermal phenomena from different classes of astrophysical objects on time-scales from ≤ 1 s to several minutes.     

The potential of ground based arrays of imaging atmospheric Cherenkov telescopes. I. Determination of shower parameters

The performance of the arrays of imaging atmospheric Cherenkov telescopes (IACTs) for detection of ≥ 100 GeV γ-rays is discussed. The effective detection area of stereoscopic multi-IACT systems is determined essentially by the total geometrical area of the array which may be covered by independent standard ≥ 3 telescope ‘cells’ with a linear size of about 100 m. We have investigated the characteristics of a quadrangular 100 × 100 m² ‘cell’ with four ‘100 GeV’ class IACTs in its corners which is recommended as an optimal design for the future IACT arrays. The idea of the ‘cell’ makes straightforward the study of the characteristics of IACT arrays. The conclusions obtained, concerning in particular the angular and energy resolutions, and the cosmic ray background rejection efficiency, are rather general and, do not depend on the specific configuration of the array.     

Nondestructive spectroscopic and petrochemical investigations of Paleoarchean spherule layers from the ICDP drill core BARB5, Barberton Mountain Land,South Africa

A Paleoarchean impact spherule‐bearing interval of the 763 m long International Continental Scientific Drilling Program (ICDP) drill core BARB5 from the lower Mapepe Formation of the Fig Tree Group, Barberton Mountain Land (South Africa) was investigated using nondestructive analytical techniques. The results of visual observation, infrared (IR) spectroscopic imaging, and micro‐X‐ray fluorescence (μXRF) of drill cores are presented. Petrographic and sedimentary features, as well as major and trace element compositions of lithologies from the micrometer to kilometer‐scale, assisted in the localization and characterization of eight spherule‐bearing intervals between 512.6 and 510.5 m depth. The spherule layers occur in a strongly deformed section between 517 and 503 m, and the rocks in the core above and below are clearly less disturbed. The μXRF element maps show that spherule layers have similar petrographic and geochemical characteristics but differences in (1) sorting of two types of spherules and (2) occurrence of primary minerals (Ni‐Cr spinel and zircon). We favor a single impact scenario followed by postimpact reworking, and subsequent alteration. The spherule layers are Al₂O₃‐rich and can be distinguished from the Al₂O₃‐poor marine sediments by distinct Al‐OH absorption features in the short wave infrared (SWIR) region of the electromagnetic spectrum. Infrared images can cover tens to hundreds of square meters of lithologies and, thus, may be used to search for Al‐OH‐rich spherule layers in Al₂O₃‐poor sediments, such as Eoarchean metasediments, where the textural characteristics of the spherule layers are obscured by metamorphism.