Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Elucidating the dynamics and mixing agents of a shallow fjord through age tracer modelling

The mixing agents and their role in the dynamics of a shallow fjord are elucidated through an Eulerian implementation of artificial tracers in a three-dimensional hydrodynamic model. The time scales of vertical mixing in this shallow estuary are short, and the artificial tracers are utilized in order to reveal information not detectable in the temperature or salinity fields. The fjord's response to external forcing is investigated through a series of model experiments in which we quantify vertical mixing, transport time scales of fresh water runoff and estuarine circulation in relation to external forcing.Using age tracers released at surface and bottom, we quantify the time scales of downward mixing of surface water and upward mixing of bottom water. Wind is shown to be the major agent for vertical mixing at nearly all depth levels in the fjord, whereas the tide or external sea level forcing is a minor agent and only occasionally more important just close to the bottom. The time scale of vertical mixing of surface water to the bottom or ventilation time scale of bottom water is estimated to be in the range 0.7 h to 9.0 days, with an average age of 2.7 days for the year 2004.The fjord receives fresh water from two streams entering the innermost part of the fjord, and the distribution and age of this water are studied using both ageing and conservative tracers. The salinity variations outside this fjord are large, and in contrast to the salinity, the artificial tracers provide a straight forward analysis of river water content. The ageing tracer is used to estimate transport time scales of river water (i.e. the time elapsed since the water left the river mouth). In May 2004, the typical age of river water leaving the fjord mouth is 5 days. As the major vertical mixing agent is wind, it controls the estuarine circulation and export of river water. When the wind stress is set to zero, the vertical mixing is reduced and the vertical salinity stratification is increased, and the river water can be effectively exported out of the fjord.We also analyse the river tracer fields and salinity field in relation to along estuary winds in order to detect signs of wind-induced straining of the along estuary density gradient. We find that events of down estuary winds are primarily associated with a reduced along estuary salinity gradient due to increased surface salinity in the innermost part of the fjord, and with an overall decrease in vertical stratification and river water content at the surface. Thus, our results show no apparent signs of wind-induced straining in this shallow fjord but instead they indicate increased levels of vertical mixing or upwelling during down estuary wind events.     

Long-term effects of tributyltin compounds on the baltic amphipod, Gammarus oceanicus

Amphipod larvae, Gammarus oceanicus, were exposed for 8 weeks to bis(tributyltin) oxide (TBTO) or tributyltin fluoride (TBTF), or for 5 weeks to leachates from tributyltin-containing antibiofouling paints. No larvae survived 8 weeks' exposure to 3 μg/litre TBTO or TBTF. Differential larval survival occurred during exposure to 0·3 gmg/litre of these same compounds. Paint leachates were shown to cause similar toxicity responses at comparable aqueous tributyltin concentrations. An examination of sublethal responses showed slight decreases in growth for larvae exposed to TBTO and to paint leachates, although responses at tributyltin levels below 1 μg/litre were not marked. Whole-animal oxygen consumption rates were not affected by low tributyltin exposure levels. While these studies demonstrate low level toxicity of tributyltins, effects on oxygen consumption and growth do not indicate a mode of action for these compounds.     

Using GPS multipath to measure soil moisture fluctuations: initial results

Measurements of soil moisture are important for studies of climate and weather forecasting, flood prediction, and aquifer recharge studies. Although soil moisture measurement networks exist, most are sparsely distributed and lack standardized instrumentation. Measurements of soil moisture from satellites have extremely large spatial footprints (40–60 km). A methodology is described here that uses existing networks of continuously-operating GPS receivers to measure soil moisture fluctuations. In this technique, incoming signals are reflected off and attenuated by the ground before reception by the GPS receiver. These multipath reflections directly affect signal-to-noise ratio (SNR) data routinely collected by GPS receivers, creating amplitude variations that are a function of ground reflectivity and therefore soil moisture content. After describing this technique, multipath reflection amplitudes at a GPS site in Tashkent, Uzbekistan are compared to estimates of soil moisture from the Noah land surface model. Although the GPS multipath amplitudes and the land surface model are uncalibrated, over the 70-day period studied, they both rise sharply following each rainfall event and slowly decrease over a period of ∼10 days.     

Remote spectroscopic identification of carbonaceous chondrite mineralogies: Applications to Ceres and Pallas

High-resolution spectroscopic observations of asteroids Ceres and Pallas have been obtained in the 1.0- to 2.6-μm region. Combined with previous spectralmeasurements at other wavelengths, this work presents the broadband spectral reflectances of these asteroids over the 0.4 to 3.6-um region. This extended coverage permits new analyses of the surface mineralogies of these objects. Using laboratory comparison spectra of meteorites and mixtures of terrestrial minerals, the surfaces of Ceres and Pallas are consistent with mixtures of opaques and hydrated silicates, such as are found in types C1 and C2 meteorites. This research emphasizes the importance of the 3-um spectral region for studying by remote methods the relationship of carbonaceous chondrite mineralogies to asteroid surfaces.     

Numerical study of droplet size dependent chemistry in oceanic,wintertime stratus cloud at southern mid-latitudes

Cloud droplet chemistry is modelled for the first 150 m of rise in a wintertime, mid-latitude, marine stratus cloud using observations made at and near the Cape Grim Baseline Station as a source of input parameters. The emphasis in this work was to study the variation in droplet chemistry as a function of both droplet size and nucleus composition, with a particular focus on the way in which oxidation of dissolved sulfur dioxide varied.At 150 m above the condensation level, solute concentration as a function of droplet size was found to increase by as much as 2 to 3 orders of magnitude for only a factor of 2 increase in droplet radius, primarily as a consequence of the 1/r dependence in the droplet growth equation. This type of size dependence exists at all levels in the model cloud, and has a significant influence on oxidation rate of sulfur dioxide in droplets growing on sulfate nuclei, oxidation by ozone being favoured in the smallest droplets, but oxidation by hydrogen peroxide being favoured in the larger droplets. Oxidation by ozone is favoured at all sizes in droplets formed on sea-salt nuclei as a result of the initially high alkalinity of these droplets, and in the cloud overall is calculated to be the more important oxidation pathway. Although based on a simplified chemical scheme, these results suggest that both size-dependent and nucleus-dependent chemistry of cloud droplets may need to be considered explicitly in cloud modelling work.Volume-weighted mean pH values in the range 5 to 6 were predicted from sensitivity studies in which input variables were varied over reasonable ranges, in agreement with two sets of bulk cloud-water pH data obtained by aircraft near Cape Grim.     

Upper limits to trace constituents in Jupiter's atmosphere from an analysis of its 5-μm spectrum

A high-resolution (0.6 cm^?1) spectrum of Jupiter at 5 μm recorded at the Kuiper Airborne Observatory is used to determine upper limits to the column density of 19 molecules. The upper limits to the mixing ratios of SiH₄, H₂S, HCN, and simple hydrocarbons are discussed with respect to current models of Jupiter's atmosphere. These upper limits are compared to expectations based upon the solar abundance of the elements. This analysis permits upper limit measurements (SiH₄), or actual detections (GeH₄), of molecules with mixing ratios with hydrogen as low as 10^?9. In future observations at 5 μm the sensitivity of remote spectroscopic analyses should permit the study of constituents with mixing ratios as low as 10^?10, which would include the hydrides of such elements as Sn and As as well as numerous organic molecules.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.