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.     

Statistical tests for regional seismic phase characterizations

In seismic analysis some assumptions are often made aboutthe data, e.g. stationarity and Gaussianity. This is not obvious for all realseismic data. Here, we use statistical tests for characterization of regionalseismic data. We apply tests for stationarity, symmetry, linearity, andtime-reversibility. In the analysis we use twelve regional seismic events inFennoscandia recorded with the seismic small-aperture arrays NORESS,ARCESS and FINESA at hypocentral distances in the range from 160 to1580 km. For the tests we use the regional phases Pn, secondary P, Sn and Lg-phases and the preceding noise. Two of the eventsare explosions, two are rockbursts and eight are earthquakes. Theperformance and possibilities of using statistical tests based on bispectra, asa complementary tool for conventional analysis of seismic phases isdemonstrated. The preceding noise recorded before the first onset of theP-wave for the twelve events is tested to be spatially stationarybetween each channel within each array and temporal stationary in 21consecutive time windows of 3.2 sec each. Also, the preceding noise issymmetric and linear. The seismic phases defined by the symmetry test asnon-Gaussian (not symmetric) are all linear. This means a linear model canbe used to characterize both the noise and the phases. The first P-phase for the two explosions is characterized as non-Gaussian at thethree arrays. For all 36 possibly first P-phase arrivals at the three arraystations, 23 are non-Gaussian. The second P-phase is non-Gaussian at13 of 36 data records, the S-phase at eleven of 36 and the Lg-phase at nine of 36. For all the four phases more than 32 of possible36 are time-reversible.     

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.     

Differential nocturnal cooling in the landscape detected by mobile measurements

Summary In June 1986 mobile air temperature measurements were performed in the Kivik area in Sweden. The measuring trips were repeated each hour during a night with calm and clear weather conditions. Along a loop, 8650 m long and traversing a hilly landscape, the air temperature was measured at four levels (0.2, 1.0, 2.0 and 3.0 m a g). In this study the results are focused on the measurements at the standard level, 2.0 m a g, in order to make it easier to compare this study with earlier mobile studies.Sudden rises in air temperature at 2.0 m occurred at a number of elevated locations along the loop, at a max. rate of 3.5°C/hour, indicative of the influence of dynamic turbulence. Lower parts of the loop did show a drop in air temperature at the same time, with a max. of 3.8°C/hour, indicative of cold air influence. In most earlier studies the mobile measurements were compensated for the nocturnal cooling in order to make it possible to directly compare the different measurement points. This study highlights the problems due to turbulence as mentioned above. It also stresses the fact that more reference measurements at more than one point along a loop are needed in hilly terrain.With 7 Figures     

Influence of tectonic structures on the Hope Slide, British Columbia, Canada

The Hope Slide, which occurred on January 9, 1965, involved an estimated 47-Mm³ of meta-volcanics and intrusive rocks. Previous workers reported the presence of tectonic structures (faults and shear zones) along the failure surface at the Hope Slide. These tectonic features were investigated in detail to assess their effects on rock-mass quality and the related implications for slope stability. This paper integrates basic field and laboratory concepts from structural and engineering geology. Subdividing the failure area into structural domains allowed distinct discontinuity sets to be associated with specific tectonic structures. The Geological Strength Index (GSI) was used to estimate the rock-mass damage related to the tectonic structures. Low GSI values were seen to outline tectonic damage zones. Point-load tests were used to characterise the compressive strength of rocks adjacent to the tectonic structures. Strength anisotropy, tentatively attributed to damage caused by a large shear zone, was observed in greenstone samples. Seepage zones along the failure surface were observed preferentially along shallow discontinuities that dipped downslope and in rock masses of good quality (GSI > 40). An alternative morphology of the slope failure is proposed by distinguishing between the extent of the surficial damage due to the rock-slope failure and the zone of failed material (depletion zone). For the first time, a kinematic mechanism for the Hope Slide is proposed, based on a preliminary 3-dimensional block model. A pre-1965 DEM was produced from estimates of material lost and gained as reported by previous workers. The pre-1965 DEM revealed that the tectonic structures recognised during fieldwork bounded the material that failed in the 1965 event.     

Groundwater – the disregarded component in lake water and nutrient budgets. Part 2: effects of groundwater on nutrients

Lacustrine groundwater discharge (LGD) transports nutrients from a catchment to a lake, which may fuel eutrophication, one of the major threats to our fresh waters. Unfortunately, LGD has often been disregarded in lake nutrient studies. Most measurement techniques are based on separate determinations of volume and nutrient concentration of LGD: Loads are calculated by multiplying seepage volumes by concentrations of exfiltrating water. Typically low phosphorus (P) concentrations of pristine groundwater often are increased due to anthropogenic sources such as fertilizer, manure or sewage. Mineralization of naturally present organic matter might also increase groundwater P. Reducing redox conditions favour P transport through the aquifer to the reactive aquifer‐lake interface. In some cases, large decreases of P concentrations may occur at the interface, for example, due to increased oxygen availability, while in other cases, there is nearly no decrease in P. The high reactivity of the interface complicates quantification of groundwater‐borne P loads to the lake, making difficult clear differentiation of internal and external P loads to surface water. Anthropogenic sources of nitrogen (N) in groundwater are similar to those of phosphate. However, the environmental fate of N differs fundamentally from P because N occurs in several different redox states, each with different mobility. While nitrate behaves essentially conservatively in most oxic aquifers, ammonium's mobility is similar to that of phosphate. Nitrate may be transformed to gaseous N₂ in reducing conditions and permanently removed from the system. Biogeochemical turnover of N is common at the reactive aquifer‐lake interface. Nutrient loads from LGD were compiled from the literature. Groundwater‐borne P loads vary from 0.74 to 2900 mg PO₄‐P m^?2 year^?1; for N, these loads vary from 0.001 to 640 g m^?2 year^?1. Even small amounts of seepage can carry large nutrient loads due to often high nutrient concentrations in groundwater. Large spatial heterogeneity, uncertain areal extent of the interface and difficult accessibility make every determination of LGD a challenge. However, determinations of LGD are essential to effective lake management. Copyright © 2014 John Wiley & Sons, Ltd.