Nonstationarity of the Mean and Unbiased Variogram Estimation: Extension of the Weighted Least-Squares Method

When concerned with spatial data, it is not unusual to observe a nonstationarity of the mean. This nonstationarity may be modeled through linear models and the fitting of variograms or covariance functions performed on residuals. Although it usually is accepted by authors that a bias is present if residuals are used, its importance is rarely assessed. In this paper, an expression of the variogram and the covariance function is developed to determine the expected bias. It is shown that the magnitude of the bias depends on the sampling configuration, the importance of the dependence between observations, the number of parameters used to model the mean, and the number of data. The applications of the expression are twofold. The first one is to evaluate a priori the importance of the bias which is expected when a residuals-based variogram model is used for a given configuration and a hypothetical data dependence. The second one is to extend the weighted least-squares method to fit the variogram and to obtain an unbiased estimate of the variogram. Two case studies show that the bias can be negligible or larger than 20%. The residual-based sample variogram underestimates the total variance of the process but the nugget variance may be overestimated.     

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO₃Fe⁺ and >CO₃FeCO₃H⁰. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t_1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t_1/2 = 41 ± 1 min and t_1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO₃FeCO₃H⁰, for which the species specific rate constant was estimated.     

Crystallization of quartz dioritic magmas at 2 and 1 kbar: experimental results

Crystallization experiments were performed on quartz diorite (~55 wt.% SiO₂, 3.1–8.4 wt.% MgO) from the G?siniec Intrusion (Bohemian Massif, SW Poland) at 1?2 kbar, 750–850°C, various mole fractions of water and with fO₂ buffered by the NNO buffer. The two natural quartz diorites (leucocratic poikilitic quartz diorite - ‘LPD’ and melanocratic quartz diorite - ‘MD’) differ in whole rock and mineral composition with MD being richer in MgO and poorer in CaO than LPD, probably due to accumulation of mafic minerals or melt removal in MD. LPD represents melt composition and is used to reconstruct crystallization conditions in the G?siniec Intrusion. The crystallization history of LPD magma, deduced from experimental and natural mineral compositions, includes a higher pressure stage probably followed by emplacement at ~2 kbar of partly crystallized magma at temperatures ~850?800°C and quick cooling. The mineral assemblage present in LPD requires water contents in the magma of at least 5 wt% and oxygen fugacity below that controlled by the NNO buffer. The compositions of mafic minerals in the MD composition were equilibrated at temperatures below 775°C and at subsolidus conditions. The equilibration was probably due to the reaction between water-rich, oxidizing residual melt and the cumulatic-restitic mineral assemblage. MD is characterized by occurrence of the euhedral cummingtonite and increasing anorthite content in the rims of plagioclase. A similar reaction was reproduced experimentally in both LPD and MD compositions indicating that cummingtonite may be a late magmatic phase in quartz dioritic systems, crystallizing very close to solidus and only from water saturated magma.     

Lagrangian model of zooplankton dispersion: numerical schemes comparisons and parameter sensitivity tests

This paper presents two comparisons or tests for a Lagrangian model of zooplankton dispersion:numerical schemes and time steps.Firstly,we compared three numerical schemes using idealized circulations.Results show that the precisions of the advanced Adams-Bashfold-Moulton(ABM) method and the Runge-Kutta(RK) method were in the same order and both were much higher than that of the Euler method.Furthermore,the advanced ABM method is more efficient than the RK method in computational memory requirements and time consumption.We therefore chose the advanced ABM method as the Lagrangian particle-tracking algorithm.Secondly,we performed a sensitivity test for time steps,using outputs of the hydrodynamic model,Symphonie.Results show that the time step choices depend on the fluid response time that is related to the spatial resolution of velocity fields.The method introduced by Oliveira et al.in 2002 is suitable for choosing time steps of Lagrangian particle-tracking models,at least when only considering advection.     

Cation adsorption on oxides and clays: The aluminum case

The sorption mechanisms for trace metal ions on montmorillonite have been investigated. Complexation with surface hydroxyl groups located on the brocken edges of platelet particles is found to occur over a pH range similar to that observed on silica and other oxides, at comparable metal/site ratios. A second mechanism involving cation exchange on the negatively charge basal plane, which does not involve proton exchange in our experimental conditions, has been invoked to explain the low pH behavior. Consistent with this cation exchange mechanism, adsorption at low pH is strongly ionic strength dependant. A quantitative model which involves both mechanisms is presented and tested against both cation and proton adsorption data.     

Using project food aid to help alleviate urban poverty - experience and issues

As urban poverty in the Third World worsens, an increasing proportion of World Food Programme (WFP) food aid is being used to support poor urban dwellers. WFP food aid has typically been used in three main ways in urban areas: as free relief after disasters (such as floods or earthquakes) have struck urban centres; as part of institutional feeding projects; and as support to urban renewal. While there have been some creative approaches to using food aid to help overcome urban poverty, the benefits have usually only been temporary. It has proved difficult to design food aid interventions for the urban poor that help to overcome the causes of poverty in sustainable ways. The challenge is to use food aid to help make permanent as well as temporary improvements in the lives and livelihoods of the poor.     

Hydrology of a spring complex, studied by geochemical time-series data, Acquarossa, Switzerland

A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO₄, 700 mg/l HCO₃, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO₂, and with an isotopic composition of δD = − 73.0‰ and δ¹⁸ O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ¹⁸ O = −10.5‰ and tritium as in recent (post-bomb) precipitation.     

Flood and earthquake disturbance of 210Pb geochronology (Lake Anterne, NW Alps)

Dating recent lake sediment records yielding disturbed ²¹⁰Pb profiles has been a problem of wide interest in palaeoclimatic and palaeoseismic studies over the last few centuries. When applied to an alpine lake sedimentary record, a high-resolution sedimentological study reveals that the ²¹⁰Pb profile is disturbed by the occurrence of single-event deposits triggered by two different mechanisms: flood events deposits and gravity reworking. Removing disturbed layers from the ²¹⁰Pb profile yields a logarithmic depth–activity relationship. Using a simple ²¹⁰Pb decay model (CFCS) provides an assessment of mean accumulation rate of `continuous sedimentation', as opposed to `event-linked sedimentation'. The correlation of the thickest four gravity-reworked deposits with historically known earthquakes permits both validation and refinement of the age–depth relationship. This refinement highlights variations in accumulation rate consistent with post-Little Ice Age climatic variations.     

On the Alignment of T Tauri Stars with the Local Magnetic Field in the Taurus Molecular Cloud Complex

Magnetic field is believed to play an important role in the collapse of a molecular cloud. In particular, due to the properties of magnetic forces, collapse should be easier along magnetic field lines. This is supported by the large-scale sheet-like structures observed in the Taurus giant molecular cloud for instance. Here we investigate whether such a preferred orientation for collapse is present at a much smaller scale, that of individual objects, i.e., about 100AU. We use recent high-angular resolution images of T Tauri stars located in the Taurus star-forming region to find the orientation of the symmetry axis of each star+jet+disk system and compare it with that of the local magnetic field. We find that (i) T Tauri stars that are associated to a jet or an outflow are generally oriented parallel to the magnetic field, as previously demonstrated. More surprising, given our current knowledge of these objects, we also find that (ii) T Tauri stars that are not at present believed to be associated to a jet or an outflow are oriented very differently, i.e., mostly perpendicular to the magnetic field. We present some implications of this puzzling new result.