How stacking disorder can conceal the actual structure of micas: the case of phengites

The present study deals with how stochastic stackings of tetrahedral/octahedral phengitic sheets bearing diverse cation distributions affect diffraction signals and the structural inferences therefrom derived. The interest for such minerals is dictated by that the stability of phengite polytypes, their cation distributions and P/T conditions of crystallization are related to each other. We focus our attention on layers’ probabilistic sequences that preserve the topology of the polytypes 2M ₁(SG: C2/c) and 3T(SG: P3₁12). Neutron diffraction intensities are modelled by a Monte Carlo approach and then used as artificial experimental data for conventional structure refinements that yield the occupancy factors in the fourfold (Si, Al) and sixfold (Al, Mg) coordination sites of 2M ₁ and 3T. The cation ordering from structure refinement tallies with the one of the “average structure” of a stochastic stacking, but it can significantly differ from those of the individual tetrahedral/octahedral sheets. For instance, sheets having ordered cation arrangements can lead to a stochastic structure which is supposed to bear a fully disordered cation partitioning according to structure refinement. This affects the configuration entropy contributions: the values obtained by conventional refinements can deviate from the correct ones up to 30 %. The analysis of the equivalent reflection intensities brings to light the anomalies hinting at the occurrence of such stacking disorder (using modelled reflections, the mean ratio between standard deviation and average intensity of symmetry equivalent reflections is ideally 0 for perfect crystal structures, but it can amount up to 6 in stochastically disordered phengites). However, taking into account the instrumental uncertainties and the deviations from ideality of actual crystals, such phenomena are very difficult to be detected experimentally.     

Changes in sediment and organic carbon accumulation in a highly-disturbed ecosystem: The Sacramento-San Joaquin River Delta (California, USA)

We used the Sacramento-San Joaquin River Delta CA (Delta, hereafter) as a model system for understanding how human activities influence the delivery of sediment and total organic carbon (TOC) over the past 50–60 years. Sediment cores were collected from sites within the Delta representing the Sacramento River (SAC), the San Joaquin River (SJR), and Franks Tract (FT), a flooded agricultural tract. A variety of anthropogenic tracers including ¹³⁷Cs, total DDE (∑DDE) and brominated diphenyl ether (BDE) congeners were used to quantify sediment accumulation rates. This information was combined with total organic carbon (TOC) profiles to quantify rates of TOC accumulation. Across the three sites, sediment and TOC accumulation rates were four to eight-fold higher prior to 1972. Changes in sediment and TOC accumulation were coincident with completion of several large reservoirs and increased agriculture and urbanization in the Delta watershed. Radiocarbon content of TOC indicated that much of the carbon delivered to the Delta is “pre-aged” reflecting processing in the Delta watershed or during transport to the sites rather than an input of predominantly contemporary carbon (e.g., 900–1400 years BP in surface sediments and 2200 yrs BP and 3610 yrs BP at the base of the SJR and FT cores, respectively). Together, these data suggest that human activities have altered the amount and age of TOC accumulating in the Delta since the 1940s.     

Inverse analysis of stochastic moment equations for transient flow in randomly heterogeneous media

We present a nonlinear stochastic inverse algorithm that allows conditioning estimates of transient hydraulic heads, fluxes and their associated uncertainty on information about hydraulic conductivity (K) and hydraulic head (h  ) data collected in a randomly heterogeneous confined aquifer. Our algorithm is based on Laplace-transformed recursive finite-element approximations of exact nonlocal first and second conditional stochastic moment equations of transient flow. It makes it possible to estimate jointly spatial variations in natural log-conductivity (Y=lnK)$(Y=\ln K)$, the parameters of its underlying variogram, and the variance–covariance of these estimates. Log-conductivity is parameterized geostatistically based on measured values at discrete locations and unknown values at discrete “pilot points”. Whereas prior values of Y at pilot point are obtained by generalized kriging, posterior estimates at pilot points are obtained through a maximum likelihood fit of computed and measured transient heads. These posterior estimates are then projected onto the computational grid by kriging. Optionally, the maximum likelihood function may include a regularization term reflecting prior information about Y. The relative weight assigned to this term is evaluated separately from other model parameters to avoid bias and instability. We illustrate and explore our algorithm by means of a synthetic example involving a pumping well. We find that whereas Y and h can be reproduced quite well with parameters estimated on the basis of zero-order mean flow equations, all model quality criteria identify the second-order results as being superior to zero-order results. Identifying the weight of the regularization term and variogram parameters can be done with much lesser ambiguity based on second- than on zero-order results. A second-order model is required to compute predictive error variances of hydraulic head (and flux) a posteriori. Conditioning the inversion jointly on conductivity and hydraulic head data results in lesser predictive uncertainty than conditioning on conductivity or head data alone.     

Petrology of lavas from the 2004–2005 flank eruption of Mt. Etna,Italy: inferences on the dynamics of magma in the shallow plumbing system

Following the 2001 and 2002–2003 flank eruptions, activity resumed at Mt. Etna on 7 September 2004 and lasted for about 6 months. This paper presents new petrographic, major and trace element, and Sr–Nd isotope data from sequential samples collected during the entire 2004–2005 eruption. The progressive change of lava composition allowed defining three phases that correspond to different processes controlling magma dynamics inside the central volcano conduits. The compositional variability of products erupted up to 24 September is well reproduced by a fractional crystallization model that involves magma already stored at shallow depth since the 2002–2003 eruption. The progressive mixing of this magma with a distinct new one rising within the central conduits is clearly revealed by the composition of the products erupted from 24 September to 15 October. After 15 October, the contribution from the new magma gradually becomes predominant, and the efficiency of the mixing process ensures the emission of homogeneous products up to the end of the eruption. Our results give insights into the complex conditions of magma storage and evolution in the shallow plumbing system of Mt. Etna during a flank eruption. Furthermore, they confirm that the 2004–2005 activity at Etna was triggered by regional movements of the eastern flank of the volcano. They caused the opening of a complex fracture zone extending ESE which drained a magma stored at shallow depth since the 2002–2003 eruption. This process favored the ascent of a different magma in the central conduits, which began to be erupted on 24 September without any significant change in eruptive style, deformation, and seismicity until the end of eruption.     

A seismic investigation into the geometry and controls upon alluvial architecture in the Walloon Subgroup,Surat Basin,Queensland

The sedimentology of the Walloon Subgroup (WSG) has been extensively studied; however, gaps exist in our understanding of the succession's alluvial architecture and the mechanisms controlling its complex internal organisation. Successful coal-seam gas development in the Surat Basin requires the construction of predictive facies models, which in turn necessitates a fulsome understanding of the geometry and controls on the spatial and temporal distribution of alluvial sub-environments. To improve our models of WSG facies, this study employs an open-source high-resolution 3D seismic dataset available on the western limb of the Surat Basin. Integration of core, wireline and seismic data has resolved the geometries of four discrete alluvial architectural elements, representing simple channel, channel belt, crevasse splay complexes and peat-mire sub-environments. Channel belts were found to be 1600–2000 m wide, simple channels 400–800 m in width and crevasse splays averaging 3.5 × 5.5 km. Coal bodies mapped from seismic attribute extractions were found to be 4.2 km² on average. The high-resolution dataset has also yielded insight into the geological controls governing the spatial and temporal distribution of these sub-environments, explaining, in part the mechanisms responsible for the complex internal distribution of facies within the WSG. In places within the study area, the WSG's sedimentary organisation appears to be initiated by the rejuvenation of deep-seated tectonic features, the expression of which is propagated upward via the mechanics of compensational stacking.     

Radionuclide Transport Behavior in a Generic Geological Radioactive Waste Repository

We performed numerical simulations of groundwater flow and radionuclide transport to study the influence of several factors, including the ambient hydraulic gradient, groundwater pressure anomalies, and the properties of the excavation damaged zone (EDZ), on the prevailing transport mechanism (i.e., advection or molecular diffusion) in a generic nuclear waste repository within a clay‐rich geological formation. By comparing simulation results, we show that the EDZ plays a major role as a preferential flowpath for radionuclide transport. When the EDZ is not taken into account, transport is dominated by molecular diffusion in almost the totality of the simulated domain, and transport velocity is about 40% slower. Modeling results also show that a reduction in hydraulic gradient leads to a greater predominance of diffusive transport, slowing down radionuclide transport by about 30% with respect to a scenario assuming a unit gradient. In addition, inward flow caused by negative pressure anomalies in the clay‐rich formation further reduces transport velocity, enhancing the ability of the geological barrier to contain the radioactive waste. On the other hand, local high gradients associated with positive pressure anomalies can speed up radionuclide transport with respect to steady‐state flow systems having the same regional hydraulic gradients. Transport behavior was also found to be sensitive to both geometrical and hydrogeological parameters of the EDZ. Results from this work can provide useful knowledge toward correctly assessing the post‐closure safety of a geological disposal system.