Acidities of confined water in interlayer space of clay minerals

The acid chemistry of confined waters in smectite interlayers have been investigated with first principles molecular dynamics (FPMD) simulations. Aiming at a systematic picture, we establish the model systems to take account of the three possible controlling factors: layer charge densities (0 e, 0.5 e and 1.0 e per cell), layer charge locations (tetrahedral and octahedral) and interlayer counterions (Na⁺ and Mg²⁺). For all models, the interlayer structures are characterized in detail. Na⁺ and Mg²⁺ show significantly different hydration characteristics: Mg²⁺ forms a rigid octahedral hydration shell and resides around the midplane, whereas Na⁺ binds to a basal oxygen atom and forms a very flexible hydration shell, which consists of five waters on average and shows very fast water exchanges. The method of constraint is employed to enforce the water dissociation reactions and the thermodynamic integration approach is used to derive the free-energy values and the acidity constants. Based on the simulations, the following points have been gained. (1) The layer charge is found to be the direct origin of water acidity enhancement in smectites because the neutral pore almost does not have influences on water dissociations but all charged pores do. (2) With a moderate charge density of 0.5 e per cell, the interlayer water shows a pKa value around 11.5. While increasing layer charge density to 1.0 e, no obvious difference is found for the free water molecules. Since 1.0 e is at the upper limit of smectites’ layer charge, it is proposed that the calculated acidity of free water in octahedrally substituted Mg²⁺-smectite, 11.3, can be taken as the lower limit of acidities of free waters. (3) In octahedrally and tetrahedrally substituted models, the bound waters of Mg²⁺ show very low pKa values: 10.1 vs 10.4. This evidences that smectites can also promote the dissociations of the coordinated waters of metal cations. The comparison between the two Mg²⁺-smectites reveals that different layer charge locations do not lead to obvious differences for bound and free water acidities.     

Packing states of ideal reservoir sands: Insights from simulation of porosity reduction by grain rearrangement

The question being tackled in this study is to which extent grain rearrangement contributes to porosity reduction in very well sorted quartzose sands (ideal reservoir sands). A numerical model, RAMPAGE (an acronym of random packing generator), has been developed to address this long-standing problem. RAMPAGE represents a synthesis of various algorithms designed to simulate packing of equal-sized spheres, which have been used to represent ideal solids, liquids, and gases, as well as natural porous media. The results of RAMPAGE simulations compare favourably to theoretical and experimental data from various disciplines and allow delineation of the field of gravitationally stable random packing of equal-sized spheres in the 2-D state space of porosity (P) versus mean coordination number (N). Three end-member packing states have been identified: random loose packing (RLP: P = 45.4%, N = 5.2), random close packing (RCP: P = 36.3%, N = 7.0), and bridged random close packing (Bridged RCP: P = 39.5%, N = 5.2). Unlike previously proposed models, RAMPAGE can simulate the transition from RLP to any other point in the stability field. The RLP state is fully consistent with wet-packed porosities of synthetic sands with lognormal mass-size distributions reported in the literature. The much higher in-situ porosity values reported for modern (air-packed) sands are unlikely to be preserved at depth on geological time scales. Data on the relation between intergranular volume and burial depth indicate that the observed intergranular volume reduction in the upper ~ 800 m of the sediment column corresponds to the evolution of RLP to RCP, and is thus fully explained by non-destructive grain rearrangement.     

昆虫多样性：一个被忽略的全球性重要问题

昆虫不仅是世界上最多的物种,同时也对生态系统功能和全球经济有着十分重要的作用。因此,昆虫多样性的保护对全球来说都有着十分重要的意义。然而,昆虫多样性常被＂生物多样性＂研究者们所忽略, 昆虫多样性与植物、气候变化的关系更是不明确。本文对将来昆虫多样性的研究方向提出了几点建议,基于中国北部两大典型的森林生态系统——东北长白山地区和华北东灵山地区。这两大地区的植被和气候已经有长期并且完整的调查,而对于其中昆虫多样性的了解却不多。因此在这两个地区开展研究认识昆虫多样性格局和进一步分析昆虫和植物的关系具有重要的科学和应用价值。     

Modelling thermal transients from magmatic underplating—an example from the Vøring margin (NE Atlantic)

The thermal impact of several kilometre-thick magmatic underplating in the lower continental crust is studied with analytical and numerical methods. Simple analytical solutions are derived for the thermal transient in the case of an infinite depth below the underplate and also for the case of a finite depth (down to the asthenosphere). It is shown that these solutions lead to simple approximations for when the transient surface heat flow is at its maximum, what the maximum is, and for how long the transient lasts. Even though these solutions assume that the underplate is emplaced instantaneously, they are useful in the interpretation of underplating over finite time spans. A numerical scheme is suggested for the modelling of underplating that handles both short time intervals as well as long intervals. The scheme treats magmatic underplating in a mass and energy conservative manner, and it is compared against the analytical solutions. Finally, the analytical and numerical results for thermal transients are applied to a transect from the Vøring margin (NE Atlantic), with respect to various degrees of early Cenozoic magmatic intrusion. It appears that more than half of the lower crustal body (LCB) in the Vøring margin must be magmatic underplating for the vitrinite reflectance to be substantially higher than for the non-magmatic case, where the LCB is assumed to comprise Caledonian crust.     

Rainfall-induced landslide event of May 2010 in the eastern part of the Czech Republic

More than 150 landslides originated in the eastern part of the Czech Republic (region of the Flysch Outer Western Carpathians—hereinafter, OWC) due to soil saturation caused by antecedent precipitation and long lasting and intensive rainfalls on 16–18 May 2010 (>300 mm as measured by some stations). As a consequence, a multitude of small failures originated 88% of which was smaller than 10⁴ m². Most landslides are characterised as shallow (<10 m) or middle–deep (10–30 m) incipient (rather short travel) landslides, debris slides and soil slips spatially clustered to a geological domain underlain by rather weak thin-bedded flysch and unconsolidated Quaternary deposits. An exception to this is represented by a kilometre-long rockslide (∼2–3 mil m³) affecting tectonically weakened and weathered claystone/mudstone-dominated flysch on the southern slope of Mt. Girová (the Beskydy Mountains). The rockslide is one of the largest long runout landslides in the territory of the Czech Republic activated over the past few decades as it reaches the dimensions of the largest documented Holocene long runout landslides in the Czech part of the OWC. A majority of the May 2010 landslide events developed inside older (Holocene or historic) landslide terrains, which points to their spatial persistency and recurrent nature. In spite of the fact that the May 2010 landslide event was not as destructive as some previous landslide activisation in the OWC region (e.g. July 1997 event), it left many slope failures at the initial stage of their potential future reactivation.     

Trust relationships between fishers and government: New challenges for the co-management arrangements in the Dutch flatfish industry

Until the 1990s fisheries were largely managed by the state. Since then, Dutch government and the sector increasingly recognized that a fishing industry cannot be managed effectively without the cooperation and participation of fishers to formulate policy and to implement and enforce laws and regulations. As a result, in the nineties, the existing neo-corporatist arrangement was replaced by a co-management system in the Dutch flatfish fishery. Co-management is often seen as leading to greater procedural legitimacy and subsequently compliance. However, constructing an effective co-management arrangement is not only a matter of building institutions but also a matter of building trust relations between the government and industry. Institutional arrangements such as co-management can contribute to these trust building processes; however, a too strong reliance on institutional arrangements can lead to distrust when new challenges are being faced and institutional arrangements fail to adapt to these changes.     

Covariance among North Sea ecosystem state indicators during the past50 years — Contrasts between coastal and open waters

Regime shift and principal component analysis of a spatially disaggregated database capturing time-series of climatic, nutrient and plankton variables in the North Sea revealed considerable covariance between groups of ecosystem indicators. Plankton and climate time-series span the period 1958–2003, those of nutrients start in 1980. In both regions, the period from 1989 to 2001 identified in principal component 1 had warmer surface waters, higher Atlantic inflow and stronger winds, than the periods before or after. However, it was preceded by a regime shift in both open (PC2) and coastal (PC3) waters during 1977 towards more hours of sunlight and higher water temperature, which lasted until 1997. The relative influence of nutrient availability and climatic forcing differed between open and coastal North Sea regions. Inter-annual variability in phytoplankton dynamics of the open North Sea was primarily regulated by climatic forcing, specifically by sea surface temperature, Atlantic inflow and co-varying wind stress and NAO. Coastal phytoplankton variability, however, was regulated by insolation and sea surface temperature, as well as Si availability, but not by N or P. Regime shifts in principal components of hydrographic and climatic variables (explaining 55 and 61% of the variance in coastal and open water variables) were detected using Rodionov's sequential t-test. These shifts in hydroclimatic variables which occurred around 1977, 1989, 1997 and 2001, were synchronized in open and coastal waters, and were tracked by open water chlorophyll and copepods, but not by coastal plankton. North–central–south or open-coastal spatial breakdowns of the North Sea explained similar amounts of variability in most ecosystem indicators with the exception of diatom abundance and chlorophyll concentration, which were clearly better explained using the open-coastal configuration.     

Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.