Application of a mixing-ratios based formulation to model mixing-driven dissolution experiments

We address the question of how one can combine theoretical and numerical modeling approaches with limited measurements from laboratory flow cell experiments to realistically quantify salient features of complex mixing-driven multicomponent reactive transport problems in porous media. Flow cells are commonly used to examine processes affecting reactive transport through porous media, under controlled conditions. An advantage of flow cells is their suitability for relatively fast and reliable experiments, although measuring spatial distributions of a state variable within the cell is often difficult. In general, fluid is sampled only at the flow cell outlet, and concentration measurements are usually interpreted in terms of integrated reaction rates. In reactive transport problems, however, the spatial distribution of the reaction rates within the cell might be more important than the bulk integrated value. Recent advances in theoretical and numerical modeling of complex reactive transport problems [De Simoni M, Carrera J, Sanchez-Vila X, Guadagnini A. A procedure for the solution of multicomponent reactive transport problems. Water Resour Res 2005;41:W11410. doi: 10.1029/2005WR004056, De Simoni M, Sanchez-Vila X, Carrera J, Saaltink MW. A mixing ratios-based formulation for multicomponent reactive transport. Water Resour Res 2007;43:W07419. doi: 10.1029/2006WR005256] result in a methodology conducive to a simple exact expression for the space–time distribution of reaction rates in the presence of homogeneous or heterogeneous reactions in chemical equilibrium. The key points of the methodology are that a general reactive transport problem, involving a relatively high number of chemical species, can be formulated in terms of a set of decoupled partial differential equations, and the amount of reactants evolving into products depends on the rate at which solutions mix. The main objective of the current study is to show how this methodology can be used in conjunction with laboratory experiments to properly describe the key processes that occur in a complex, geochemically-active system under chemical equilibrium conditions. We model three CaCO₃ dissolution experiments reported in Singurindy et al. [Singurindy O, Berkowitz B, Lowell RP. Carbonate dissolution and precipitation in coastal environments: Laboratory analysis and theoretical consideration. Water Resour Res 2004;40:W04401. doi: 10.1029/2003WR002651, Singurindy O, Berkowitz B, Lowell RP. Correction to Carbonate dissolution and precipitation in coastal environments: laboratory analysis and theoretical consideration. Water Resour Res 2005;41:W11701. doi: 10.1029/2005WR004433], in which saltwater and freshwater were mixed in different proportions. The integrated reaction rate within the cell estimated from the experiments are modeled independently by means of (a) a state-of-the-art reactive transport code, and (b) the uncoupled methodology of [12, 13], both of which use dispersivity as a single, adjustable parameter. The good agreement between the results from both methodologies demonstrates the feasibility of using simple solutions to design and analyze laboratory experiments involving complex geochemical problems.     

Short-term effects of changes in water management on the limnological characteristics and zooplankton of a eutrophic Mediterranean coastal lagoon (NE Iberian Peninsula)

The Ter Vell (NE Iberian Peninsula) is a eutrophic coastal lagoon which has been flooded by the excess irrigation water and the agricultural runoff during the last decades. Between 1999 and 2003, restoration measures were applied to improve its water quality. At the same time, but independently, agricultural water management drastically reduced the freshwater inflow. The short-term effects of these management actions on the limnological characteristics of the lagoon were analysed by comparing two hydrological cycles, one before (1999/2000) and the other one after (2002/2003) the actions. The two cycles are illustrative of opposite situations in the hydrological functioning of coastal wetlands. In the first, the lagoon was exorheic, with prolonged flooding periods and a low residence time; in the second, it had a more endorheic character, with scarce water inputs and prolonged periods of confinement. Consequently, nitrogen inputs diminished and organic load and salinity increased as the internal loading and the accumulation effects became more relevant. These effects were actually caused by the drastic reduction in the freshwater inflow which prevented, in turn, the success of the restoration measures. The zooplankton community of the Ter Vell lagoon was not significantly altered by the hydrological change, at least in the short-term, and rotifers and cladocerans, mainly those species indicative of eutrophy, dominated the community.     

Plurigaussian modeling of geological domains based on the truncation of non-stationary Gaussian random fields

The plurigaussian model is used in mining engineering, oil reservoir characterization, hydrology and environmental sciences to simulate the layout of geological domains in the subsurface, while reproducing their spatial continuity and dependence relationships. However, this model is well-established only in the stationary case, when the spatial distribution of the domains is homogeneous in space, and suffers from theoretical and practical impediments in the non-stationary case. To overcome these limitations, this paper proposes extending the model to the truncation of intrinsic random fields of order k with Gaussian generalized increments, which allows reproducing spatial trends in the distribution of the geological domains. Methodological tools and algorithms are presented to infer the model parameters and to construct realizations of the geological domains conditioned to existing data. The proposal is illustrated with the simulation of rock type domains in an ore deposit in order to demonstrate its applicability. Despite the limited number of conditioning data, the results show a remarkable agreement between the simulated domains and the lithological model interpreted by geologists, while the conventional stationary plurigaussian model turns out to be unsuccessful.     

Interaction of multiple ice streams on the Malin Shelf during deglaciation of the last British–Irish Ice Sheet

The Malin Shelf, off north-west Ireland, was an important zone of confluence for marine-based ice streams of the former British–Irish Ice Sheet (BIIS). Legacy geophysical datasets are used to construct models of the seismic character, relative age and distribution of shelf sediments and landforms. Buried and surface landform assemblages provide evidence that during deglaciation of the Late Devensian BIIS, the region was occupied not by a single Hebrides Ice Stream as previously proposed, but by four discrete ice streams, here referred to as the Sea of the Hebrides (SHIS), Inner Hebrides, North Channel and Tory Island ice streams. Our observations of stratigraphic relationships between the deposits of these ice streams indicate physical interactions between them during shelf deglaciation. We interpret an initial dominant cross-shelf flow along the SHIS impeding cross-shelf ice flow from other ice sheet sectors. Following withdrawal of the SHIS grounding line from the shelf edge to mid-shelf bathymetric highs during deglaciation, a reconfiguration of ice sheet flow paths allowed the expansion of smaller cross-shelf ice streams draining central Scotland and north-western Ireland. This internal dynamic behaviour provides a possible physical analogue for time-transgressive flow patterns reported for outlets draining the West Antarctic Ice Sheet.     

Air masses and aerosols chemical components in the free troposphere at the subtropical northeast atlantic region

The dynamics and the aerosol chemistry of the air masses reaching the free troposphere of the subtropical Northeast Atlantic region during the period 1995–98 have been studied. Seven days backward trajectories were calculated daily with HYSPLIT-4 model for Izaña Global Atmospheric Watch (GAW) Observatory (28.3^°N 16.5^°W, 2367 m a.s.l.). These back-trajectories were classified by means of a k-means clustering strategy. The daily air masses have been coded using 16 variables to detect the aerosol load of each one of them. Four clusters were found: Cluster 1, representative of Atlantic oceanic middle troposphere air masses, (OMT), has an average frequency of occurrence of 50.6%. Cluster 2, which includes air masses originated in the African continent (AfD), has been recorded in a 19.8% of time. Cluster 3 represents a mixture at least of two of the next sources: Europe, Africa and Ocean, (EAM), with a frequency of 12.7%. Finally, Cluster 4 includes air masses with a high load of maritime aerosols, (MaA), and it has been detected in a 16.9%. An analysis of four aerosol components: NO₃ ^?, NH₄ ⁺, non-sea-salt-SO₄ ^2?, and mineral dust and its relation with the origin and transport of the air masses have been done. The highest quantities of mineral dust and nss-SO₄ ^2? are linked with African air masses with a mean value of 86.5 and 1.9 μg/m³ respectively. Whereas the highest levels of NO₃ ^?, 1.0 μg/m³, and NH₄ ⁺, 0.4 μg/m³, were obtained for AfD and EAM. The lowest levels were associated with OMT and MaA air masses types: 12.7, 0.6, 0.2, and 0.5 μg/m³ for dust, NO₃ ^?, NH₄ ⁺, and nss-SO₄ ^2? in average for the four studied years. However, it is remarkable that the values of the median for dust are 2.2 and 3.5 μg/m³ in clusters MaA and OMT respectively. Using non-parametric statistical tests the distributions of concentrations in each cluster by year have been compared in order to detect similarities. The results show that the aerosol loads of OMT and MaA air masses are quite similar and the same occurs for AfD and EAM air masses. However, the correlation analysis between the levels of anions and ammonium evidenced important differences among the air mass types. In AfD air masses is clear a low correlation between levels of nss-SO₄ ^2? and NH₄ ⁺ (r ² = 0.08) suggesting that the sulfate speciation was dominated by sulfate species others than ammonium sulfate, such as calcium sulfate. CaSO₄ ?2H₂O (gypsum) is mainly present in the coarse mode, where the radiative effects of sulfate are less important that in the accumulative mode. For OMT air masses is noticeable an important increasing on the correlation between the levels of anions and those of NH₄ ⁺ for the two last years of the study period (1997–1998, r ² = 0.61 –0.85%) with respect to the first ones (1995–1996, r ² = 0.25–0.49%), coinciding with the second strongest ENSO (El Niño Southern Oscillation) event recorded. This behavior indicates a change in the speciation of the aerosol component.     

Current and future atmospheric circulation at 500 hPa over Greenland simulated by the CMIP3 and CMIP5 global models

The Greenland ice sheet is projected to be strongly affected by global warming. These projections are either issued from downscaling methods (such as Regional Climate Models) or they come directly from General Circulation Models (GCMs). In this context, it is necessary to evaluate the accuracy of the daily atmospheric circulation simulated by the GCMs, since it is used as forcing for downscaling methods. Thus, we use an automatic circulation type classification based on two indices (Euclidean distance and Spearman rank correlation using the daily 500 hPa geopotential height) to evaluate the ability of the GCMs from both CMIP3 and CMIP5 databases to simulate the main circulation types over Greenland during summer. For each circulation type, the GCMs are compared to three reanalysis datasets on the basis of their frequency and persistence differences. For the current climate (1961–1990), we show that most of the GCMs do not reproduce the expected frequency and the persistence of the circulation types and that they simulate poorly the observed daily variability of the general circulation. Only a few GCMs can be used as reliable forcings for downscaling methods over Greenland. Finally, when applying the same approach to the future projections of the GCMs, no significant change in the atmospheric circulation over Greenland is detected, besides a generalised increase of the geopotential height due to a uniform warming of the atmosphere.     

Understanding fracture distribution and its relation to knickpoint evolution in the Rio Icacos watershed (Luquillo Critical Zone Observatory,Puerto Rico) using landscape-scale hydrogeophysics

The Rio Icacos watershed in the Luquillo Mountains (Puerto Rico) is unique due to its extremely rapid weathering rates. The watershed is incised into a quartz diorite that has developed a large knickzone defining the river profile. Regolith thickness within the watershed generally decreases from 20 to 30 m at the ridges to several meters in the quartz diorite-dominated valley to tens of centimeters near the major river knickpoint, as determined from previous studies. Above the knickzone, we observe spheroidal corestones, but below this weathering is much less apparent. Measured erosion rates from previous studies are also high in the knickzone compared with upper elevations within the river profile. A suite of near-surface geophysical methods (i.e. ground penetrating radar and terrain conductivity) capable of fast data acquisition in rugged landscapes, was deployed at kilometer scales to characterize critical zone structure. Concentrations of chaotic ground penetrating radar (GPR) reflections and diffraction hyperbolas with low electrical conductivity were observed in vertical zones that outcrop at the land surface as areas of intense fracturing and spheroidally weathered corestones. The width of these fractured and weathered zones showed an increase with proximity to the knickpoint, and was attributed to dilation of these sub-vertical fractures near the knickpoint, as postulated theoretically by a stress model calculated for the topographic variability across the knickzone in the Rio Icacos, and that shows a release of compressive stress near the knickpoint. We hypothesize that erosion rates increase in the knickzone because of this inferred dilation of fractures. Specifically, opened fractures could enhance access of water and in turn promote spalling, erosion, and spheroidal weathering. This study shows that ground-based hydrogeophysical methods used at the landscape-scale (traditionally applied at smaller scales) can be used to explore critical zone architecture at the scales needed to explain the extreme variability in erosion rates across river profiles. © 2018 John Wiley & Sons, Ltd.     

Nankai Trough and Zenisu Ridge: a deep-sea submersible survey

Eight submersible dives between 3000 and 4200 m water depth were made off southern Japan in the eastern Nankai subduction zone. Benthic communities associated with chemosynthetic processes were discovered along the 800 m wide active tectonic zone, at the toe of the accretionary prism. A benthic community was also discovered along a zone of active compression, at the foot of Zenisu Ridge, 30 km south of Nankai Trough. Temperature measurements within the sediments below the benthic communities confirm that upward motion of interstitial water occurs there. Studies of water samples indicate advection of methane and light hydrocarbons. Specimens of the benthic community have been shown to have included in their shells carbonate resulting from methane consumption. Thus the benthic communities are related to overpressure-driven fluid advection along tectonic zones with active surface deformation. A 300 m high active scarp at the toe of the accretionary prism is related to relative motion in a 280° direction which is close to the 305° average direction of subduction in this area. The dives establish further that compressive deformation is presently occurring at the foot of Zenisu Ridge. The previous interpretation of the Zenisu Ridge as a zone of recent north-south intraplate shortening, 40 km south of the Nankai Trench, is confirmed. We conclude that tectonic evolution might well lead to future detachment of the Zenisu Ridge and overthrusting of this large piece of oceanic crust over the continental margin. Such a process might be an efficient one to emplace ophiolites over continents.     

Conditional Simulation of Nongaussian Random Functions

This paper presents a conditional simulation procedure that overcomes the limits of gaussian models and enables one to simulate regionalized variables with highly asymmetrical histograms or with partial or total connectivity of extreme values. The philosophy of the method is similar to that of sequential indicator technique, but it is more accurate because it is based on a complete bivariate model by means of an isofactorial law. The resulting simulations, which can be continuous or categorical, not only honor measured values at data points, but also reproduce the mono and bivariate laws of the random function associated to the regionalized variable, that is, every one or two-point statistic: histogram, variogram, indicator variograms. The sequential isofactorial method can also be adapted to conditional simulation of block values, without resorting to point–support simulations.