Numerical estimation of effective diffusion coefficients for charged porous materials based on micro-scale analyses

In order to describe diffusive transport of solutes through a porous material, estimation of effective diffusion coefficients is required. It has been shown theoretically that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by the tortuosity (tensor) (Bear, 1988 [1]). Given detailed information of the pore geometry at the micro-scale the tortuosity of different materials can be accurately estimated using homogenization procedures. However, many engineering materials (e.g., clays and shales) are characterized by electrical surface charges on particles of the porous material which strongly affect the (diffusive) transport properties of ions. For these type of materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying micro-scale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters (Jougnot et al., 2009; Pivonka et al., 2009; Revil and Linde, 2006 2, 3 and 4). In this paper we employ a recently proposed up-scaled Poisson–Nernst–Planck type of equation (PNP) and its micro-scale counterpart to estimate effective ion diffusion coefficients in thin charged membranes. We investigate a variety of different pore geometries together with different surface charges on particles. Here, we show that independent of the charges on particles, a (generalized) tortuosity factor can be identified as function of the pore morphology only using the new PNP model. On the other hand, all electro-static interactions of ions and charges on particles can consistently be captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this formulation allows to consistently take into account electrochemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations.     

Rapid growth of an Archean continent by arc magmatism

The voluminous Meso- to Neoarchean rocks exposed in the Beartooth Mountains of the northern Wyoming Province of western North America comprise the Long Lake Magmatic Complex (LLMC), a variably metamorphosed and deformed association of igneous and meta-igneous plutonic rocks with SiO₂ ranging from at least 52 to 78 wt%. Within this compositional range, rock types include lineated amphibolites to hornblende-bearing gneisses of intermediate composition and multiple generations of foliated to unfoliated granitoids. Emplacement ages range between approximately 2.79 and 2.83 Ga, based on U–Pb zircon geochronology (SHRIMP). Field relations, elemental compositions, and geochronology indicate that these rocks do not represent a single fractional crystallization sequence, but rather, the LLMC was constructed by injection of numerous, discrete magmas as sill-like bodies over an ∼40 Ma period. Although there is a continuum of compositions in the LLMC, trace element abundances can be used to distinguish distinct sources and petrogenetic processes that can be broadly extrapolated to at least 3 compositional groupings: (1) trondhjemitic to granitic intrusive rocks with SiO₂ >70 wt%, (2) variably metamorphosed granodioritic orthogneisses with SiO₂ between 63 and 70 wt%, and (3) amphibole-bearing mafic to intermediate gneisses with SiO₂ between 52 and 63 wt%. Despite the range of SiO₂ contents, maximum LREE abundances are similar across the compositional range and, consequently, exhibit a wide range of (La/Yb)_n ratios (∼20–130). All LLMC rocks share a relative depletion in HFSE abundances similar to modern convergent margin magmas. Initial Sr and Nd isotopic compositions across the compositional range are consistently offset from typical bulk silicate earth (BSE) values and preclude unaltered derivation from primitive or depleted mantle. Common Pb isotopic data define a single array that lies above model crustal growth curves and, along with the Nd and Sr data, suggest relatively uniform interaction with, or derivation from, older lithosphere. The combined isotopic and elemental data suggest the LLMC resulted from simultaneous, rapid, and voluminous production of diverse magmas that represent melting of isotopically similar, but compositionally distinct, crustal and mantle sources. Dynamically, Meso- to Neo-archean crustal growth in the northern Wyoming Province appears to require an environment similar to a modern ocean–continent convergent margin with a comparable rate of crustal production and diversity of magma series. The resultant crust and associated mantle lithosphere (keel) appear to have suffered little-to-no modification prior to Laramide (Cretaceous) uplift and exposure.     

An EPR study of native radiation-induced paramagnetic defects in sudoite (di–trioctahedral Al–Mg chlorite) from the alteration halo related to unconformity-type uranium deposits

Natural radiation-induced defects were identified in specimens of sudoite (Al–Mg di-trioctahedral chlorite) related to unconformity-type uranium deposits at the base of the Athabasca Group (Saskatchewan, Canada), using electron paramagnetic resonance (EPR) spectroscopy at X- and Q-band frequencies. X-band spectra indicate the presence of a main native defect, named the A_s-center, whose EPR signal is dominated by an axially distorted spectrum with apparent principal components as follows: g _// = 2,051 and g _⊥ = 2,005, and a secondary defect with apparent component g = 2,025. The study of oriented specimens shows that the main defect has its g _// component perpendicular to the (ab) plane of sudoite. The A_s-center corresponds to an electron hole located on oxygen atoms of the structure and is likely associated with Si, according to the lack of hyperfine structure. The A_s-center in sudoite has EPR parameters similar to the A-center in kaolinite and dickite, and the A_i-center in illite. The saturation behavior of EPR spectra as a function of power demonstrates that native defects of sudoite are different from those known in other clays, such as kaolinite, dickite or smectite, but are similar to those of illite. The isochronal annealing data suggest that the main defect in sudoite is stable to more than 300°C. The corresponding defects characterized in sudoite may have the potential for tracing past radionuclide migration around unconformity-type uranium deposits.     

Assessing the response of watersheds to catastrophic (logging) and possible secular (global temperature change) perturbations using sediment-chemical chronologies

Geochemical profiles of sediment cores from two oligotrophic lakes (Elk and Mullett) in northern Lower Michigan were studied to examine the response and recovery of watersheds to large-scale logging that occurred between 1850 and 1920. Specific questions addressed were: can the impact of extensive clear-cutting of forests be recognized in the sediment-chemical chronologies, can states of system stability be identified prior to the logging, and are there indications that the systems are recovering and possibly returning to a stable state? To answer these questions, elements were put into four groups as proxies for watershed runoff or export (e.g., Al, Mg), pollution (e.g., Pb, Cu), redox (e.g., Fe, As), and productivity (e.g., Ca, P). It was observed that vertical patterns of all proxies were influenced by logging and the early increases in concentration of pollution proxies were due to increased watershed export, not pollution. System stability might be recognized by relatively symmetrical vertical patterns among all of the proxies or secular changes of slowly increasing or decreasing vertical concentration trajectories. Some pre-logging trajectories were punctuated by episodes of slightly elevated concentrations that appear to be related to comparatively warmer periods during the Little Ice Age. Iron and Mn enrichments caused by increased watershed runoff might be misinterpreted as paleo-redox horizons. Results are interpreted to indicate that (1) reference conditions may be better defined as the temporal trends among proxy groups and not individual concentrations, (2) simply assuming pre-1800 conditions as a reference may not be appropriate, (3) inter-proxy group comparisons are needed to help for interpretations of intra-proxy group patterns, (4) the possible regime shift identified here might be expected for other ecosystems because of the intensity of human disturbances and secular changes, and (5) without consideration of a possible regime shift, recovery from logging is estimated to be on the order of 75–130 a, but shorter if regime shifts are considered.     

Simultaneous quantification of dissolved organic carbon fractions and copper complexation using solid-phase extraction

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.     

Solar shield: forecasting and mitigating space weather effects on high-voltage power transmission systems

In this paper, central elements of the Solar Shield project, launched to design and establish an experimental system capable of forecasting the space weather effects on high-voltage power transmission system, are described. It will be shown how Sun–Earth system data and models hosted at the Community Coordinated Modeling Center (CCMC) are used to generate two-level magnetohydrodynamics-based forecasts providing 1–2 day and 30–60 min lead-times. The Electric Power Research Institute (EPRI) represents the end-user, the power transmission industry, in the project. EPRI integrates the forecast products to an online display tool providing information about space weather conditions to the member power utilities. EPRI also evaluates the economic impacts of severe storms on power transmission systems. The economic analysis will quantify the economic value of the generated forecasting system. The first version of the two-level forecasting system is currently running in real-time at CCMC. An initial analysis of the system’s capabilities has been completed, and further analysis is being carried out to optimize the performance of the system. Although the initial results are encouraging, definite conclusions about system’s performance can be given only after more extensive analysis, and implementation of an automatic evaluation process using forecasted and observed geomagnetically induced currents from different nodes of the North American power transmission system. The final output of the Solar Shield will be a recommendation for an optimal forecasting system that may be transitioned into space weather operations.     

A field study (Massachusetts, USA) of the factors controlling the depth of groundwater flow systems in crystalline fractured-rock terrain

Groundwater movement and availability in crystalline and metamorphosed rocks is dominated by the secondary porosity generated through fracturing. The distributions of fractures and fracture zones determine permeable pathways and the productivity of these rocks. Controls on how these distributions vary with depth in the shallow subsurface (<300 m) and their resulting influence on groundwater flow is not well understood. The results of a subsurface study in the Nashoba and Avalon terranes of eastern Massachusetts (USA), which is a region experiencing expanded use of the fractured bedrock as a potable-supply aquifer, are presented. The study logged the distribution of fractures in 17 boreholes, identified flowing fractures, and hydraulically characterized the rock mass intersecting the boreholes. Of all fractures encountered, 2.5% are hydraulically active. Boreholes show decreasing fracture frequency up to 300 m depth, with hydraulically active fractures showing a similar trend; this restricts topographically driven flow. Borehole temperature profiles corroborate this, with minimal hydrologically altered flow observed in the profiles below 100 m. Results from this study suggest that active flow systems in these geologic settings are shallow and that fracture permeability outside of the influence of large-scale structures will follow a decreasing trend with depth.     

A Decade of Change in the Skidaway River Estuary. III. Plankton

The Skidaway River estuary, GA (USA), a tidally dominated subtropical system surrounded by extensive Spartina salt marshes, is experiencing steady increases in nutrients, chlorophyll, and particulate matter and decline in dissolved oxygen, associated with cultural eutrophication. A long-term study is documenting changes in these parameters: previous papers Verity (Estuaries 25:944–960, 2002a, Estuaries 25:961–975, b) reported on hydrography, nutrients, chlorophyll, and particulate matter during 1986–1996; plankton community responses are reported here. Phytoplankton, bacteria, heterotrophic nanoplankton and dinoflagellates, ciliates, and copepods exhibited strong seasonal cycles in abundance driven by temperature and resource availability, typically with summer maxima and winter minima. However, cultural eutrophication coincided with altered planktonic food webs as autotrophic and heterotrophic communities responded to increasing concentrations and changing ratios of inorganic and organic nutrients, potential prey, and predators. Small (<8 μm) photosynthetic nanoplankton increased in absolute concentration and also relative to larger cells. In contrast, diatoms did not show consistent increases in abundance, despite significant long-term increases in ambient silicate concentrations. Mean annual bacteria concentrations approximately doubled, and eukaryotic organisms in the microbial food web (heterotrophic and mixotrophic flagellates, dinoflagellates, ciliates, and metazoan zooplankton) also increased. All plankton groups except copepods showed trends of increasing annual amplitudes between seasonal high and low values, with higher peak concentrations each year. These observations suggest that the eutrophication signal was gradually becoming uncoupled from regulatory mechanisms. Theory and evidence from other more impacted waters suggest that, if these patterns continue, changes in the structure and function of higher trophic levels will ensue.