Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10^?6to 3 × 10^?5 moles 1^?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1^?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.     

Numerical modeling of two-phase hysteresis combined with an interface condition for heterogeneous porous media

This paper presents a numerical implementation of two-phase capillary hysteresis and its combination with a capillary interface condition for the treatment of heterogeneities. The hysteresis concepts chosen in this work are first implemented in a node-centered FV discretization scheme and subsequently combined with the interface condition that predicts sharp saturation discontinuities at material interfaces, based on a pressure equilibrium concept. This approach allows for the approximation of history-dependent, and at the same time discontinuous, saturations at material interfaces. The resulting model provides a well-defined evolution of the hysteretic capillary pressure–saturation relationships at material interfaces that is independent of the grid spacing. As demonstrated with a simple 1-D example, this concept therefore offers the advantage that the solution of a two-phase flow problem involving hysteresis does not relate to the grid resolution at the material interfaces.     

Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Node-centered finite volume discretizations for the numerical simulation of multiphase flow in heterogeneous porous media

Three node-centered finite volume discretizations for multiphase porous media flow are presented and compared. By combination of these methods two additional discretization methods are generated. The ability of these schemes to describe flows at textural interfaces of different geologic formations is investigated. It was found that models with nonzero-entry pressures for the capillary pressure-saturation relationship in conjunction with the Box discretization may give rise to spurious oscillations for flows around low permeable lenses. Furthermore, the applicability and sensitivity of the discretization methods with regard to the used computational grids is discussed. The schemes are used for the numerical study of two-phase flow in porous media with zones of different material properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

Growth rates of monomineralic, polycrystalline åkermanite (Ca₂MgSi₂O₇) rims produced by solid-state reactions between monticellite (CaMgSiO₄) and wollastonite (CaSiO₃) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10^?15.8±0.1 m² s^?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E _a = 204 ± 18 kJ/mol and D ₀ = 10^?8.6±1.6 m² s^?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO₂ binary system, where grain boundary diffusion controls rim growth.     

It starts at home? Climate policies targeting household consumption and behavioral decisions are key to low-carbon futures

Through their consumption behavior, households are responsible for 72% of global greenhouse gas emissions. Thus, they are key actors in reaching the 1.5 °C goal under the Paris Agreement. However, the possible contribution and position of households in climate policies is neither well understood, nor do households receive sufficiently high priority in current climate policy strategies. This paper investigates how behavioral change can achieve a substantial reduction in greenhouse gas emissions in European high-income countries. It uses theoretical thinking and some core results from the HOPE research project, which investigated household preferences for reducing emissions in four European cities in France, Germany, Norway and Sweden. The paper makes five major points: First, car and plane mobility, meat and dairy consumption, as well as heating are the most dominant components of household footprints. Second, household living situations (demographics, size of home) greatly influence the household potential to reduce their footprint, even more than country or city location. Third, household decisions can be sequential and temporally dynamic, shifting through different phases such as childhood, adulthood, and illness. Fourth, short term voluntary efforts will not be sufficient by themselves to reach the drastic reductions needed to achieve the 1.5 °C goal; instead, households need a regulatory framework supporting their behavioral changes. Fifth, there is a mismatch between the roles and responsibilities conveyed by current climate policies and household perceptions of responsibility. We then conclude with further recommendations for research and policy.     

Late Glacial ice advances in southeast Tibet

The sensitivity of Tibetan glacial systems to North Atlantic climate forcing is a major issue in palaeoclimatology. In this study, we present surface exposure ages of erratic boulders from a valley system in the Hengduan Mountains, southeastern Tibet, showing evidence of an ice advance during Heinrich event 1. Cosmogenic nuclide analyses (¹⁰Be and ²¹Ne) revealed consistent exposure ages, indicating no major periods of burial or pre-exposure. Erosion-corrected (3 mm/ka) ¹⁰Be exposure ages range from 13.4 to 16.3 ka. This is in agreement with recalculated exposure ages from the same valley system by [Tschudi, S., Schäfer, J.M., Zhao, Z., Wu, X., Ivy-Ochs, S., Kubik, P.W., Schlüchter, C., 2003. Glacial advances in Tibet during the Younger Dryas? Evidence from cosmogenic ¹⁰Be, ²⁶Al, and ²¹Ne. Journal of Asian Earth Sciences 22, 301–306.]. Thus this indicates that local glaciers advanced in the investigated area as a response to Heinrich event 1 cooling and that periglacial surface adjustments during the Younger Dryas overprinted the glacial morphology, leading to deceptively young exposure ages of certain erratic boulders.     

Sedimentary evolution of a late Pleistocene wetland indicating extreme coastal uplift in southern Tanzania

Facies analyses of Pleistocene deposits from southern coastal Tanzania (Lindi District) document that sediments formed in a wetland evolving on a coastal terrace in the Lindi Fracture Zone foreland. The exposed succession shows a marked sedimentary change from tidal to terrestrial facies. ¹⁴C analyses on gastropod shells indicate the emergence of the Lindi coast at ∼ 44 ¹⁴C ka BP. Emergence and subsequent elevation of terraces to 21 m above present-day sea level was linked to the falling eustatic sea level prior to the last glacial maximum, and to a periodic elevation due to extensional tectonic episodes in the eastern branch of the East African Rift System (EARS). Since ∼ 44 ¹⁴C ka BP tectonic uplift at the coast was 80-110 m, comparable to that in the extreme uplift areas of the EARS.     

A diverse Pleistocene marsupial trackway assemblage from the Victorian Volcanic Plains,Australia

A diverse assemblage of late Pleistocene marsupial trackways on a lake bed in south-western Victoria provides the first information relating to the gaits and morphology of several megafaunal species, and represents the most speciose and best preserved megafaunal footprint site in Australia. The 60–110 ka volcaniclastic lacustrine sedimentary rocks preserve trackways of the diprotodontid Diprotodon optatum, a macropodid (probably Protemnodon sp.) and a large vombatid (perhaps Ramsayia magna or ‘Phascolomys’ medius) and possible prints of the marsupial lion, Thylacoleo carnifex. The footprints were imprinted within a short time period, demonstrating the association of the taxa present, rather than the time-averaged accumulations usually observed in skeletal fossil deposits. Individual manus and pes prints are distinguishable in some trackways, and in many cases some digital pad morphology is also present. Several parameters traditionally used to differentiate ichnotaxa, including trackway gauge and the degree of print in-turning relative to the midline, are shown to be subject to significant intraspecific variation in marsupials. Sexual dimorphism in the trackway proportions of Diprotodon, and its potential for occurrence in all large bodied, quadrupedal marsupials, is identified here for the first time.     

The Glarus thrust: excursion guide and report of a field trip of the Swiss Tectonic Studies Group (Swiss Geological Society, 14.–16. 09. 2006)

This excursion guide results form a field trip to the Glarus nappe complex organized by the Swiss Tectonic Studies Group in 2006. The aim of the excursion was to discuss old and recent concepts related to the evolution of the Glarus thrust. The major aspects were (i) the interplay between deformation, fluid flow and geochemical alteration, (ii) episodic versus continuous deformation and fluid flow, and (iii) the link between large-scale structures, microstructures, and geochemical aspects. Despite 150 years of research in the Glarus nappe complex and the new results discussed during the excursion, there exist controversies that still are unsolved.