Bicontinuous and mixed gels in binary mixtures of patchy colloidal particles

We investigate the thermodynamics and percolation regimes of model binary mixtures of patchy colloidal particles. The particles of each species have three sites of two types, one of which promotes bonding of particles of the same species while the other promotes bonding of different species. We find up to four percolated structures at low temperatures and densities: two gels where only one species percolates, a mixed gel where particles of both species percolate but neither species percolates separately, and a bicontinuous gel where particles of both species percolate separately forming two interconnected networks. The competition between the entropy and the energy of bonding drives the stability of the different percolating structures. Appropriate mixtures exhibit one or more connectivity transitions between the mixed and bicontinuous gels, as the temperature and/or the composition changes.

Poder poluente de águas residuárias de suinocultura após utilização de um tratamento integrado

Em experimento de campo, avaliou-se o potencial de impacto ambiental de águas residuárias de suinocultura, acondicionadas em um tanque de estocagem, com distintos tempos de retenção hidráulica e aplicadas, posteriormente, em lisímetros preenchidos com solos arenosos, argilosos e de texturas médias. Para tal, foram determinados os valores de pH nos solos e as quantificações das concentrações de zinco e cobre na água residuária in natura e, após os quatro tempos de retenção hidráulica do tanque de estocagem, nos percolados dos lisímetros e nos solos. Os resultados mostram que a estocagem não foi eficiente na redução, aos níveis exigidos pela legislação, das concentrações de zinco e cobre nos efluentes do tanque de estocagem. A aplicação no solo gerou reduções eficientes nas concentrações de zinco e cobre. Por fim, enfocando a contribuição fertilizante destas águas residuárias, o solo argiloso foi o mais beneficiado com este sistema integrado de tratamento, contribuindo para a redução das concentrações de zinco e cobre para valores abaixo dos permitidos pelas legislações, o que protegeria o lençol freático da contaminação por esses dois metais pesados.

Monitoramento sanitário de um sistema integrado de tratamento de águas residuárias da suinocultura

Objective. To assess the potential for contamination of wastewaters from pig farming. Methods. Wastewaters from pig farming were stored in a tank. After 0, 30, 60, 90, and 120 days of hydraulic retention, they were added to lysimeters filled with argillaceous, sandy, or medium soil. Finally, these lysimeters were submitted to simulations of either a rainy season or a dry season. The number of colony-forming units (CFUs) of total coliforms, fecal coliforms, and fecal streptococci was measured in the effluents of the storage tank (for the various periods of hydraulic retention), in the percolate from the lysimeters, and in the three types of soil. The microbiological analyses were carried out using the membrane filter technique. The pH analyses were done potentiometrically. Results. For the three microorganisms, the largest decrease in bacterial counts in the storage tanks occurred with 90 or 120 days of retention. There was a marked decrease in the bacterial count in the percolates of the three soils. For the three soil types the greatest reduction in bacterial counts was found in medium soil, due to its acidity (pH < 7.0). Hydraulic retention was not sufficient to ensure the sanitary adequacy of the wastewaters and their use for irrigation, given that fecal coliform values were above 1 000 CFU per 100 mL. Therefore, adding the residues to the soil was considered a second stage of treatment. Conclusions. The retention of wastewaters followed by adding them to soil was effective in minimizing the contaminating effect of pig farming residues. The storage time for wastewaters from pig farming could be decreased from 120 to 90 days.

CO2 Production of Soil Microbiota in the Presence of Ametryne and Biofertilizer

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Biogeochemistry of an Amazonian podzol-ferralsol soil system with white kaolin

The podzol-ferralsol soil systems, which cover great areas of Amazonia and other equatorial regions, are frequently associated with kaolin deposits and store and export large amounts of carbon. Although natural organic matter (NOM) plays a key role in their dynamics, little is known about their biogeochemistry. In order to assess the specific role of dissolved organic matter (DOM) on NOM storage in deep horizons and to determine possible relationships between kaolin formation and DOM properties, we studied the groundwater composition of a typical podzol-ferralsol soil catena from the Alto Rio Negro region, Brazil. Groundwater was sampled using tension-free lysimeters placed according to soil morphology. DOC, E-H, p(H), and dissolved Si, Al3+, Fe2+, and Fe3+ were analyzed for all samples and values are given in a database. Quantification of other dissolved ions, small carboxylic acids and SUVA(254) index and acid-base microtitration was achieved on selected samples. Part of the DOM produced by the hydromorphic podzols is directly exported to the blackwater streams; another part percolates at greater depth, and more than 90% of it adsorbs in the Bh-Bhs horizons, allowing carbon storage at depth. Humic substances are preferentially adsorbed with regard to small carboxylic compounds. With regard to kaolin genesis, kaolinite precipitation is favored by Al release from NOM mineralization within the Bh-Bhs and kaolin bleaching is ensured by iron reduction due to acidity and relatively low E-H. Fe2+ mobility can be related to small E-H variations and enhanced by the significant concentration of small carboxylic acids. The long-term result of these processes is the thickening of the kaolin, and it can be inferred that kaolin is likely to occur where active, giant podzols are close to a slope gradient sufficient enough to lower the deep water table.

Molekulardynamik-Untersuchungen zur atomistischen Struktur & Dynamik von binären Mischgläsern

Mit Hilfe von Molekulardynamik-Computersimulationen werdenin dieser Arbeit die Struktur und Dynamik von Gläsern undSchmelzen der Systeme 'NSx'=(Na2O)(xSiO2), mit x=2,3,5, und'AS2'=(Al2O3)(2SiO2) untersucht. Zur Beschreibung dermikroskopischen Wechselwirkungen dient ein Modellpotenzial,das auf einem effektiven Paarpotenzial aus der Literaturaufbaut. Simuliert wurden Teilchentrajektorien über mehrereNanosekunden im Bereich 6100 K >= T >= 2100 K sowie dieGlasstruktur bei 100 K (NSx) bzw. 300 K (AS2). Das Aufbrechen der tetraedrischen Netzwerkstruktur durch denNetzwerkmodifikator Na2O führt zur Ausbildung einerzusätzlichen Struktur auf intermediären Längenskalen, diebei allen Systemen NSx etwa dem Abstand übernächster Na-bzw. Si-Nachbarn eines Na-Atoms entspricht. Die diffusiveDynamik ist in allen Systeme NSx bis zu drei Größenordnungenschneller als in SiO2 . Sie nimmt mit wachsenderNa-Konzentration zu. Die Na-Diffusion zeigtArrhenius-Verhalten; hierbei vollführen die Na-Atome einaktiviertes Hüpfen durch eine erstarrte Si-O-Matrix. DieZustandsdichten werden bis ca. 20 THz durch dominanteNa-Moden bestimmt. Bei hohen Frequenzen weichen die für SiO2 typischen intratetraedrischen Si-O-Schwingungsmodenauf.Im Gegensatz zu Na2O wird Al2O3 in die tetraedrischeNetzwerkstruktur eingebunden. AS2 zeigt eine überwiegend ausAlO4- und SiO4-Tetraedern verknüpfte Polyederstruktur, beider sich die AlO4-Tetraeder lokal anders anordnen als dieSiO4-Tetraeder, um Ladungsausgleich zu gewährleisten. Esbilden sich typische 3(Si,Al)O4-Bausteine ('3-Cluster'). Sie führen auf intermediären Längenskalen zur Ausbildungeines Al-reichen perkolierenden Netzwerks, das dieSiO4-Struktur durchdringt. Im Vergleich zu SiO2 erhöht sichdie diffusive Dynamik aller Komponenten in AS2 um ca. zweiGrößenordnungen. Die intratetraedrischenAl-O-Steckschwingungsmoden sind wesentlich weicher als die typischen intratetraedrischen Si-O-Moden des SiO2.

Importance of vegetation, topography and flow paths for water transit times of base flow in alpine headwater catchments

The mean transit time (MTT) of water in a catchment gives information about storage, flow paths, sources of water and thus also about retention and release of solutes in a catchment. To our knowledge there are only a few catchment studies on the influence of vegetation cover changes on base flow MTTs. The main changes in vegetation cover in the Swiss Alps are massive shrub encroachment and forest expansion into formerly open habitats. Four small and relatively steep headwater catchments in the Swiss Alps (Ursern Valley) were investigated to relate different vegetation cover to water transit times. Time series of water stable isotopes were used to calculate MTTs. The high temporal variation of the stable isotope signals in precipitation was strongly dampened in stream base flow samples. MTTs of the four catchments were 70 to 102 weeks. The strong dampening of the stable isotope input signal as well as stream water geochemistry points to deeper flow paths and mixing of waters of different ages at the catchments' outlets. MTTs were neither related to topographic indices nor vegetation cover. The major part of the quickly infiltrating precipitation likely percolates through fractured and partially karstified deeper rock zones, which increases the control of bedrock flow paths on MTT. Snow accumulation and the timing of its melt play an important role for stable isotope dynamics during spring and early summer. We conclude that, in mountainous headwater catchments with relatively shallow soil layers, the hydrogeological and geochemical patterns (i.e. geochemistry, porosity and hydraulic conductivity of rocks) and snow dynamics influence storage, mixing and release of water in a stronger way than vegetation cover or topography do.

Strontium chemistry of anhydrite from DSDP/ODP Hole 504B

A unique record of the chemical evolution of seawater during hydrothermal recharge into oceanic crust is preserved by anhydrite from the volcanic sequences and sheeted dike complex in ODP Hole 504B. Chemical and isotopic analyses 87Sr/86Sr, delta18O, delta34S of anhydrite constrain the changing composition of fluids due to reaction with basalt. There is a general trend of decreasing 87Sr/86Sr of anhydrite, corresponding to the minor incorporation of basaltic strontium with depth in the volcanic rocks. 87Sr/86Sr ratios decrease rapidly with depth in the dikes to values identical to host basalt (0.7029). Sr/Ca ratios (<0.1 mmol/mol) suggest that recharge fluids have very low Sr concentrations and fluids evolve by first precipitating Sr-bearing phases before extensive exchange of Sr with the host basalt. There is a background trend of decreasing sulfate delta18O with depth from +12-13? in the lower volcanics to +7? in the lower sheeted dikes recording an increase in recharge fluid temperature from c. 150° to c. 250°C, and confirming the presence of sulfate in hydrothermal fluids at elevated temperatures. From the amount of anhydrite recovered from Hole 504B and the amount of seawater sulfur that has been reduced to sulfide, a minimum seawater recharge flux can be calculated. This value is 4-25 times lower than estimates of high-temperature fluid fluxes based on either thermal constraints or global chemical budgets and suggests that there is significant deficit of seawater-derived sulfur in the oceanic crust. Only a minor proportion of the seawater that percolates into the crust near the axis is heated to high temperatures and exits as black smoker-type fluids. A significant proportion of the axial heat loss must be advected at 200-250°C by sulfate-bearing hydrothermal solutions that egress diffusely from the crust. These fluids penetrate into the dikes and exchange both heat and chemical tracers without the extensive clogging of porosity by anhydrite precipitation, which would halt hydrothermal circulation for any reasonable fluid flux. The heating of the major proportion of hydrothermal fluids to only moderate temperatures (c. 250°C) reconciles estimates of hydrothermal fluxes derived from thermal models and global geochemical budgets. The flux of hydrothermal sulfate would be of a magnitude similar to the riverine input, and oxygen-isotopic exchange at 200-250°C between dissolved sulfate and recharge fluids during hydrothermal circulation provides a mechanism to continuously buffer seawater sulfate oxygen to the light isotopic composition observed.

Physical properties and alpha-/gamma-HCH concentrations in sea-ice and snow samples obtained during a CCGS Amundsen cruise, eastern Beaufort Sea

The alpha- and gamma-hexachlorocyclohexanes (HCHs) are being scavenged from the atmosphere by falling snow, with the average total scavenging ratios (WT) of 3.8 x 10**4 and 9.6 x 10**3, respectively. After deposition, HCH snow concentrations can decrease by 40% because of snowpack ventilation and increase by 50% because of upward migration of brine from the ice. HCH vertical distribution in sufficiently cold winter sea ice, which maintains brine volume fractions <5%, reflects the ice growth history. Initially, the entrapment of brine (and HCHs) in ice depends on the rates of ice growth and desalination. However, after approximately the first week of ice formation, ice growth rate becomes dominant. Deviations of HCH concentrations from the values predicted by the ice bulk salinity (rate of brine entrapment) can be explained by spatial variability of HCHs in surface water. HCH burden in the majority of the ice column remains locked throughout most of the season until the early spring when snow meltwater percolates into the ice, delivering HCHs to the upper ocean via desalination by flushing. Percolation can lead to an increase in alpha- and gamma-HCH in the sea ice by up to 2%-18% and 4%-32%, respectively.

The behaviour of granular material in pure shear, direct shear and simple shear

In biaxial compression tests, the stress calculations based on boundary information underestimate the principal stresses leading to a significant overestimation of the shear strength. In direct shear tests, the shear strain becomes highly concentrated in the mid-plane of the sample during the test. Although the stress distribution within the specimen is heterogeneous, the evolution of the stress ratio inside the shear band is similar to that inferred from the boundary force calculations. It is also demonstrated that the dilatancy in the shear band significantly exceeds that implied from the boundary displacements. In simple shear tests, the stresses acting on the wall boundaries do not reflect the internal state of stress but merely provide information about the average mobilised wall friction. It is demonstrated that the results are sensitive to the initial stress state defined by K0 = sh/sv. For all cases, non-coaxiality of the principal stress and strain-rate directions is examined and the corresponding flow rule is identified. Periodic cell simulations have been used to examine biaxial compression for a wide range of initial packing densities. Both constant volume and constant mean stress tests have been simulated. The characteristic behaviour at both the macroscopic and microscopic scales is determined by whether or not the system percolates (enduring connectivity is established in all directions). The transition from non-percolating to percolating systems is characterised by transitional behaviour of internal variables and corresponds to an elastic percolation threshold, which correlates well with the establishment of a mechanical coordination number of ca. 3.0. Strong correlations are found between macroscopic and internal variables at the critical state.

Evidence for the removal of CFC-11, CFC-12, and CFC-113 at the groundwater–surface water interface in the Everglades

Poor agreement between 3H/3He ages and CFC-11 and CFC-12 ages suggests that CFCs may not be conservative tracers in the Everglades National Park. 3H/3He ages were used to calculate the expected concentration of CFC-11 and CFC-12 in groundwater from wells 2 to 73 m deep. The expected concentrations of CFCs were compared to the measured concentrations and plots of the % CFC-12 and CFC-11 remaining offered no evidence that significant CFC removal was occurring in the groundwater at depths ≥2 m, suggesting that CFC removal occurs at shallower depths. Except where CFC contamination was suspected, CFC-11, CFC-12 and CFC-113 concentrations in fresh surface water were nearly always below solubility equilibrium with the atmosphere. Measurements of CFC-11, CFC-12 and CFC-113 in pore water indicate a 50–90% decrease in concentration 5 cm below the groundwater–surface water (GW–SW) interface. In the same 5 cm interval CH4 concentrations increased by 300–1000%. This suggested that CFCs were removed at the GW–SW interface, possibly by methane-producing bacteria. CFC derived recharge ages should therefore be viewed with caution when recharging water percolates through anoxic methanogenic sediments.

(Tables 1-3) Geochemical composition of seepage water in soils obtained in Schleswig-Holstein, Germany

Under defined laboratory and field conditions, the investigation of percolating water through soil columns (podsol, lessive and peat) down to groundwater table shows that the main factors which control the chemical characteristics of the percolates are: precipitation, evaporation, infiltration rate, soil type, depth and dissolved organic substances. Evaporation and percolation velocity influences the Na+, SO4**2- and Cl- concentrations. Low percolation velocity leads also to longer percolation times and water logging in less permeable strata, which results in lower Eh-values and higher CO2-concentrations due to low gas exchange with the atmosphere. Ca2+ and Mg2+ carbonate concentration depends on soil type and depth. Metamorphism and decomposition of organic substances involve NO3 reduction and K+, Mg2+, SO4**2-, CO2, Fe2+,3+ transport. The analytical data were evaluated with multi variate statistical methods.

Predicting water permeability in sedimentary rocks from capillary imbibition and pore structure

In this paper, absolute water permeability is estimated from capillary imbibition and pore structure for 15 sedimentary rock types. They present a wide range of petrographic characteristics that provide degrees of connectivity, porosities, pore size distributions, water absorption coefficients by capillarity and water permeabilities. A statistical analysis shows strong correlations among the petrophysical parameters of the studied rocks. Several fundamental properties are fitted into different linear and multiple expressions where water permeability is expressed as a generalized function of the properties. Some practical aspects of these correlations are highlighted in order to use capillary imbibition tests to estimate permeability. The permeability–porosity relation is discussed in the context of the influence of pore connectivity and wettability. As a consequence, we propose a generalized model for permeability that includes information about water fluid rate (water absorption coefficient by capillarity), water properties (density and viscosity), wetting (interfacial tension and contact angle) and pore structure (pore radius and porosity). Its application is examined in terms of the type of pores that contribute to water transport and wettability. The results indicate that the threshold pore radius, in which water percolates through rock, achieves the best description of the pore system. The proposed equation is compared against Carman–Kozeny's and Katz–Thompson's equations. The proposed equation achieves very accurate predictions of the water permeability in the range of 0.01 to 1000 mD.