Anionic clay-Pt metal nanoparticle composite through intercalation of hexachloroplatinate in nickel zinc hydroxysalt

Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl6]2− in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers.

Tropical dryland agroforestry on clay soils: : Analysis of systems based on Acacia senegal in the Blue Nile region, Sudan

Acacia senegal, the gum arabic producing tree, is the most important component in traditional dryland agroforestry systems in the Blue Nile region, Sudan. The aim of the present study was to provide new knowledge on the potential use of A. senegal in dryland agroforestry systems on clay soils, as well as information on tree/crop interaction, and on silvicultural and management tools, with consideration on system productivity, nutrient cycling and sustainability. Moreover, the aim was also to clarify the intra-specific variation in the performance of A. senegal and, specifically, the adaptation of trees of different origin to the clay soils of the Blue Nile region. In agroforestry systems established at the beginning of the study, tree and crop growth, water use, gum and crop yields, nutrient cycling and system performance were investigated for a period of four years (1999 to 2002). Trees were grown at 5 x 5 m and 10 x 10 m spacing alone or in mixture with sorghum or sesame; crops were also grown in sole culture. The symbiotic biological N2 fixation by A. senegal was estimated using the 15N natural abundance (δ15N) procedure in eight provenances collected from different environments and soil types of the gum arabic belt and grown in clay soil in the Blue Nile region. Balanites aegyptiaca (a non-legume) was used as a non-N-fixing reference tree species, so as to allow 15N-based estimates of the proportion of the nitrogen in trees derived from the atmosphere. In the planted acacia trees, measurements were made on shoot growth, water-use efficiency (as assessed by the δ13C method) and (starting from the third year) gum production. Carbon isotope ratios were obtained from the leaves and branch wood samples. The agroforestry system design caused no statistically significant variation in water use, but the variation was highly significant between years, and the highest water use occurred in the years with high rainfall. No statistically significant differences were found in sorghum or sesame yields when intercropping and sole crop systems were compared (yield averages were 1.54 and 1.54 ha-1 for sorghum and 0.36 and 0.42 t ha-1 for sesame in the intercropped and mono-crop plots, respectively). Thus, at an early stage of agroforestry system management, A. senegal had no detrimental effect on crop yield, but the pattern of resource capture by trees and crops may change as the system matures. Intercropping resulted in taller trees and larger basal and crown diameters as compared to the development of sole trees. It also resulted in a higher land equivalent ratio. When gum yields were analysed it was found that a significant positive relationship existed between the second gum picking and the total gum yield. The second gum picking seems to be a decisive factor in gum production and could be used as an indicator for the total gum yield in a particular year. In trees, the concentrations of N and P were higher in leaves and roots, whereas the levels of K were higher in stems, branches and roots. Soil organic matter, N, P and K contents were highest in the upper soil stratum. There was some indication that the P content slightly increased in the topsoil as the agroforestry plantations aged. At a stocking of 400 trees ha-1 (5 x 5 m spacing), A. senegal accumulated in the biomass a total of 18, 1.21, 7.8 and 972 kg ha-1of N, P, K and OC, respectively. Trees contributed ca. 217 and 1500 kg ha-1 of K and OC, respectively, to the top 25-cm of soil over the first four years of intercropping. Acacia provenances of clay plain origin showed considerable variation in seed weight. They also had the lowest average seed weight as compared to the sandy soil (western) provenances. At the experimental site in the clay soil region, the clay provenances were distinctly superior to the sand provenances in all traits studied but especially in basal diameter and crown width, thus reflecting their adaptation to the environment. Values of δ13C, indicating water use efficiency, were higher in the sand soil group as compared to the clay one, both in leaves and in branch wood. This suggests that the sand provenances (with an average value of -28.07 ) displayed conservative water use and high drought tolerance. Of the clay provenances, the local one (Bout) displayed a highly negative (-29.31 ) value, which indicates less conservative water use that resulted in high productivity at this particular clay-soil site. Water use thus appeared to correspond to the environmental conditions prevailing at the original locations for these provenances. Results suggest that A. senegal provenances from the clay part of the gum belt are adapted for a faster growth rate and higher biomass and gum productivity as compared to provenances from sand regions. A strong negative relationship was found between the per-tree gum yield and water use efficiency, as indicated by δ13C. The differences in water use and gum production were greater among provenance groups than within them, suggesting that selection among rather than within provenances would result in distinct genetic gain in gum yield. The relative δ15N values ( ) were higher in B. aegyptiaca than in the N2-fixing acacia provenances. The amount of Ndfa increased significantly with age in all provenances, indicating that A. senegal is a potentially efficient nitrogen fixer and has an important role in t agroforestry development. The total above-ground contribution of fixed N to foliage growth in 4-year-old A. senegal trees was highest in the Rahad sand-soil provenance (46.7 kg N ha-1) and lowest in the Mazmoom clay-soil provenance (28.7 kg N ha-1). This study represents the first use of the δ15N method for estimating the N input by A. senegal in the gum belt of Sudan. Key words: Acacia senegal, agroforestry, clay plain, δ13C, δ15N, gum arabic, nutrient cycling, Ndfa, Sorghum bicolor, Sesamum indicum

Development of analytical methods for the separation of plutonium, americium, curium and neptunium from environmental samples

In this work, separation methods have been developed for the analysis of anthropogenic transuranium elements plutonium, americium, curium and neptunium from environmental samples contaminated by global nuclear weapons testing and the Chernobyl accident. The analytical methods utilized in this study are based on extraction chromatography. Highly varying atmospheric plutonium isotope concentrations and activity ratios were found at both Kurchatov (Kazakhstan), near the former Semipalatinsk test site, and Sodankylä (Finland). The origin of plutonium is almost impossible to identify at Kurchatov, since hundreds of nuclear tests were performed at the Semipalatinsk test site. In Sodankylä, plutonium in the surface air originated from nuclear weapons testing, conducted mostly by USSR and USA before the sampling year 1963. The variation in americium, curium and neptunium concentrations was great as well in peat samples collected in southern and central Finland in 1986 immediately after the Chernobyl accident. The main source of transuranium contamination in peats was from global nuclear test fallout, although there are wide regional differences in the fraction of Chernobyl-originated activity (of the total activity) for americium, curium and neptunium.

What are the driving factors influencing the size distribution of airborne synthetic clay particles emitted from a jet milling process?

In the field of workplace air quality, measuring and analyzing the size distribution of airborne particles to identify their sources and apportion their contribution has become widely accepted, however, the driving factors that influence this parameter, particularly for nanoparticles (< 100 nm), have not been thoroughly determined. Identification of driving factors, and in turn, general trends in size distribution of emitted particles would facilitate the prediction of nanoparticles’ emission behavior and significantly contribute to their exposure assessment. In this study, a comprehensive analysis of the particle number size distribution data, with a particular focus on the ultrafine size range of synthetic clay particles emitted from a jet milling machine was conducted using the multi-lognormal fitting method. The results showed relatively high contribution of nanoparticles to the emissions in many of the tested cases, and also, that both surface treatment and feed rate of the machine are significant factors influencing the size distribution of the emitted particles of this size. In particular, applying surface treatments and increasing the machine feed rate have the similar effect of reducing the size of the particles, however, no general trend was found in variations of size distribution across different surface treatments and feed rates. The findings of our study demonstrate that for this process and other activities, where no general trend is found in the size distribution of the emitted airborne particles due to dissimilar effects of the driving factors, each case must be treated separately in terms of workplace exposure assessment and regulations.

Effect of soil variability on the bearing capacity of clay and in slope stability problems

Site-specific geotechnical data are always random and variable in space. In the present study, a procedure for quantifying the variability in geotechnical characterization and design parameters is discussed using the site-specific cone tip resistance data (qc) obtained from static cone penetration test (SCPT). The parameters for the spatial variability modeling of geotechnical parameters i.e. (i) existing trend function in the in situ qc data; (ii) second moment statistics i.e. analysis of mean, variance, and auto-correlation structure of the soil strength and stiffness parameters; and (iii) inputs from the spatial correlation analysis, are utilized in the numerical modeling procedures using the finite difference numerical code FLAC 5.0. The influence of consideration of spatially variable soil parameters on the reliability-based geotechnical deign is studied for the two cases i.e. (a) bearing capacity analysis of a shallow foundation resting on a clayey soil, and (b) analysis of stability and deformation pattern of a cohesive-frictional soil slope. The study highlights the procedure for conducting a site-specific study using field test data such as SCPT in geotechnical analysis and demonstrates that a few additional computations involving soil variability provide a better insight into the role of variability in designs.

Invertebrate predation and trophic cascades in a pelagic food web : The multiple roles of Chaoborus flavicans (Meigen) in a clay-turbid lake

In lake ecosystems, both fish and invertebrate predators have dramatic effects on their prey communities. Fish predation selects large cladocerans while invertebrate predators prefer prey of smaller size. Since invertebrate predators are the preferred food items for fish, their occurrence at high densities is often connected with the absence or low number of fish. It is generally believed that invertebrate predators can play a significant role only if the density of planktivorous fish is low. However, in eutrophic clay-turbid Lake Hiidenvesi (southern Finland), a dense population of predatory Chaoborus flavicans larvae coexists with an abundant fish population. The population covers the stratifying area of the lake and attains a maximum population density of 23000 ind. m-2. This thesis aims to clarify the effects of Chaoborus flavicans on the zooplankton community and the environmental factors facilitating the coexistence of fish and invertebrate predators. In the stratifying area of Lake Hiidenvesi, the seasonal succession of cladocerans was exceptional. The spring biomass peak of cladocerans was missing and the highest biomass occurred in midsummer. In early summer, the consumption rate by chaoborids clearly exceeded the production rate of cladocerans and each year the biomass peak of cladocerans coincided with the minimum chaoborid density. In contrast, consumption by fish was very low and each study year cladocerans attained maximum biomass simultaneously with the highest consumption by smelt (Osmerus eperlanus). The results indicated that Chaoborus flavicans was the main predator of cladocerans in the stratifying area of Lake Hiidenvesi. The clay turbidity strongly contributed to the coexistence of chaoborids and smelt at high densities. Turbidity exceeding 30 NTU combined with light intensity below 0.1 μE m-2 s-1provides an efficient daytime refuge for chaoborids, but turbidity alone is not an adequate refuge unless combined with low light intensity. In the non-stratifying shallow basins of Lake Hiidenvesi, light intensity exceeds this level during summer days at the bottom of the lake, preventing Chaoborus forming a dense population in the shallow parts of the lake. Chaoborus can be successful particularly in deep, clay-turbid lakes where they can remain high in the water column close to their epilimnetic prey. Suspended clay alters the trophic interactions by weakening the link between fish and Chaoborus, which in turn strengthens the effect of Chaoborus predation on crustacean zooplankton. Since food web management largely relies on manipulations of fish stocks and the cascading effects of such actions, the validity of the method in deep clay-turbid lakes may be questioned.

Field performance of in-service cast iron gas reticulation pipe buried in reactive clay

Field instrumentation of an in-service cast iron gas pipe buried in a residential area is detailed in this paper. The aim of the study was to monitor the long-term pipe behavior to understand the mechanisms of pipe bending in relation to ground movement as a result of seasonal fluctuation of soil moisture content. Field data showed that variation of soil temperature, suction, and moisture content are closely related to the prevailing climate. Change of soil temperature is generally related to the ambient air temperature, with a variation of approximately −3°C −3°C per meter depth from the ground surface in summer (decrease with depth) and winter (increase with depth). Seasonal cyclic variation in moisture content was observed with maxima in February and March, and a minimum around September. The pipe top was under tensile strain during summer and subsequently subjected to compressive strain as soil swelling occurred as a result of increase in moisture content. The study suggests that downward pipe bending occurs in summer because of soil shrinkage, while upward pipe bending occurs in winter when the soil swells.

Influence of drying on the liquid limit behaviour of a marine clay

The possible mechanisms of particle aggregation and reduction in liquid limit of the Cochin marine clay on drying are investigated. Mineralogical analysis showed the absence of halloysite in the marine specimen. Experimental results also ruled out the possibility of cementitious material being responsible for particle aggregation and reduction in clay plasticity on drying. The presence of calcium and magnesium as the predominant exchangeable ions and of a high pore salt concentration facilitates strong interparticle attraction and small particle separations; the latter leads to development of significant capillary stresses that permits an intimate contact of particles and growth of strong van der Waals' and Coulombic bonds.

pH mediated delamination of anionic clay-like nickel-zinc hydroxysalt in water through intercalation of zwitterionic p-aminobenzoate ions

p-aminobenzoate could be intercalated into the anionic clay, Ni3Zn2(OH)(8)(OAc)(2)center dot 2H(2)O at a high pH (similar to 10). When the pH was reduced to similar to 7 while washing colloidal dispersion due to delamination was observed. The development of partial positive charge on the amine end of the intercalated anion causes repulsion between the layers leading to delamination and colloidal dispersion of monolayers in water. The layers could be restacked from the colloid to form the parent solid either by increasing the pH or by evaporation.

Indentation of sintered alumina clay composite - an experimental discussion of a combined Boussinesq and blister stress field approach

Surface elastic strain field generated in conical indentation of sintered alumina clay composite was measured to verify the suitability of a superposed combination of Boussinesq and blister stress fields, used previously for analysing the indentation problem. The residual strain measured in the elastic hinterland is used to estimate the blister field strength without any reference to stress relation within that field. The approach may be useful in fracture studies of brittle materials.

Revised Cam-Clay Model

The Cam-clay models, or any other plasticity-based models, do not make distinction between the mode of stress transfer in coarse- and fine-grained soils. An examination of behavior at micro level in fine-grained soils, from the consideration of load transfer through physico-chemical interactions, suggests that the plastic compressions result from the grouping of particles into larger clusters and that elastic compressions result from the decrease in the spacing between particles. During shearing, these clusters gradually get dismembered, releasing the locked-in energy. The effect of such dismembering of clusters can be easily incorporated into the original Cam-clay model, and better predictions can be obtained with the associated flow rule, itself, for both normally and over consolidated states. The method essentially defines the hardening of yield surfaces with internal changes in the spacing between particles, instead of changes in externally observed plastic strains. The approach describes the behavior of over consolidated soils as yielding along successfively hardening Roscoe surfaces with gradually varying plastic properties.