Comparing the effects of pH on the sorption of metals by soil and by goethite, and on uptake by plants

The effects of soil pH on sorption of cadmium, zinc, nickel and cobalt were studied by changing the pH of a soil and measuring sorption. Results were compared with published results for effects of pH on sorption of cadmium, zinc and nickel by goethite. In a further experiment, the effects of pH on the uptake of zinc and cobalt by subterranean clover were measured. Effects of pH on sorption were described in terms of the concentration of metal ions required to produce equal sorption. Where the metal ions were incubated with the soil, unit increase in pH decreased the concentration of metal ions required about 10-fold for zinc, about 7-fold for nickel, about 6-fold for cobalt, and about 4-fold for cadmium. When the soil was mixed with a large volume of solution, the effects were similar for zinc and cadmium but slightly smaller for cobalt and slightly larger for nickel. In all cases, the magnitude of the effect varied somewhat with pH. Sorption was greater with a dilute background electroiyte than with a concentrated one and the effects of pH were greater. The effects for soil were smaller than effects of pH on sorption by iron oxides for which unit increase in pH can decrease the required concentration of Zinc 35-fold and cadmium 11-fold. These results are consistent with adsorption of divalent ions on a variable charge surface that is negatively charged. They are not consistent with the adsorption of monovalent metal ions on a variable charge surface. This mechanism requires at least a 10-fold effect of pH. They show that the change in electric potential with change in pH is smaller for reacting surfaces in soil than for goethite. The effects of changing pH on the amounts of zinc and cobalt fertilizer required for equal uptake by plants was even smaller with unit increase in pH, causing a 1.4-fold increase in the amount of fertilizer required, that is, a 1.4-fold decrease in fertilizer effectiveness.     

Electrical conductivity in the precambrian lithosphere of western canada

The subcrustal lithosphere underlying the southern Archean Churchill Province (ACP) in western Canada is at least one order of magnitude more electrically conductive than the lithosphere beneath adjacent Paleoproterozoic crust. The measured electrical properties of the lithosphere underlying most of the Paleoproterozoic crust can be explained by the conductivity of olivine. Mantle xenolith and geological mapping evidence indicate that the lithosphere beneath the southern ACP was substantially modified as a result of being trapped between two nearly synchronous Paleoproterozoic subduction zones. Tectonically induced metasomatism thus may have enhanced the subcrustal lithosphere conductivity of the southern ACP.     

Farm management factors associated with bulk tank somatic cell count in Irish dairy herds

The relationship between bulk tank somatic cell count (SCC) and farm management and infrastructure was examined using data from 398 randomly selected, yet representative, Irish dairy farms where the basal diet is grazed grass. Median bulk tank SCC for the farms was 282,887 cells/ml ranging from 82,209 to 773,028 cells/ml. Two questionnaires were administered through face-to-face contact with each farmer. Herd-level factors associated with bulk tank SCC were determined using linear models with annual somatic cell score (i.e., arithmetic mean of the natural logarithm of bulk tank SCC) included as the dependent variable. All herd level factors were analysed individually in separate regression models, which included an adjustment for geographical location of the farm; a multiple regression model was subsequently developed. Management practices associated with low SCC included the use of dry cow therapy, participation in a milk recording scheme and the use of teat disinfection post-milking. There was an association between low SCC and an increased level of hygiene and frequency of cleaning of the holding yard, passageways and cubicles. Herd management factors associated with bulk tank SCC in Irish grazing herds are generally in agreement with most previous studies from confinement systems of milk production.     

Testing a mechanistic model. III. The effects of pH on fluoride retention by a soil

The pH of a soil was altered by incubating it with either lime or acid at 60°C for 1 day. Subsamples were then mixed with fluoride solutions in order to measure the effects of pH on fluoride retention. The results were compared with those previously obtained with phosphate on the same soil. At equal concentration of total fluorine in solution, fluoride retention was greatest at about pH 5.5 and decreased at both lower and higher pH. The decrease at low pH appeared to be caused by the formation of complexes between fluoride and aluminium in solution. As a result, only a small proportion of the total fluorine in solution was present as fluoride ions. At equal concentrations of fluoride ions, fluoride retention decreased with increasing pH. It was shown that this decrease could be explained by decreases in the electrostatic potential of the variable charge materials. The decrease in potential was steeper than that required to describe phosphate retention. This is consistent with the plane of adsorption of fluoride ions being closer to the plane of adsorption of H⁺ and OH^? ions.     

Colossal Magnetoresistance Without Mn3+/Mn4+ Double Exchange in the Stoichiometric Pyrochlore Tl2Mn2O7

Structural analysis from powder neutron and single-crystal x-ray diffraction data for a sample of the Tl2Mn2O7 pyrochlore, which exhibits colossal magnetoresistance (CMR), shows no deviations from ideal stoichiometry. This analysis gives an Mn-O distance of 1.90 angstroms, which is significantly shorter than the Mn-O distances (1.94 to 2.00 angstroms) observed in phases based on LaMnO3 perovskites that exhibit CMR. Both results in Tl2Mn2O7 indicate oxidation states very close to Tl23+Mn24+O7. Thus, Tl2Mn2O7 has neither mixed valence for a double-exchange magnetic interaction nor a Jahn-Teller cation such as Mn3+, both of which were thought to have an important function in CMR materials. An alternate mechanism for CMR in Tl2Mn2O7 based on magnetic ordering driven by superexchange and strong spin-fluctuation scattering above the Curie temperature is proposed here.     

Testing a mechanistic model. VI. Molecular modelling of the effects of pH on phosphate and on zinc retention by soils

Both phosphate and metal cations such as zinc can be retained by oxides of iron and aluminium. Yet the phosphate-retaining and zinc-retaining materials in soil appear to differ in their behaviour from that of pure oxides of iron and aluminium. In most soils, the electrostatic potentials of retaining materials appear to be negative at normal soil pH values. The changes in potential with pH, and consequent change in retention, also appear to differ from those of pure oxides. A model of a pure oxide was modified in an attempt to simulate the observed behaviour of soil. The most effective modification was to include a negative charge in the oxide. Such a charge could have arisen from solid–state diffusion of anions into the oxide, or by close association with permanently charged clays. The inclusion of this charge changes the direction of the effect of pH on phosphate retention. If the amount of negative charge is large enough, the paradoxical situation can arise in which the potential of a ‘variable-charge’ surface is not affected by pH. This is consistent with observed effects of pH on zinc retention by soils.     

Testing a mechanistic model. X. The effect of pH and electrolyte concentration on borate sorption by a soil

Borate sorption by a soil was measured with 0.01, 0.1, or 1.0 M sodium chloride as background electrolyte and samples of soil with a range of pH values achieved by incubating with either calcium carbonate or hydrochloric acid for 24 h at 60°C.
Borate sorption generally increased with increasing pH. The more concentrated the electrolyte, the steeper the increase. At low pH, increasing the salt concentration decreased borate sorption; at high pH, it increased sorption. There was an intermediate pH at which salt had no effect on borate sorption. The point of zero salt effect on borate sorption was at a higher pH than the point of zero salt effect on pH. This result was explained by a mechanism in which borate ions react with variable charge surfaces which are heterogeneous and for which part of the heterogeneity is in the electric potential of the surfaces. It cannot be explained by mechanisms which do not take into account the effects of the electric potential of the reacting surfaces on the reaction with borate ions. Although the behaviour of borate was broadly consistent with that of other anions, it differed in that about half of the heterogeneity had to be allocated to the binding constant for borate ions. It was suggested that this was because reaction with organic matter was more important for borate than for other anions.