Quantifying yield behaviour in metals by X-ray nanotomography.

Nanoindentation of engineering materials is commonly used to study, at small length scales, the continuum mechanical properties of elastic modulus and yield strength. However, it is difficult to measure strain hardening via nanoindentation. Strain hardening, which describes the increase in strength with plastic deformation, affects fracture toughness and ductility, and is an important engineering material property. The problem is that the load-displacement data of a single nanoindentation do not provide a unique solution for the material's plastic properties, which can be described by its stress-strain behaviour. Three-dimensional mapping of the displacement field beneath the indentation provides additional information that can overcome this difficulty. We have applied digital volume correlation of X-ray nano-tomographs of a nanoindentation to measure the sub-surface displacement field and so obtain the plastic properties of a nano-structured oxide dispersion strengthened steel. This steel has potential applications in advanced nuclear energy systems, and this novel method could characterise samples where proton irradiation of the surface simulates the effects of fast neutron damage, since facilities do not yet exist that can replicate this damage in bulk materials.

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga.

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.

Trace metal concentrations in shallow ground water.

Trace metal clean sampling and analysis techniques were used to examine the temporal patterns of Hg, Cu, and Zn concentrations in shallow ground water, and the relationships between metal concentrations in ground water and in a hydrologically connected river. Hg, Cu, and Zn concentrations in ground water ranged from 0.07 to 4.6 ng L-1, 0.07 to 3.10 micrograms L-1, and 0.17 to 2.18 micrograms L-1, respectively. There was no apparent seasonal pattern in any of the metal concentrations. Filtrable Hg, Cu, and Zn concentrations in the North Branch of the Milwaukee River ranged from below the detection limit to 2.65 ng Hg L-1, 0.51 to 4.30 micrograms Cu L-1, and 0.34 to 2.33 micrograms Zn L-1. Thus, metal concentrations in ground water were sufficiently high to account for a substantial fraction of the filtrable trace metal concentration in the river. Metal concentrations in the soil ranged from 8 to 86 ng Hg g-1, 10 to 39 micrograms Cu g-1, and 15 to 84 micrograms Zn g-1. Distribution coefficients, KD, in the aquifer were 7900, 22,000, and 23,000 L kg-1 for Hg, Cu, and Zn, respectively. These values were three to 40 times smaller than KD values observed in the Milwaukee River for suspended particulate matter.

Determination of silver speciation in natural waters. 1. Laboratory tests of Chelex-100 chelating resin as a competing ligand.

Batch and column experiments were performed to investigate the suitability and chemical characteristics of Chelex-100 for use as a competing ligand in ionic silver (Ag(I)) speciation determinations in natural waters. A conditional stability constant (Kcond) for Ag+ chelation by iminodiacetate groups on the surface of Chelex resin was determined by fitting results of batch and column experiments with an equilibrium speciation model. Results of experiments in which Chelex competed with cyanide ion and thiosulfate ion for aqueous Ag+ were fitted well by a model in which log Kcond(Ag-Chelex) was set to 7.2. This value is similar to literature equilibrium constants for a 1:1 Ag(+)-EDTA chelate. In batch experiments with Chelex, equilibration times of 24 h were found to be sufficient to bring samples close to equilibrium. Effects of resin counterion and total Ag(I) concentration on extent of Ag(I) chelation were found to be minor. Effect of pH on Ag(I) chelation was minor over a range of 6-10. Column experiments (detention time = 6 s, empty-column basis) in which thiosulfate competed with Chelex for Ag(I) gave similar results to batch experiments with thiosulfate. This implies that batch and column experiments could be compared to explore ligands in natural water systems with different rates of dissociation.

Determination of silver speciation in natural waters. 2. Binding strength of silver ligands in surface freshwaters.

Three competing ligand methods were compared to determine characteristics of Ag(I) complexation by dissolved and colloidal ligands present in three rivers and one sewage treatment plant effluent. Iminodiacetate groups on Chelex-100 resin (used in batch and column experiments) and diethyldithiocarbamate (DDC) were used as competing ligands. Results of batch Chelex and DDC competition experiments show good agreement with regard to relative extent of Ag binding by natural ligands among the three river systems. Results of both methods also show a possible correlation between extent of Ag(I) complexation and organic matter concentration and/or Fe concentration. Fraction of Ag(I) associated with Chelex in both batch and column Chelex experiments was similar in each of the four systems tested, indicating that lability of Ag complexes does not change significantly on time scales ranging from seconds to 24 h. Results of Chelex and DDC competition were compared using a model based on a hypothetical single natural ligand. Under the experimental conditions used, this model quantified Ag(I) complexes with log Kcond values from approximately 12 to 14. For the three rivers studied, ligands with silver-association characteristics similar to those of reduced sulfur groups (log K = 14-16) present at subnanomolar concentrations likely dominate Ag(I) speciation in these systems. A weaker ligand (e.g., log Kcond < 12) at concentrations > 0.7 nM dominated Ag(I) speciation in the treatment plant effluent. This may result from elevated concentration of metals that compete for reduced sulfur groups rather than from a lower total concentration of these groups.

Partitioning of total mercury and methylmercury to the colloidal phase in freshwaters.

Using tangential flow ultrafiltration, total mercury (HgT) and methylmercury (MeHg) concentrations in the colloidal phase (0.4 microm-10 kDa) were determined for 15 freshwaters located in the upper Midwest (Minnesota, Michigan, and Wisconsin) and the Southern United States (Georgia and Florida). Unfiltered concentrations were typical of those reported for freshwater and ranged from 0.9 to 27.1 ng L(-1) HgT and from 0.08 to 0.86 ng L(-1) MeHg. For some rivers, HgT and MeHg in the colloidal phase comprised up to 72% of the respective unfiltered concentration. On average, however, HgT and MeHg concentrations were evenly distributed between the particulate (>0.4 microm), colloidal, and dissolved (<10 kDa) phases. The pool of Hg in the colloidal phase decreased with increasing specific conductance. Results from experiments on freshwaters with artificially elevated specific conductance suggest that HgT and MeHg may partition to different subfractions of colloidal material. The colloidal-phase HgT correlation with filtered organic carbon (OC(F)) was generally poor (r2 < 0.14; p > 0.07), but the regression of MeHg with OC(F) was strong, especially in the upper Midwest (r2 = 0.78; p < 0.01). On a mass basis, colloidal-phase Hg concentrations were similar to those of unimpacted sediments in the Midwest. Mercury to carbon ratios averaged 352 pg of HgT/mg of C and 25 pg of MeHg/mg of C and were not correlated to ionic strength. The log of the partition coefficient (log K(D)) for HgT and MeHg ranged from 3.7 to 6.4 and was typical of freshwater values determined using a 0.4 microm cutoff between the particulate phase and the dissolved phase. Log K(D) calculated using the <10 kDa fraction as "dissolved" ranged from 4.3 to 6.6 and had a smaller standard deviation about the mean. In addition, our data support the "particle concentration effect" (PCE) hypothesis that the association of Hg with colloids in the filter-passing fraction can lower the observed log K(D). The similarity between colloidal and particulate-phase partition coefficients suggests that colloidal mass and not preferential colloidal partitioning drives the PCE.

The effects of diazepam on "fear" reactions in rats are modulated by environmental constraints on the rat's defensive repertoire.

The simultaneous effects of diazepam on three shock-induced reactions in rats were studied in order to determine the reliability of these behaviors as indices of anxiolytic drug action. Rats were injected with 1 mg/kg of diazepam or vehicle, placed in a 2-compartment chamber containing bedding material, and shocked with 1, 2, or 6 mA when they first touched a wire-wrapped prod attached to one end of the chamber. Diazepam-treated animals displayed significantly less burying behavior, but paradoxically, they also displayed more passive avoidance behavior and fewer exploratory side-transitions than vehicle-injected controls. Defensive burying behavior tended to be negatively correlated with passive avoidance behavior and positively correlated with exploratory side transitions. When the "competitive" relationship between defensive burying and passive avoidance was eliminated by testing rats in a 2-compartment chamber not containing bedding material, diazepam produced a significant suppression of passive avoidance and a significant increase in exploratory side-transitions, compared to control. Taken together, these results suggested that the validity of any single behavioral model of anxiolytic drug action might vary as a function of environmental constraints on the subjects' defensive repertoire.

Ground water as a silica source for diatom production in a precipitation-dominated lake.

The short-term, seasonal input of ground water to a small, precipitation-dominated oligotrophic lake in northern Wisconsin amounts to less than 10 percent of the annual water budget of the lake but accounts for nearly all the external silica loading. Silica is a necessary nutrient for diatoms. A large spring diatom bloom occurs coincident with high silica inputs from ground water when other possible silica sources are low. The mass budgets of ground water and silica in the lake system demonstrate the importance of ground-water solute inputs to the lake.

A simplified phosphorus analysis technique.

A simplified method for the analysis of total P(TP), total dissolved P(TDP) and dissolved reactive P (DRP) in multiple water samples has been developed. The reported modification utilizes a single digestion reagent and a single "mixed reagent" to eliminate neutralization, transfer and dilution steps normally required in total P analyses. The method results in a 70 percent decrease in analysis time for multiple samples, a reduction in the glassware required, and about a 30 percent increase in sensitivity. The method can be directly applied to water samples with P levels of 2 to 1100 ug P/l. Reproducibility and precision measurements compare to or exceed commonly used P techniques.

Adenosine Triphosphate Content of Selenastrum capricornutum.

The adenosine triphosphate content of Selenastrum capricornutum was maintained within 1.4 to 3.4 mug of adenosine triphosphate/mg (dry weight) of living biomass at different growth stages in media of different phosphorus concentrations.