Trace metal speciation in the Pieman River catchment, western Tasmania

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

Strain gradients in Cu-Fe thin films and multilayers during micropillar compression

Plastic strain gradients can influence the work-hardening behaviour of metals due to the accumulation of geometrically necessary discolations at the micron/submicron scale. A finite element model based on the conventional theory of mechanism-based strain-gradient plasticity has been developed to simulate the micropillar compression of Cu–Fe thin films and multilayers. The modelling results show that the geometric constraints lead to inhomogeneous deformation in the Cu layers, which agrees well with the bulging of Cu layers observed experimentally. Plastic strain gradients develop inside the individual layers, leading to extra work-hardening due to the accumulation of geometrically necessary dislocations. In the multilayer specimens, the Cu layers deform more severely than the Fe layers, resulting in the development of tensile stresses in the Fe layers. It is proposed that these tensile stresses are responsible for the development of micro-cracks in the Fe layers.

Electromagnetic interference shielding and radiation absorption in thin polypyrrole films

Results of permittivity measurements, electromagnetic interference shielding effectiveness, and heat generation due to microwave absorption in conducting polymer coated textiles are reported and discussed. The intrinsically conducting polymer, polypyrrole, doped with anthraquinone-2-sulfonic acid (AQSA) or para-toluene-2-sulfonic acid (pTSA) was applied on textile substrates and the resulting materials were investigated in the frequency range 1–18 GHz. The 0.54 mm thick conducting textile/polypyrrole composites absorbed up to 49.5% of the incident 30–35 W microwave radiation. A thermography station was used to monitor the temperature of these composites during the irradiation process, where absorption was confirmed via visible heat losses. Samples with lower conductivity showed larger temperature increases caused by microwave absorption compared to samples with higher conductivity. A sample with an average sheet resistivity of 150 Ω/sq. showed a maximum temperature increase of 5.27 °C, whilst a sample with a lower resistivity (105 Ω/sq.) rose by 3.85 °C.