A copper-hydrogen peroxide redox system induces dityrosine cross-links and chemokine oligomerisation

The activity of the chemoattractant cytokines, the chemokines, in vivo is enhanced by oligomerisation and aggregation on glycosaminoglycan (GAG), particularly heparan sulphate, side chains of proteoglycans. The chemokine RANTES (CCL5) is a T-lymphocyte and monocyte chemoattractant, which has a minimum tetrameric structure for in vivo activity and a propensity to form higher order oligomers. RANTES is unusual among the chemokines in having five tyrosine residues, an amino acid susceptible to oxidative cross-linking. Using fluorescence emission spectroscopy, Western blot analysis and LCMS-MS, we show that a copper/H2O2 redox system induces the formation of covalent dityrosine cross-links and RANTES oligomerisation with the formation of tetramers, as well as higher order oligomers. Amongst the transition metals tested, namely copper, nickel, mercury, iron and zinc, copper appeared unique in this respect. At high (400 µM) concentrations of H2O2, RANTES monomers, dimers and oligomers are destroyed, but heparan sulphate protects the chemokine from oxidative damage, promoting dityrosine cross-links and multimer formation under oxidative conditions. Low levels of dityrosine cross-links were detected in copper/H2O2-treated IL-8 (CXCL8), which has one tyrosine residue, and none were detected in ENA-78 (CXCL5), which has none. Redox-treated RANTES was fully functional in Boyden chamber assays of T-cell migration and receptor usage on activated T-cells following RANTES oligomerisation was not altered. Our results point to a protective, anti-oxidant, role for heparan sulphate and a previously unrecognised role for copper in chemokine oligomerisation that may offer an explanation for the known anti-inflammatory effect of copper-chelators such as penicillamine and tobramycin.

Pathways utilized by heavy metal pollutants in urban stormwater runoff

The research concerned the assessment of the pathways utilized by heavy metal pollutants in urban stormwater runoff. A separately sewered urban residential catchment of approximately 107 hectares in Chelmsley Wood, north-east Birmingham was the subject of the field investigation. The catchment area, almost entirely residential, had no immediate industrial heavy metal input, however, industry was situated to the north of the catchment. The perimeter of the catchment was bounded by the M6 motorway on the northern and eastern sides and was believed to contribute to aerial deposition. Metal inputs to the ground surface were assumed to be confined to normal suburban activities, namely, aerial deposition, vehicular activity and anthropological activities. A programme of field work was undertaken over a 12 month period, from July 1983 to July 1984. Monthly deposition rates were monitored using a network of deposit cannisters and roadside sediment and soil samples were taken. Stormwater samples were obtained for 19 separate events. All samples were analysed for iron, lead, zinc, copper, chromium, nickel and cadmium content. Rainfall was recorded on site with additional meteorological data obtained from local Meteorological Offices. Use was made of a simple conceptual model designed for the catchment to substantiate hypotheses derived from site investigations and literature, to investigate the pathways utilized for the transportation of heavy metals throughout the catchment.

The influence of environment on foliose lichen growth and its biological significance

Radial growth and growth in mass of lichens is influenced by climatic and microclimatic factors and also by substratum factors such as rock and bark texture, chemistry, and nutrient enrichment. Seasonal fluctuations in growth, as measured by radial growth rate (RaGR) per month, often correlate best with average or total rainfall, the number of rain days, or rainfall in a specific season. Temperature is also considered to be an important climatic factor in some studies. Interactions between microclimatic factors and especially light intensity, temperature, and moisture are the most important in determining local annual growth rates. The physical and chemical nature of the substratum has a profound influence on the growth of foliose lichens. Hence, the effects of texture, porosity, rate of drying, and the physical changes of the substratum on growth are likely to influence lichen distributions. Bird droppings may influence growth and survival by smothering the thalli, altering the pH, or adding inhibitory and stimulatory compounds. Nitrogen and phosphate availability may also influence growth. Chemical factors may also have an important influence on lichens of maritime rocks, the effect of salinity and calcium ions being of particular importance. Zinc, copper, and mercury may also be important in lichen growth as they have been shown to affect the chlorophyll content of lichen algae. Effects of environmental factors on growth influence the competitive ability of lichens thus influencing their ecology and distribution.

Textural and microstructural studies of zinc sulfide and associated phases in certain base metal deposits

A textural and microstructural study of a variety of zinc sulfide-containing ores has been undertaken, and the possible depositional and deformational controls of textural and microstructural development considered. Samples for the study were taken from both deformed and undeformed zinc ores of the Central U.S. Appalachians, and deformed zinc ores of the English Pennines. A variety of mineralogical techniques were employed, including transmitted and reflected light microscopy of etched and unetched material, transmission electron microscopy and electron microprobe analysis. For the Pennine zinc sulfides, spectroscopic, x-ray diffraction and fluid inclusion studies were also undertaken. Optical and electron optical examination of the Appalachian material confirmed the suitability of zinc sulfide for detailed study with such techniques. Growth and deformation-related microstructures could be distinguished from specimen-preparation induced artifacts. A deformationally-mduced lamelliform optical anisotropy is seen to be developed in areas hosting a dense planar microstructure of {111} twin- and slip-planes. The Pennine zinc sulfide texturally records a changing depositional environment. Thus, for example, delicately growth- zoned crystals are truncated and cross-cut by solution disconformities. Fluid inclusion studies indicate a highly saline (20-25 wt. % equiv. NaCl), low temperature (100-150°C.) fluid. Texturally, two varieties of zinc sulfide can be recognised; a widely developed, iron- banded variety, and a paragenetically early variety, banded due to horizons rich in crystal defects and microscopic inclusions. The zinc sulfide takes the form of a disordered 3C-polytype, with much of the disorder being deformational in origin. Twin- and slip-plane fabrics are developed . A deformation-related optical anisotropy is seen to overprint growth-related anisotropy, along with cuprian alteration of certain {111} deformation planes.

The creep behaviour of pressure diecast zinc-aluminium based alloys

The creep behaviour of three pressure diecast commercial zinc-aluminium based alloys: Mazak 3, corresponding to BS 1004A, and the new alloys ZA.8 and ZA.27 with a series of alloys with compositions ranging from 0% to 30% aluminium was investigated. The total creep elongation of commercial alloys was shown to be well correlated using an empirical equation. Based on this a parametrical relationship was derived which allowed the total creep extension to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of creep of the alloys could be made under different conditions. Deviation from the normal creep kinetics occurred in alloys ZA.8 and ZA.27 at very low stresses, 150°C, due to structural coarsening combined with partial transformation of ε -phase into T' phase. The extent of primary creep was found to increase with aluminium content, but secondary creep rates decreased in the order Mazak 3, ZA.8 and ZA.27. Thus, based on the above equation, ZA.8 was found to have a substantially better total creep resistance than ZA.27, which in turn was marginally better than Mazak 3 for strains higher than 0.5%, but inferior for smaller strains, due to its higher primary creep extension. The superior creep resistance of ZA.8 was found to be due to the presence of strictly-orientated, thin plate-like precipitates of ε(CuZn4) phase in the zinc matrix of the eutectic and the lamellarly decomposed β phase, in which the precipitation morphology and orientation of ε in the zinc matrix was determined. Over broad ranges of temperature and stresses, the stress exponents and activation energies for creep were found to be consistent with some proposed creep rate mechanisms; i.e. viscous glide for Mazak 3, dislocation climb over second phase particles for ZA.8 and dislocation climb for ZA.27, controlled by diffusion in the zinc-rich phase. The morphology of aluminium and copper-rich precipitates formed from the solid solution of zinc was clearly revealed. The former were found to further increase the creep rate of inherently low creep resistant zinc, but the latter contributed significantly to the creep resistance. Excess copper in the composition, however, was not beneficial in improving the creep resistance. Decomposition of β in copper-containing alloys was found to be through a metastable Zn-Al phase which is strongly stabilised by copper, and the final products of the decomposition had a profound effect on the creep strength of the alloys. The poor creep resistance of alloy ZA.27 was due to the presence of particulate products derived from decomposed β-phase and a large volume of fine, equiaxed products of continuously decomposed α-dendrites.

The fatigue properties of pressure diecast zinc-aluminium based alloys

The fatigue behaviour of the cold chamber pressure-die-cast alloys: Mazak3, ZA8, ZA27, M3K, ZA8K, ZA27K, K1, K2 and K3 was investigated at temperature of 20°C. The alloys M3K, ZA8K and ZA27K were also examined at temperatures of 50 and 100°C. The ratio between fatigue strength and tensile strength was established at 20°C at 107 cycles. The fatigue life prediction of the alloys M3K, ZA8K and ZA27K was formulated at 20, 50 and 100°C. The prediction formulae were found to be reasonably accurate. All of the experimental alloys were heterogeneous and contained large but varying amounts of pores. These pores were a major contribution and dominated the alloys fatigue failure. Their effect, however, on tensile failure was negligible. The ZA27K possessed the highest tensile strength but the lowest fatigue strength. The relationship between the fracture topography and the microstructure was also determined by the use of a mixed signal of a secondary electron and a back-scattered electron on the SEM. The tensile strength of the experimental alloys was directly proportional to the aluminium content within the alloys. The effect of copper content was also investigated within the alloys K1, K2, ZA8K and K3 which contained 0%, 0.5%, 1.0% and 2.0% respectively. It was determined that the fatigue and tensile strengths improved with higher copper contents. Upon ageing the alloys Mazak3, ZA8 and ZA27 at an ambient temperature for 5 years, copper was also found to influence and maintain the metastable Zn-Al (αm) phase. The copper free Mazak3 upon ageing lost this metastable phase. The 1.0% copper ZA8 alloy had lost almost 50% of its metastable phase. Finally the 2.0% copper ZA27 had merely lost 10% of its metastable phase. The cph zinc contained a limited number of slip systems, therefore twinning deformation was unavoidable in both fatigue and tensile testing.

The creep properties of a series of zinc-rich zinc-aluminium alloys

The compressive creep behaviour of six sand cast zinc-rich alloys: No3 and No5, corresponding to BS 1004A and BS 1004B, respectively, alloy No2, ILZRO,.16 and two newer alloys ACuZinc5 and ACuZinc10 was investigated. The total creep contraction of the alloys was found to be well correlated using an empirical equation. On the basis of this equation, a parametrical relationship was derived which allowed the total creep contraction to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of compressive creep of the alloys could be made under different testing conditions. The primary creep and secondary creep rates were found for the alloys at different temperatures and stresses. Generally, the primary creep contraction was found to increase with copper content, whereas secondary creep rates decreased in the order No3, ACuZinc10, ACuZinc5 and No2. ILZRO.16 was tested only at the highest stress and two higher temperatures. The results showed that ILZRO.16 had higher creep resistance than all the other alloys. Thus, based on the above empirical equation, alloy No2 was found to have a substantially better total creep resistance than alloys No3 and No5, and slightly better than ACuZinc5 and ACuZinc10 for strains up to 1%. Both ACuZinc alloys had higher creep strength than commercial alloys No3 and No5. Alloy No5 had much higher creep resistance than alloy No3 under all conditions. The superior creep resistance of alloy No2 was considered to be due to the presence of small precipitates of -phase in the zinc matrix and a regular eutectic morphology. The stress exponents and activation energies for creep under different testing conditions were found to be consistent with some established creep-controlling mechanisms; i.e. dislocation climb for alloy No3, dislocation climb over second phase particles for alloys No5, No2, ACuZinc10, controlled by lattice diffusion in the zinc-rich phase. The lower creep resistance of alloy No3 was mainly due to the lower creep strength of copper-free primary particles having greater volume than eutectic in the microstructure. Alloys No5, ACuZinc5 and ACuZinc10 showed much better creep resistance than alloy No3, based on the precipitation-hardening due to the presence of small -phase precipitates. The primary dendrites in both ACuZinc alloys however were not of much benefit in improving the creep resistance of the alloys.

Melting and solidification of Zinc-Aluminium alloys

Following a scene-setting introduction are detailed reviews of the relevant scientific principles, thermal analysis as a research tool and the development of the zinc-aluminium family of alloys. A recently introduced simultaneous thermal analyser, the STA 1500, its use for differential thermal analysis (DTA) being central to the investigation, is described, together with the sources of support information, chemical analysis, scanning electron microscopy, ingot cooling curves and fluidity spiral castings. The compositions of alloys tested were from the binary zinc-aluminium system, the ternary zinc-aluminium-silicon system at 30%, 50% and 70% aluminium levels, binary and ternary alloys with additions of copper and magnesium to simulate commercial alloys and five widely used commercial alloys. Each alloy was shotted to provide the smaller, 100mg, representative sample required for DTA. The STA 1500 was characterised and calibrated with commercially pure zinc, and an experimental procedure established for the determination of DTA heating curves at 10°C per minute and cooling curves at 2°C per minute. Phase change temperatures were taken from DTA traces, most importantly, liquidus from a cooling curve and solidus from both heating and cooling curves. The accepted zinc-aluminium binary phase diagram was endorsed with the added detail that the eutectic is at 5.2% aluminium rather than 5.0%. The ternary eutectic trough was found to run through the points, 70% Al, 7.1% Si, 545°C; 50% Al, 3.9% Si, 520°C; 30% Al, 1.4% Si, 482°C. The dendrite arm spacing in samples after DTA increased with increasing aluminium content from 130m at 30% to 220m at 70%. The smallest dendrite arm spacing of 60m was in the 30% aluminium 2% silicon alloy. A 1kg ingot of the 10% aluminium binary alloy, insulated with Kaowool, solidified at the same 2°C per minute rate as the DTA samples. A similar sized sand casting was solidified at 3°C per minute and a chill casting at 27°C per minute. During metallographic examination the following features were observed: heavily cored phase which decomposed into ' and '' on cooling; needles of the intermetallic phase FeAl4; copper containing ternary eutectic and copper rich T phase.