A rapid change in magma plumbing taps porphyry copper deposit-forming magmas.

Porphyry-type deposits are a vital source of green technology metals such as copper and molybdenum. They typically form in subduction-related settings from large, long-lived magmatic systems. The most widely accepted model for their formation requires that mantle-derived magmas undergo an increase in volatiles and ore-forming constituents in mid- to lower crustal reservoirs over millions of years, however, this is mostly based on observations from shallow, sporadically exposed parts of porphyry systems. To examine this paradigm, we have evaluated the timeframe and geochemical signatures of magmatism in a ~ 8 km palaeodepth cross-section through plutonic and volcanic rocks of the classic Yerington magmatic system, Nevada. We show that the magmas in the upper parts of the system (< 8 km) underwent a major and rapid change in chemistry over a period of < 200 kyrs that is coincident with the initiation of ore formation. We attribute this change to a shift from extraction of quartz monzodiorite and quartz monzonite magmas evolving in mid-crustal reservoirs, and that had relatively poor ore-forming potential, to extraction of volatile-rich granitic magmas from greater (~ 30 km) depths. As the granites crystallised, late stage melts were intruded through the carapace as aplite dykes which contain traceable expressions of the porphyry deposit-forming fluids. The rapid nature of the shift in ore-forming potential narrows the temporal-geochemical footprint of magmas associated with porphyry mineralisation and provides new constraints for exploration models.

The α-ß phase transition in volcanic cristobalite.

Cristobalite is a common mineral in volcanic ash produced from dome-forming eruptions. Assessment of the respiratory hazard posed by volcanic ash requires understanding the nature of the cristobalite it contains. Volcanic cristobalite contains coupled substitutions of Al3+ and Na+ for Si4+; similar co-substitutions in synthetic cristobalite are known to modify the crystal structure, affecting the stability of the α and ß forms and the observed transition between them. Here, for the first time, the dynamics and energy changes associated with the α-ß phase transition in volcanic cristobalite are investigated using X-ray powder diffraction with simultaneous in situ heating and differential scanning calorimetry. At ambient temperature, volcanic cristobalite exists in the α form and has a larger cell volume than synthetic α-cristobalite; as a result, its diffraction pattern sits between ICDD α- and ß-cristobalite library patterns, which could cause ambiguity in phase identification. On heating from ambient temperature, volcanic cristobalite exhibits a lower degree of thermal expansion than synthetic cristobalite, and it also has a lower α-ß transition temperature (∼473 K) compared with synthetic cristobalite (upwards of 543 K); these observations are discussed in relation to the presence of Al3+ and Na+ defects. The transition shows a stable and reproducible hysteresis loop with α and ß phases coexisting through the transition, suggesting that discrete crystals in the sample have different transition temperatures.

The surface reactivity and implied toxicity of ash produced from sugarcane burning.

Sugarcane combustion generates fine-grained particulate that has the potential to be a respiratory health hazard because of its grain size and composition. In particular, conversion of amorphous silica to crystalline forms during burning may provide a source of toxic particles. In this study, we investigate and evaluate the toxicity of sugarcane ash and bagasse ash formed from commercial sugarcane burning. Experiments to determine the main physicochemical properties of the particles, known to modulate biological responses, were combined with cellular toxicity assays to gain insight into the potential reactions that could occur at the particle-lung interface following inhalation. The specific surface area of the particles ranged from ∼16 to 90 m(2) g(-1) . The samples did not generate hydroxyl- or carbon-centered radicals in cell-free tests. However, all samples were able to 'scavenge' an external source of hydroxyl radicals, which may be indicative of defects on the particle surfaces that may interfere with cellular processes. The bioavailable iron on the particle surfaces was low (2-3 µmol m(-2) ), indicating a low propensity for iron-catalyzed radical generation. The sample surfaces were all hydrophilic and slightly acidic, which may be due to the presence of oxygenated (functional) groups. The ability to cause oxidative stress and membrane rupture in red blood cells (hemolysis) was found to be low, indicating that the samples are not toxic by the mechanisms tested. Cytotoxicity of sugarcane ash was observed, by measuring lactate dehydrogenase release, after incubation of relatively high concentrations of ash with murine alveolar macrophage cells. All samples induced nitrogen oxide release (although only at very high concentrations) and reactive oxygen species generation (although the bagasse samples were less potent than the sugarcane ash). However, the samples induced significantly lower cytotoxic effects and nitrogen oxide generation when compared with the positive control.

Automated mineralogical analysis of PM10: new parameters for assessing PM toxicity.

This work provides the first automated mineralogical/phase assessment of urban airborne PM10 and a new method for determining particle surface mineralogy (PSM), which is a major control on PM toxicity in the lung. PM10 was analyzed on a TEOM filter (Aug.-Sept. 2006 collection) from the London Air Quality Network Bexley, East London, U.K. A cross-section of the filter was analyzed using a QEMSCAN automated mineralogical analysis system which provided 381,981 points of analysis for 14,525 particles over a period of 9 h 54 min. The method had a detection limit for individual mineral components of 0.05 ppm (by area). Particle shape and mineralogical characteristics were determined for particles in the size ranges PM(10-4), PM(4-2.5), and PM(2.5-0.8). The PM(2.5-0.8) fraction contained 2 orders of magnitude more mineral particles than the PM(10-4) and PM(4-2.5) fractions, however the PM(10-4) fraction forms 94% and 79% of the mineral mass and surface area, respectively. PSM of the PM10 was dominated by gypsum (36%), plagioclase (16%), Na sulphates (8%), and Fe-S-O phases (8%) in the PM(10-2.5), which may be important in explaining the toxicity of the coarse fraction. The wider implications of the study are discussed.

Generation of crystalline silica from sugarcane burning.

Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 5558-5565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt% silica, mostly in the form of amorphous silica bodies (with trace impurities e.g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056 degrees C, which is sufficient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt% SiO(2), mostly in an amorphous form, but with up to 3.5 wt% quartz. Both quartz and cristobalite were identified in the sugarcane bagasse ash (5-15 wt% and 1-3 wt%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and cristobalite in bagasse ash is significant as the ash is recycled onto the fields where erosion and/or mechanical disturbance could break down the deposits and re-suspend respirable-sized particulate. Appropriate methods for treatment and disposal of bagasse ash must, therefore, be employed and adequate protection given to workers exposed to these dusts.

Lichen biomonitoring near Karabash smelter town, ural mountains, Russia, one of the most polluted areas in the world.

Biogeochemical signatures were investigated in transplanted and native lichens near a major pollution source using sensitive multi-element chemical analysis. Transplants were established across a 60 km transect centred on the smelter town of Karabash, Ural Mountains, Russia. Statistically significant trends in element concentrations were recorded, some below one part per million. Fine metal particles are accumulated from pollution aerosols. Prolonged exposure may lead to cellular damage and enhanced accumulation or element loss. 206Pb: 207Pb isotope ratios are similar to those associated with airborne particles in Europe and Russia; an outlier near Kyshtym with a lower ratio indicates a source with a higher 235U : 238U ratio. The method is discrete, sensitive, able to detect short-term pollution episodes and useful for understanding element cycling, which is of critical importance for human and environmental health.