The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

High temperature behavior of electrostatic precipitator ash from municipal solid waste combustors

International audienceMunicipal solid waste (MSW) flue gas residues require further treatment prior to disposal or reuse, and vitrification is one of the main solidification-stabilization processes.This paper investigates the high temperature behavior of MSW flue gas residues, performed in laboratory experiments up to 1400°C, and coupled with thermogravimetric analyses, X-ray diffraction, chemical and electron microprobe analyses. Melting temperatures of electrostatic precipitator (ESP) ash are in the range of 1202-1272 °C, whereas semi-dry scrubber residues melt between 1900 and 2300 °C. The mean liquidus temperature of flue gas residues can be simply evaluated as a function of their CaO content, by using the CaO-SiO2-Al2O3 ternary diagram. For ESP ash, the liquidus phase is a Zn-rich aluminous spinel, followed by anorthite at 1225 °C, and melilite at 1190 °C. The total mass loss reaches 18 wt.% at 1300 °C. Moreover, 90% of evaporation takes place below 1000 °C, linked to evaporation of C, Cl, S, Na, K, and of the toxic metals Hg, Cd, Pb, Cu. Due to the high partial pressure of chlorine during heating, chloride is the most probable form of evaporation for Cd, Pb, and Cu. However, most of Zn, Cr, Ni, Sb and Sn remain in the vitrified product

The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

Lead Isotopic Composition of Fly Ash and Flue Gas Residues from Municipal Solid Waste Combustors in France: Implications for Atmospheric Lead Source Tracing.

Fly ash and flue gas residues from eight municipal solid waste combustors (MSWC) in France (1992-93 and 1998/2002) were analyzed for their Pb isotopic composition. Fly ashes are more representative of solid residual particles, whereas flue gas residues reflect mostly the composition of gas phases. Both sample types contain hundreds to thousands of micrograms of metals per gram. Leaching experiments showed that metals are present in condensed phases, probably as sulfates and chlorides, and suggest that Cd, Pb, and Zn are highly fractionated from one another during volatilization/condensation processes occurring during combustion. Although all the samples analyzed define a fairly restricted range in Pb isotopic compositions (206Pb/207Pb = 1.148-1.158 and 208Pb/206Pb = 2.101-2.114) compared to other environmental samples, some MSWC produce materials having distinct isotopic compositions, whereas others display very similar ones. Isotopic heterogeneity is also measured between samples from a single MSWC. This is interpreted as resulting from the heterogeneity of the waste source materials. The range of Pb isotopic composition of incinerator materials form a well-defined linear array in the 208Pb/206Pb versus 206Pb/207Pb diagram. This array is compatible with the previously reported European standard pollution (ESP) line and most probably represent the average lead isotopic composition of industrial atmospheric emissions in France, with the following ratios: 206Pb/207Pb = 1.154 ± 0.003 and 208Pb/206Pb = 2.107 ± 0.003 (1)

Vapor-Melt Exchange -- Constraints on Chondrite Formation Conditions and Processes

The bulk volatile contents of chondritic meteorites provide clues to their origins. Matrix and chondrules carry differing abundances of moderately volatile elements, with chondrules carrying a refractory signature. At the high temperatures of chondrule formation and the low pressures of the solar nebula, many elements, including Na and Fe, should have been volatile. Yet the evidence is that even at peak temperatures, at or near the liquidus, Na and Fe (as FeO and Fe-metal) were present in about their current abundances in molten chondrules. This seems to require very high solid densities during chondrule formation to prevent significant evaporation. Evaporation should also be accompanied by isotopic mass fractionation. Evidence from a wide range of isotopic systems indicates only slight isotopic mass fractionations of moderately vola-tile elements, further supporting high solid densities. However, olivine-rich, FeO-poor chondrules commonly have pyroxene-dominated outer zones that have been interpreted as the prod-ucts of late condensation of SiO2 into chondrule melts. Late condensation of more refractory SiO2 is inconsistent with the apparent abundances of more volatile Na, FeO and Fe-metal in many chondrules. Despite significant recent experimental work bearing on this problem, the conditions under which chondrules behaved as open systems remain enigmatic

Assessment of diseases susceptibility of peach cultivars in experimental plots and on-farm for organic and low-input systems. Baseline of French case studies

Despite a high turn-over of new peach cultivars, their suitability for organic and low-input systems remains unknown for most of them. Diseases susceptibility is an important criteria to consider since diseases control is a bottleneck to peach production in theses systems. Since 2001, 81 peach cultivars were assessed in 2 experimental sites and 7 on-farm plots

Thermal fatigue as the origin of regolith on small asteroids

Space missions and thermal infrared observations3 have shown that small asteroids (kilometre-sized or smaller) are covered by a layer of centimetre-sized or smaller particles, which constitute the regolith. Regolith generation has traditionally been attributed to the fall back of impact ejecta and by the break-up of boulders bymicrometeoroid impact. Laboratory experiments6 and impact models, however, show that crater ejecta velocities are typically greater than several tens of centimetres per second,which corresponds to the gravitational escape velocity of kilometre-sized asteroids.Therefore, impact debris cannot be the main source of regolith on small asteroids. Here we report that thermal fatigue, a mechanism of rock weathering and fragmentation with no subsequent ejection, is the dominant process governing regolith generation on small asteroids.We find that thermal fragmentation induced by the diurnal temperature variations breaks up rocks larger than a few centimetres more quickly than do micrometeoroid impacts. Because thermal fragmentation is independent of asteroid size, this process can also contribute to regolith production on larger asteroids. Production of fresh regolith originatingin thermal fatigue fragmentationmay be an important process for the rejuvenation of the surfaces of near-Earth asteroids, and may explain the observed lack of low-perihelion, carbonaceous, near-Earth asteroids

Evolution of oxygen isotopic composition in the inner solar nebula

Changes in the chemical and isotopic composition of the solar nebula with time are reflected in the properties of different constituents that are preserved in chondritic meteorites. CR carbonaceous chondrites are among the most primitive of all chondrite types and must have preserved solar nebula records largely unchanged. We have analyzed the oxygen and magnesium isotopes in a range of the CR constituents of different formation temperatures and ages, including refractory inclusions and chondrules of various types. The results provide new constraints on the time variation of the oxygen isotopic composition of the inner (<5 AU) solar nebula - the region where refractory inclusions and chondrules most likely formed. A chronology based on the decay of short-lived 26Al (t1/2 ~ 0.73 Ma) indicates that the inner solar nebula gas was 16O-rich when refractory inclusions formed, but less than 0.8 Ma later, gas in the inner solar nebula became 16O-poor and this state persisted at least until CR chondrules formed ~1-2 Myr later. We suggest that the inner solar nebula became 16O-poor because meter-size icy bodies, which were enriched in 17,18O due to isotopic self-shielding during the ultraviolet photo dissociation of CO in the protosolar molecular cloud or protoplanetary disk, agglomerated outside the snowline, drifted rapidly towards the Sun, and evaporated at the snowline. This led to significant enrichment in 16O-depleted water, which then spread through the inner solar system. Astronomical studies of the spatial and/or temporal variations of water abundance in protoplanetary disks may clarify these processes.Comment: 27 pages, 5 figure

Magmatic sulfides in the porphyritic chondrules of EH enstatite chondrites

The nature and distribution of sulfides within 17 porphyritic chondrules of the Sahara 97096 EH3 enstatite chondrite have been studied by backscattered electron microscopy and electron microprobe in order to investigate the role of gas–melt interactions in the chondrule sulfide formation. Troilite (FeS) is systematically present and is the most abundant sulfide within the EH3 chondrite chondrules. It is found either poikilitically enclosed in low-Ca pyroxenes or scattered within the glassy mesostasis. Oldhamite (CaS) and niningerite [(Mg,Fe,Mn)S] are present in ≈60% of the chondrules studied. While oldhamite is preferentially present in the mesostasis, niningerite associated with silica is generally observed in contact with troilite and low-Ca pyroxene. The Sahara 97096 chondrule mesostases contain high abundances of alkali and volatile elements (average Na2O = 8.7 wt.%, K2O = 0.8 wt.%, Cl = 7100 ppm and S = 3700 ppm) as well as silica (average SiO2 = 62.8 wt.%). Our data suggest that most of the sulfides found in EH3 chondrite chondrules are magmatic minerals that formed after the dissolution of S from a volatile-rich gaseous environment into the molten chondrules. Troilite formation occurred via sulfur solubility within Fe-poor chondrule melts followed by sulfide saturation, which causes an immiscible iron sulfide liquid to separate from the silicate melt. The FeS saturation started at the same time as or prior to the crystallization of low-Ca pyroxene during the high temperature chondrule forming event(s). Protracted gas–melt interactions under high partial pressures of S and SiO led to the formation of niningerite-silica associations via destabilization of the previously formed FeS and low-Ca pyroxene. We also propose that formation of the oldhamite occurred via the sulfide saturation of Fe-poor chondrule melts at moderate S concentration due to the high degree of polymerization and the high Na-content of the chondrule melts, which allowed the activity of CaO in the melt to be enhanced. Gas–melt interactions thus appear to be a key process that may control the mineralogy of chondrules in the different classes of chondrite