Basaltic explosive volcanism: Constraints from deposits and models

Basaltic pyroclastic volcanism takes place over a range of scales and styles, from weak discrete Strombolian explosions (～10²–10³ kg s^?1) to Plinian eruptions of moderate intensity (10⁷–10⁸ kg s^?1). Recent well-documented historical eruptions from Etna, Kīlauea and Stromboli typify this diversity. Etna is Europe's largest and most voluminously productive volcano with an extraordinary level and diversity of Strombolian to subplinian activity since 1990. Kīlauea, the reference volcano for Hawaiian fountaining, has four recent eruptions with high fountaining (>400 m) activity in 1959, 1960, 1969 (–1974) and 1983–1986 (–2008); other summit (1971, 1974, 1982) and flank eruptions have been characterized by low fountaining activity. Stromboli is the type location for mildly explosive Strombolian eruptions, and from 1999 to 2008 these persisted at a rate of ca. 9 per hour, briefly interrupted in 2003 and 2007 by vigorous paroxysmal eruptions. Several properties of basaltic pyroclastic deposits described here, such as bed geometry, grain size, clast morphology and vesicularity, and crystal content are keys to understand the dynamics of the parent eruptions.The lack of clear correlations between eruption rate and style, as well as observed rapid fluctuations in eruptive behavior, point to the likelihood of eruption style being moderated by differences in the fluid dynamics of magma and gas ascent and the mechanism by which the erupting magma fragments. In all cases, the erupting magma consists of a mixture of melt and gaseous bubbles. The depth and rate of degassing, melt rheology, bubble rise and coalescence rates, and extent of syn-eruptive microlite growth define complex feedbacks that permit reversible shifts between fragmentation mechanisms and in eruption style and intensity. However, many basaltic explosive eruptions end after an irreversible shift to open-system outgassing and microlite crystallization in melt within the conduit.Clearer understanding of the factors promoting this diversity of basaltic pyroclastic eruptions is of fundamental importance in order to improve understanding of the range of behaviors of these volcanoes and assess hazards of future explosive events at basaltic volcanoes. The three volcanoes used for this review are the sites of large and growing volcano-tourism operations and there is a public need both for better knowledge of the volcanoes’ behavior and improved forecasting of the likely course of future eruptions.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.     

Low-pressure,water-assisted anatexis of basic dykes in a contact metamorphic aureole,Fuerteventura (Canary Islands): oxygen isotope evidence for a meteoric fluid origin

Migmatites produced by low-pressure anatexis of basic dykes are found in a contact metamorphic aureole around a pyroxenite–gabbro intrusion (PX2), on Fuerteventura. Dykes outside and inside the aureole record interaction with meteoric water, with low or negative δ¹⁸O whole-rock values (+0.2 to −3.4‰), decreasing towards the contact. Recrystallised plagioclase, diopside, biotite and oxides, from within the aureole, show a similar evolution with lowest δ¹⁸O values (−2.8, −4.2, −4.4 and −7.6‰, respectively) in the migmatite zone, close to the intrusion. Relict clinopyroxene phenocrysts preserved in all dykes, retain typically magmatic δ¹⁸O values up to the anatectic zone, where the values are lower and more heterogeneous. Low δ¹⁸O values, decreasing towards the intrusion, can be ascribed to the advection of meteoric water during magma emplacement, with increasing fluid/rock ratios (higher dyke intensities towards the intrusion acting as fluid-pathways) and higher temperatures promoting increasing exchange during recrystallisation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Enhancing understanding of breakdown and collapse in the Yorkshire Dales using ground penetrating radar on cave sediments

Historical evidence shows block breakdown and collapse are actively occurring in large fault aligned caverns in the Yorkshire Dales karst. Deployment of ground penetrating radar at two such sites has provided detailed images of the sedimentary sequences below the present day cavern floor but no large blocks are imaged within the sediments. Solutional processes must be removing limestone from the sediment to allow continued cavern growth. Possible mechanisms to account for the lack of large blocks within the sediment fill are discussed.     

Shear strength characterization of municipal solid waste at the Suzhou landfill, China

The current practice of slope stability analysis for a municipal solid waste (MSW) landfill usually overlooks the dependence of waste properties on the fill age or embedment depth. Changes in shear strength of MSW as a function of fill age were investigated by performing field and laboratory studies on the Suzhou landfill in China. The field study included sampling from five boreholes advanced to the bottom of the landfill, cone penetration tests and monitoring of pore fluid pressures. Twenty-six borehole samples representative of different fill ages (0 to 13 years) were used to perform drained triaxial compression tests. The field and laboratory study showed that the waste body in the landfill can be sub-divided into several strata corresponding to different ranges of fill age. Each of the waste strata has individual composition and shear strength characteristics. The triaxial test results showed that the MSW samples exhibited a strain-hardening and contractive behavior. As the fill age of the waste increased from 1.7 years to 11 years, the cohesion mobilized at a strain level of 10% was found to decrease from 23.3 kPa to 0 kPa, and the mobilized friction angle at the same strain level increasing from 9.9° to 26°. For a confinement stress level greater than 50 kPa, the shear strength of the recently-placed MSW seemed to be lower than that of the older MSW. This behavior was consistent with the cone penetration test results. The field measurement of pore pressures revealed a perched leachate mound above an intermediate cover of soils and a substantial leachate mound near the bottom of the landfill. The measurements of shear strength properties and pore pressures were utilized to assess the slope stability of the Suzhou landfill.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.