ESEEM of industrial quartz powders: insights into crystal chemistry of Al defects

A set of raw industrial materials, that is, pure quartz and quartz-rich mixtures, were investigated through electron paramagnetic resonance and electron spin echo-envelope modulation spectroscopies, with the aim of evaluating the effective role played by defect centres and of assessing whether they can be used to monitor changes in the physical properties of quartz powders with reference to their health effects. The obtained results point to two interactions of the Al defect centres with H⁺, hosted in sites within the channels parallel and perpendicular to the c axis of quartz, respectively. These two Al/H⁺ (h_Al) centres exhibit a weak chemical bond, and their relative amounts appear to be modified/controlled by the thermo-mechanical processes underwent by powders. Indeed, a mechanically promoted inter-conversion between the two kinds of site is suggested. As a consequence, the h_Al centres are effective in monitoring even modest activations of powders, through thermal or mechanical processes, and they are also supposed to play a specific, relevant role in quartz reactivity during the considered industrial processes.     

Shoshonite and sub-alkaline magmas from an ultrapotassic volcano: Sr–Nd–Pb isotope data on the Roccamonfina volcanic rocks,Roman Magmatic Province,Southern Italy

The Roccamonfina volcano is characterised by two stages of volcanic activity that are separated by volcano-tectonic caldera collapses. Ultrapotassic leucite-bearing rocks are confined to the pre-caldera stage and display geochemical characteristics similar to those of other volcanoes in the Roman Province. After the major sector collapse of the volcano, occurred at ca. 400 ka, shoshonitic rocks erupted from cinder cones and domes both within the caldera and on the external flanks of the pre-caldera Roccamonfina volcano. On the basis of new trace element and Sr–Nd–Pb isotope data, we show that the Roccamonfina shoshonitic rocks are distinct from shoshonites of the Northern Roman Province, but are very similar to those of the Neapolitan volcanoes. The last phases of volcanic activity erupted sub-alkaline magmas as enclaves in trachytic domes, and as lavas within the Monte Santa Croce dome. Ultrapotassic rocks of the pre-caldera composite volcano are plagioclase-bearing leucitites characterised by high levels of incompatible trace elements with an orogenic signature having troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of ⁸⁷Sr/⁸⁶Sr range from 0.70926 to 0.70999, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51213 to 0.51217, while the lead isotope rations vary between 18.788–18.851 for ²⁰⁶Pb/²⁰⁴Pb, 15.685–15.701 for ²⁰⁷Pb/²⁰⁴Pb, and 39.048–39.076 for ²⁰⁸Pb/²⁰⁴Pb. Shoshonites show a similar pattern of trace element depletions and enrichments to the earlier ultrapotassic leucite-bearing rocks but have a larger degree of differentiation and lower concentrations of incompatible trace elements. On the other hand, shoshonitic rocks have Sr, Nd, and Pb isotopes consistently different than pre-caldera ultrapotassic leucite-bearing rocks. ⁸⁷Sr/⁸⁶Sr ranges from 0.70665 to 0.70745, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51234 to 0.51238, ²⁰⁶Pb/²⁰⁴Pb ranges from 18.924 to 19.153, ²⁰⁷Pb/²⁰⁴Pb ranges from 15.661 to 15.694, and ²⁰⁸Pb/²⁰⁴Pb ranges from 39.084 to 39.212. High-K calc-alkaline samples have intermediate isotopic values between ultrapotassic plagioclase leucitites and shoshonites, but the lowest levels of incompatible trace element contents. It is argued that ultrapotassic magmas were generated in a modified lithospheric mantle after crustal-derived metasomatism. Interaction between the metasomatic agent and lithospheric upper mantle produced a low-melting point metasomatised veined network. The partial melting of the veins alone produced pre-caldera leucite-bearing ultrapotassic magmas. It was possibly triggered by either post-collisional isotherms relaxation or increasing T°C due increasing heat flow through slab tears. Shoshonitic magmas were generated by further melting, at higher temperature, of the same metasomatic assemblage with addition 10–20% of OIB-like astenospheric mantle material. We suggest that addition of astenospheric upper mantle material from foreland mantle, flowing through slab tearing after collision was achieved. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Volcanoes and human history

The study of volcanic hazards leads inevitably to questions of how past cultures have lived in volcanically active regions of the world. Here we summarize linkages between volcanological, archaeological and anthropological studies of historic and prehistoric volcanic eruptions, with the goal of evaluating the impact of past eruptions on human populations to better prepare for future events. We use examples from papers collected in this volume to illustrate ways in which volcanological studies aid archaeological investigations by providing basic stratigraphic markers and information about the nature and timing of specific volcanic events. We then turn to archaeological perspectives, which provide physical evidence of the direct impacts of volcanic eruptions, such as site abandonment and human migration, as well as indirect impacts on local cultures as reflected in human artifacts. Finally we review anthropological studies of societal responses to past and recent volcanic eruptions. We pay particular attention to both the psychological impact of catastrophic events and records of these impacts encoded within oral traditions. Taken together these studies record drastic short-term eruption impacts but adaptation to volcanic activity over the longer term, largely through strategies of adaptive land use.     

High-temperature emplacement of the Cerro Galán and Toconquis Group ignimbrites (Puna plateau,NW Argentina) determined by TRM analyses

Estimates of pyroclastic flow emplacement temperatures in the Cerro Galán ignimbrite and Toconquis Group ignimbrites were determined using thermal remanent magnetization of lithic clasts embedded within the deposits. These ignimbrites belong to the Cerro Galán volcanic system, one of the largest calderas in the world, in the Puna plateau, NW Argentina. Temperature estimates for the 2.08-Ma Cerro Galán ignimbrite are retrieved from 40 sites in 14 localities (176 measured clasts), distributed at different distances from the caldera and different stratigraphic heights. Additionally, temperature estimates were obtained from 27 sample sites (125 measured clasts) from seven ignimbrite units forming the older Toconquis Group (5.60–4.51 Ma), mainly outcropping along a type section at Rio Las Pitas, Vega Real Grande. The paleomagnetic data obtained by progressive thermal demagnetization show that the clasts of the Cerro Galán ignimbrite have one single magnetic component, oriented close to the expected geomagnetic field at the time of emplacement. Results show therefore that most of the clasts acquired a new magnetization oriented parallel to the magnetic field at the moment of the ignimbrite deposition, suggesting that the clasts were heated up to or above the highest blocking temperature (T _b) of the magnetic minerals (T _b = 580°C for magnetite; T _b = 600–630°C for hematite). We obtained similar emplacement temperature estimations for six out of the seven volcanic units belonging to the Toconquis Group, with the exception of one unit (Lower Merihuaca), where we found two distinct magnetic components. The estimation of emplacement temperatures in this latter case is constrained at 580–610°C, which are lower than the other ignimbrites. These estimations are also in agreement with the lowest pre-eruptive magma temperatures calculated for the same unit (i.e., 790°C; hornblende–plagioclase thermometer; Folkes et al. 2011b). We conclude that the Cerro Galán ignimbrite and Toconquis Group ignimbrites were emplaced at temperatures equal to or higher than 620°C, except for Lower Merihuaca unit emplaced at lower temperatures. The homogeneity of high temperatures from proximal to distal facies in the Cerro Galán ignimbrite provides constraints for the emplacement model, marked by a relatively low eruption column, low levels of turbulence, air entrainment, surface–water interaction, and a high level of topographic confinement, all ensuring minimal heat loss.     

The Cloud Ice Mountain Experiment (CIME) 1998: experiment overview and modelling of the microphysical processes during the seeding by isentropic gas expansion

The second field campaign of the Cloud Ice Mountain Experiment (CIME) project took place in February 1998 on the mountain Puy de Dôme in the centre of France. The content of residual aerosol particles, of H₂O₂ and NH₃ in cloud droplets was evaluated by evaporating the drops larger than 5 μm in a Counterflow Virtual Impactor (CVI) and by measuring the residual particle concentration and the released gas content. The same trace species were studied behind a round jet impactor for the complementary interstitial aerosol particles smaller than 5 μm diameter. In a second step of experiments, the ambient supercooled cloud was converted to a mixed phase cloud by seeding the cloud with ice particles by the gas release from pressurised gas bottles. A comparison between the physical and chemical characteristics of liquid drops and ice particles allows a study of the fate of the trace constituents during the presence of ice crystals in the cloud.In the present paper, an overview is given of the CIME 98 experiment and the instrumentation deployed. The meteorological situation during the experiment was analysed with the help of a cloud scale model. The microphysics processes and the behaviour of the scavenged aerosol particles before and during seeding are analysed with the detailed microphysical model ExMix. The simulation results agreed well with the observations and confirmed the assumption that the Bergeron–Findeisen process was dominating during seeding and was influencing the partitioning of aerosol particles between drops and ice crystals. The results of the CIME 98 experiment give an insight on microphysical changes, redistribution of aerosol particles and cloud chemistry during the Bergeron–Findeisen process when acting also in natural clouds.     

Behaviour of H2O2, NH3, and black carbon in mixed-phase clouds during CIME

We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H₂O₂, NH₃ and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H₂O₂ and NH₃ are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H₂O₂ is driven by co-condensation with water vapour onto ice crystals while NH₃ uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH₄⁺ in the ice could explain this result. Finally, it appears that the H₂O₂–SO₂ reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.     

Viscosity of hydrous Etna basalt: implications for Plinian-style basaltic eruptions

Water dissolved in a silicate melt can strongly influence its physical properties and thus magma behavior during crystallization, degassing, foaming and fragmentation. Etna is a basaltic volcano whose activity is dominated by effusive eruptions which have long represented a threat to the densely populated, surrounding area. Recently, recognition of the products of a Plinian eruption (122 B.C.) has raised further issues for hazard assessment at Etna and other basaltic volcanoes. Constraining the behavior of Etna magma under conditions relevant to both effusive and explosive hazards requires viscosity data under conditions near the glass transition. Here we have investigated the viscosity of hydrous Etna lava in order to better understand eruptive processes which characterize this volcano. The experimental methods which have been used include piston cylinder synthesis of the hydrated melts, micropenetration viscometry for low-temperature viscosity measurements, and near-infrared spectroscopy for the evaluation of sample homogeneity and measurements of water content. Additionally, scanning calorimetric determinations were performed to check whether incipient crystallization had occurred. Sample compositions were determined using electron microprobe analysis and ⁵⁷Fe Mössbauer spectroscopy. Results from this study are compared with previous reports of trachytic, phonolitic and model calc-alkaline rhyolite (HPG8) compositions. The viscosity of the basaltic melt (dry and wet) has been parameterized in terms of temperature and water content via the non-Arrhenian equation: log₁₀-=-4.643+(5,812.44-427.042H₂O)/(T(K)-499.31+28.742ln(H₂O)) where - is the viscosity in Pa s, H₂O is the water content in wt%, and T is the temperature in Kelvin. We observe that the viscosity of alkali basalt (at more than 0.5 wt% H₂O) is similar to that of an alkaline trachyte (Agnano-Monte Spina eruption, Phlegrean Fields) and much higher than that of a peralkaline phonolite (Teide, Tenerife) at similar silica contents and NBO/T. For water contents above 1.5 wt%, the viscosity of the basalt is similar to that of rhyolitic melts with similar water contents. At temperatures ranging from 1,050 to 1,150 °C and with water contents between 0.5 and 2.3 wt% (eruptive conditions), the viscosities calculated using the equation defined in this study are (1) in reasonable agreement with those calculated using Shaw's model, and (2) much lower than those experimentally determined in a previous study. However, outside these temperature and water content ranges, the agreement with Shaw's model (1972) breaks down.     

Volcanology,history and myths of the Lake Albano maar (Colli Albani volcano,Italy)

The polygenetic Albano maar is the most recent centre of the Colli Albani volcano, located just few kilometres to the south-east of Roma. Presently the maar hosts a 167.5 m deep crater lake, the deepest in Europe. The maar is to be considered quiescent, as phreatic activity is documented throughout the Holocene. This paper illustrates the close relationships between the activity of the maar and the history of settlement in the Roman region as recorded in the geology, archaeology, history and legends of the area. Severe fluctuations of the groundwater table and catastrophic overflows of the Lake Albano from the maar rim had occurred prior to and after the early prehistoric settlements dated in the maar area at the Eneolithic times (ca. III millennium B.C.). Repeated lahars occurred along the northwestern slope of the maar filling in the paleodrainage network and forming a vast plain. Paleohydraulic analyses on fluvial and lahar deposits originated from the Holocene phreatic activity of the Albano maar indicate sediment–water flows in excess of hundreds of cubic metres per second. Absolute age determinations of the paleosoil underlying one of the most recent deposits of the lahar succession at 5800 ± 100 yr B.P. (¹⁴C CAL) are in perfect agreement with the age of the overlying Eneolithic age settlements. The last catastrophic overflow is described in the Roman literature as a consequence of the anger of Poseidon against the Romans in 398 B.C. for their war against the Etruscans. In 394 B.C. the Romans decided to prevent the repetition of such events by the excavation through the maar crater wall of a 1.5 km long drain tunnel, which is still operational, keeping the lake 70 m below the lowest point of the maar rim. This tunnel drain may be regarded as the first prevention device for volcanic hazard in history and shows an unprecedented development of the engineering technology under the pressure of hazard perception. The surprising and still largely unknown results of this study are very important to redefine the hazard of the Roman region.     

Modeling ground deformations of Panarea volcano hydrothermal/geothermal system (Aeolian Islands, Italy) from GPS data

Panarea volcano (Aeolian Islands, Italy) was considered extinct until November 3, 2002, when a submarine gas eruption began in the area of the islets of Lisca Bianca, Bottaro, Lisca Nera, Dattilo, and Panarelli, about 2.5 km east of Panarea Island. The gas eruption decreased to a state of low degassing by July 2003. Before 2002, the activity of Panarea volcano was characterized by mild degassing of hydrothermal fluid. The compositions of the 2002 gases and their isotopic signatures suggested that the emissions originated from a hydrothermal/geothermal reservoir fed by magmatic fluids. We investigate crustal deformation of Panarea volcano using the global positioning system (GPS) velocity field obtained by the combination of continuous and episodic site observations of the Panarea GPS network in the time span 1995–2007. We present a combined model of Okada sources, which explains the GPS results acquired in the area from December 2002. The kinematics of Panarea volcano show two distinct active crustal domains characterized by different styles of horizontal deformation, supported also by volcanological and structural evidence. Subsidence on order of several millimeters/year is affecting the entire Panarea volcano, and a shortening of 10⁻⁶ year⁻¹ has been estimated in the Islets area. Our model reveals that the degassing intensity and distribution are strongly influenced by geophysical-geochemical changes within the hydrothermal/geothermal system. These variations may be triggered by changes in the regional stress field as suggested by the geophysical and volcanological events which occurred in 2002 in the Southern Tyrrhenian area.     

The Holocene Secche di Lazzaro phreatomagmatic succession (Stromboli,Italy): evidence of pyroclastic density current origin deduced by facies analysis and AMS flow directions

The edifice of Stromboli volcano gravitationally collapsed several times during its volcanic history (>100 ka–present). The largest Holocene event occurred during the final stage of the Neostromboli activity (∼13–5 ka), and was accompanied by the emplacement of phreatomagmatic and lahar deposits, known as the Secche di Lazzaro succession. A stratigraphic and paleomagnetic study of the Secche di Lazzaro deposits allows the interpretation of the emplacement and the eruptive processes. We identify three main units within the succession that correspond to changing eruption conditions. The lower unit (UA) consists of accretionary lapilli-rich, thinly bedded, parallel- to cross-stratified ash deposits, interpreted to indicate the early stages of the eruption and emplacement of dilute pyroclastic density currents. Upward, the second unit (UB) of the deposit is more massive and the beds thicker, indicating an increase in the sedimentation rate from pyroclastic density currents. The upper unit (UC) caps the succession with thick, immediately post-eruptive lahars, which reworked ash deposited on the volcano’s slope. Flow directions obtained by Anisotropy of Magnetic Susceptibility (AMS) analysis of the basal bed of UA at the type locality suggest a provenance of pyroclastic currents from the sea. This is interpreted to be related to the initial base-surges associated with water–magma interaction that occurred immediately after the lateral collapse, which wrapped around the shoulder of the sector collapse scar. Upward in the stratigraphy (upper beds of UA and UB) paleoflow directions change and show a provenance from the summit vent, probably related to the multiple collapses of a vertical, pulsatory eruptive column.