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  • kinetics  (286)
  • 04. Solid Earth::04.06. Seismology::04.06.05. Historical seismology
  • 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
  • 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
  • Mt. Etna
  • Springer  (305)
  • Springer-Verlag  (6)
  • Copernicus  (2)
  • EGU
  • Essen : Verl. Glückauf
  • Institute of Physics
  • 2010-2014  (28)
  • 1995-1999  (287)
Collection
Keywords
Years
Year
  • 1
    Publication Date: 2017-04-04
    Description: Here, we report the first continuous data of geochemical parameters acquired directly from the active summit crater of Vulcano. This approach provides a means to better investigate deep geochemical processes associated with the degassing system of Vulcano Island. In particular, we report on soil CO2 fluxes from the upper part of Vulcano, a closed-conduit volcano, from September 2007 to October 2010. Large variations in the soil CO2 and plume SO2 fluxes (order of magnitude), coinciding with other discontinuous geochemical parameters (CO2 concentrations in fumarole gas) and physical parameters (increase of shallow seismic activity and fumarole temperatures) have been recorded. The results from this work suggest new prospects for strengthening geochemical monitoring of volcanic activity and for improving the constraints in the construction of a “geochemical model”, this being a necessary condition to better understand the functioning of volcanic systems.
    Description: Published
    Description: 1859-1863
    Description: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Description: 4V. Vulcani e ambiente
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: 1R. Reti di monitoraggio e Osservazioni
    Description: JCR Journal
    Description: restricted
    Keywords: Vulcano Island ; Geochemical monitoring ; CO2 flux ; CO2 fumaroles ; SO2 flux ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2017-04-04
    Description: Ash fallout collected during 4 days of sampling at Stromboli confirms that a crystal-rich (HP) degassed magma erupts during the Strombolian explosions that are characteristic of the normal activity of this volcano. We identified 3 different types of juvenile ash fragments (fluidal, spongy and dense), which formed through different mechanisms of fragmentation of the low-viscosity, physically heterogeneous (in terms of the size and spatial distribution of bubbles) shoshonitic magma. A small amount (less than 3 vol%) of volatile-rich magma with low porphyricity (LP), erupted as highly vesicular ash fragments, has been collected, together with the HP magma, during normal strombolian explosions. Laboratory experiments and the morphological, textural and compositional investigations of ash fragments reveal that the LP ash is fresh and not recycled from the last paroxysm (15 March 2007). We suggest that small droplets of LP magma are dragged to the surface by the time-variable but persistent supply of deep derived CO2-rich gas bubbles. This coupled ascent of bubbles and LP melts is transient and does not perturb the dynamics of the HP magma within the shallow reservoir. This finding provides a new perspective on how the Stromboli volcano works and has important implications for monitoring strategies.
    Description: Published
    Description: 471-477
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli ; Strombolian activity ; Ash ; Paroxysms ; Clast morphology ; Glass chemistry ; Bubble ascent ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2017-04-04
    Description: Recent stratigraphic studies at Vesuvius have revealed that, during the past 4,000 years, long lasting, moderate to low-intensity eruptions, associated with continuous or pulsating ash emission, have repeatedly occurred. The present work focuses on the AS1a eruption, the first of a series of ash-dominated explosive episodes which characterized the period between the two Subplinian eruptions of 472 AD and 1631 AD. The deposits of this eruption consist of an alternation of massive and thinly laminated ash layers and minor well sorted lapilli beds, reflecting the pulsatory injection into the atmosphere of variably concentrated ash-plumes alternating with Violent Strombolian stages. Despite its nearly constant chemical composition, the juvenile material shows variable external clast morphologies and groundmass textures, reflecting the fragmentation of a magma body with lateral and/or vertical gradients in both vesicularity and crystal content. Glass compositions and mineralogical assemblages indicate that the eruption was fed by rather homogeneous phonotephritic magma batches rising from a reservoir located at ~ 4 km (100 MPa) depth, with fluctuations between magma delivery and magma discharge. Using crystal size distribution (CSD) analyses of plagioclase and leucite microlites, we estimate that the transit time of the magma in the conduit was on the order of ~ 2 days, corresponding to an ascent rate of around 2 × 10−2 ms−1. Accordingly, assuming a typical conduit diameter for this type of eruption, the minimum duration of the AS1a event is between about 1.5 and 6 years. Magma fragmentation occurred in an inertially driven regime that, in a magma with low viscosity and surface tension, can act also under conditions of slow ascent.
    Description: Published
    Description: 699-715
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Ash emission activity ; Tephrite ; Vesuvius ; Stratigraphy ; Textural analyses ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2017-04-04
    Description: Using a lava flow emplacement model and a satellite-based land cover classification, we produce a map to allow assessment of the type and quantity of natural, agricultural and urban land cover at risk from lava flow invasion. The first step is to produce lava effusion rate contours, i.e., lines linking distances down a volcano’s flank that a lava flow will likely extend if fed at a given effusion rate from a predetermined vent zone. This involves first identifying a vent mask and then running a downhill flow path model from the edge of every pixel around the vent mask perimeter to the edge of the DEM. To do this, we run a stochastic model whereby the flow path is projected 1,000 times from every pixel around the vent mask perimeter with random noise being added to the DEM with each run so that a slightly different flow path is generated with each run. The FLOWGO lava flow model is then run down each path, at a series of effusion rates, to determine likely run-out distance for channel-fed flow extending down each path. These results are used to plot effusion rate contours. Finally, effusion rate contours are projected onto a land classification map (produced from an ASTER image of Etna) to assess the type and amount of each land cover class falling within each contour. The resulting maps are designed to provide a quick look-up capability to assess the type of land at risk from lava extending from any location at a range of likely effusion rates. For our first (2,000 m) vent zone case used for Etna, we find a total of area of ~680 km2 is at risk from flows fed at 40 m3 s−1, of which ~6 km2 is urban, ~150 km2 is agriculture and ~270 km2 is grass/woodland. The model can also be run for specific cases, where we find that Etna’s 1669 vent location, if active today, would likely inundate almost 11 km2 of urban land, as well as 15.6 km2 of agricultural land, including 9.5 km2 of olive groves and 5.2 km2 of vineyards and fruit/nut orchards.
    Description: Published
    Description: 1001-1027
    Description: 3.6. Fisica del vulcanismo
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Lava flow ; Risk ; FLOWGO ; ASTER image ; Land classification ; Mt. Etna ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
    Publication Date: 2017-04-04
    Description: The persistent normal activity of Stromboli is occasionally interrupted by sudden and highly energetic explosive events called Strombolian paroxysms. These phenomena together with landslide-generated tsunamis represent the most hazardous manifestations of present-day volcanic activity at Stromboli. The most recent paroxysms, on 5 April 2003 and 15 March 2007, have drawn attention to these energetic events because they significantly threatened inhabitants and tourists. Historical accounts and field evidence indicate, however, that even larger paroxysms, in terms of volume, dispersal of products and intensity of explosive phenomena, occurred in the recent past. During these paroxysms incipiently welded spatter deposits mantled the north and south rims of the Sciara del Fuoco down to low elevations, extending much farther than the similar deposits from recent observed events (5 April 2003 and 15 March 2007). In order to identify, characterize and discriminate among products of these outstanding spatter-forming eruptions, more than 50 stratigraphic sections were measured and sampled. Stratigraphic, sedimentological and radiometric (14C) data indicate that only two paroxysms produced spatter that reached very low elevations and inhabited areas: the first occurred in the 16th century and the last in AD 1930. Analysis of texture and deposit components reveals that the early phases of the two eruptions were driven by distinctly different eruptive dynamics. Both identified paroxysms are at least one order of magnitude greater than any similar event observed by monitoring systems at Stromboli. These two large paroxysms were the most powerful volcanic events at Stromboli in the last eighteen centuries.
    Description: Published
    Description: 1229-1243
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli ; Paroxysms ; Spatter ; Basaltic explosive volcanism ; Volcanic hazard ; 04. Solid Earth::04.04. Geology::04.04.10. Stratigraphy ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
    Publication Date: 2017-04-04
    Description: Seismic activity, ground deformation, and soil and fumarole temperatures acquired during 2004–2007 at Vulcano (Aeolian Islands) are analysed and the time relations among the different time series are discussed. Changes in temperature of fumarolic gases took place during four ‘‘anomalous’’ periods (November 2004–March 2005; October 2005–February 2006; August–October 2006; July–December 2007) at the same time as an increasing number of volcano-seismic events. In particular, the temperatures at high temperature vents and at steam heated soil ranged in time from 180 to 440 C and from 20 to 90 C, respectively. The maximum daily number of volcano-seismic events was 57, reached during the second anomalous period. This seismicity, characterised by focal depth generally lower than 1 km below sea level (b.s.l.) and composed of different kinds of events associated to both resonance and shear failure processes, is related to the shallow dynamics of the hydrothermal system. During the analysed period, very few volcano-tectonic earthquakes took place and tilt recordings showed no sharp or important changes. In light of such observations, the increases in both temperature and volcano-seismic events number were associated to increases in the release of gas from a deep and stable magma body, without magma intrusions within the shallow hydrothermal system. Indeed, a greater release of gas from depth leads to increased fluid circulation, that can promote increases in volcano-seismic events number by both fracturing processes and resonance and vibration in cracks and conduits. The different trends observed in the measured geochemical and geophysical series during the anomalous periods can be due to either time changes in the medium permeability or a changing speed of gas release from a deep magma body. Finally, all the observed variations, together with the changing temporal distribution of the different seismic event kinds, suggest that the hydrothermal system at Vulcano can be considered unsteady and dynamic.
    Description: Published
    Description: 167–182
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: JCR Journal
    Description: reserved
    Keywords: Volcano seismolog ; soil and fumarole temperatures ; tilt data ; hydrothermal system ; Vulcano Island ; volcanic unrest ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2020-02-24
    Description: Explosions of hot water, steam, and gas are common periodic events of subaerial geothermal systems. These highly destructive events may cause loss of life and substantial damage to infrastructure, especially in densely populated areas and where geothermal systems are actively exploited for energy. We report on the occurrence of a large number of explosion craters associated with the offshore venting of gas and thermal waters at the volcanic island of Panarea, Italy, demonstrating that violent explosions similar to those observed on land also are common in the shallow submarine environment. With diameters ranging from 5 to over 100 m, the observed circular seafloor depressions record a history of major gas explosions caused by frequent perturbation of the submarine geothermal system over the past 10,000 years. Estimates of the total gas flux indicate that the Panarea geothermal system released over 70 Mt of CO2 over this period of time, suggesting that CO2 venting at submerged arc volcanoes contributes significantly to the global atmospheric budget of this greenhouse gas. The findings at Panarea highlight that shallow submarine gas explosions represent a previously unrecognized volcanic hazard around populated volcanic islands that needs to be taken into account in the development of risk management strategies.
    Description: Published
    Description: 1937-1944
    Description: 1.3. TTC - Sorveglianza geodetica delle aree vulcaniche attive
    Description: JCR Journal
    Description: restricted
    Keywords: Gas explosions . ; Geothermal systems ; Submarine gas venting ; Volcanic CO2 flux ; Volcanic hazards ; Panarea island ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
    Publication Date: 2017-04-04
    Description: Active volcanoes are thought to be important contributors to the atmospheric mercury (Hg) budget, and this chemical element is one of the most harmful atmospheric pollutants, owing to its high toxicity and long residence time in ecosystems. There is, however, considerable uncertainty over the magnitude of the global volcanic Hg flux, since the existing data on volcanogenic Hg emissions are sparse and often ambiguous. In an attempt to extend the currently limited dataset on volcanogenic Hg emissions, we summarize the results of Hg flux measurements at seven active open-conduit volcanoes; Stromboli, Asama, Miyakejima, Montserrat, Ambrym, Yasur, and Nyiragongo.. Data from the domebuilding Soufriere Hills volcano are also reported. Using our determined mercury to SO2 mass ratios in tandem with the simultaneously-determined SO2 emission rates, we estimate that the 7 volcanoes have Hg emission rates ranging from 0.2 to 18 t yr-1 (corresponding to a total Hg flux of ~41 t·yr-1). Based on our dataset and previous work, we propose that a Hg/SO2 plume ratio ~10-5 is bestrepresentative of gas emissions from quiescent degassing volcanoes. Using this ratio, we infer a global volcanic Hg flux from persistent degassing of ~95 t·yr-1
    Description: Published
    Description: 497-510
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: restricted
    Keywords: Volcanogenic mercury ; Mercury ; Volcanic plume ; Mercury flux ; Mercury inventories ; Atmospheric mercury ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.02. Exploration geophysics::04.02.01. Geochemical exploration ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
    Publication Date: 2017-04-04
    Description: During 2007–2008, three CO2 flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO2 flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m−2 day−1 (April 2008) with total emission rates of 164±9.5 (March 2007), 59±2.5 (December 2007) and 109±6.6 t day−1 (April 2008). The mean CO2 flux estimated from the entire crater floor area was 1,102 g m−2 day−1 for April 2008 with a total emission rate of 144±5.9 t day−1. Significant change in CO2 flux was not detected during the period of survey, and the mapping of the CO2 flux highlighted lineaments reflecting the main local and regional tectonic patterns. The 3He/4He ratio (as high as 8.1 RA) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO2/3He ratios for the high 3He/4He gases tend to have the MORB-like values (1.41×109), and the CO2/3He ratios for the lower 3He/4He gases fall within the range for the arc-type gases. The high 3He/4He ratios, the MORB-like CO2/3He ratios for the high 3He/4He gases and high proportion of MORB-CO2 (M=25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.
    Description: Published
    Description: 423-441
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: El Chichon ; CO2 soil flux ; Crater Lake ; Gas geochemistry ; He-C isotopes ; Fumarolic and bubbling gases ; Tectonics ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.05. Geomagnetism::04.05.08. Instruments and techniques ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
    Publication Date: 2020-02-24
    Description: On 27 February 2007, a new eruption occurred on Stromboli which lasted until 2 April. It was characterized by effusive activity on the Sciara del Fuoco and by a paroxysmal event (15 March). This crisis represented an opportunity for us to refine the model that had been developed previously (2002-2003 eruption) and to improve our understanding of the relationship between the magmatic dynamics of the volcano and the geochemical variations in the fluids. In particular, the evaluation of the dynamic equilibrium between the volatiles (CO2 and SO2) released from the magma and the corresponding fluids discharged from the summit area allowed us to evaluate the level of criticality of the volcanic activity. One of the major accomplishments of this study is a four-year database of summit soil CO2 flux on the basis of which we define the thresholds (Low-Medium-High) for this parameter that are empirically based on the natural volcanological evolution of Stromboli. The SO2 fluxes of the degassing plume and the CO2 fluxes emitted from the soil at Pizzo Sopra la Fossa are also presented. Noteworthy geochemical signals of volcanic unrest have been clearly identified before, during, and after the effusive activity. These signals were found almost simultaneously in the degassing plume (SO2 flux) and in soil degassing (CO2 flux) at the summit, although the two degassing processes are shown to be clearly different. The interpretation of the results will be useful for future volcanic surveillance at Stromboli.
    Description: In press
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli Volcano ; CO2 soil flux ; Geochemical monitoring ; 2007 eruption ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
    Publication Date: 2017-04-04
    Description: We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO2 in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ13C of volcanic CO2 between −0.9±0.27‰ and −1.41± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work values of Etna CO2 from~ −4‰, in the 1970’s and the 1980’s, to~ −1‰ at the present time (2009). This shift toward more positive δ13C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO2 emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.
    Description: Published
    Description: 531-542
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: restricted
    Keywords: Volcanic plume ; Carbon isotope ; Etna ; Magmatic degassing ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2017-04-04
    Description: Destructive volcaniclastic flows are among the most recurrent and dangerous natural phenomena in volcanic areas. They can originate not only during or shortly after an eruption (syn-eruptive) but also during a period of volcanic quiescence (inter-eruptive), when heavy and/or persistent rains remobilize loose pyroclastic deposits. The area in Italy most prone to such flows is that of the Apennine Mountains bordering the southern Campania Plain. These steep slopes are covered by pyroclastic material of variable thickness (a few cm to several m) derived from the explosive activity of the Somma-Vesuvius and Campi Flegrei volcanoes a few tens of kilometers to the west. The largest and most recent devastating event occurred on May 5, 1998, causing the death of more than 150 people and considerable damage to villages at the foot of the Apennine Mountains. This tragic event was only the most recent of a number of volcaniclastic flows affecting the area in both historical and prehistoric times. Historical accounts report that more than 500 events have occurred in the last five centuries and that more than half of these occurred in the last 100 years, causing hundreds of deaths. In order to improve volcaniclastic flow hazard zonation and risk mitigation in the study area, we produced a zonation map that identifies the drainage basins potentially prone to disruption. This map was obtained by combining morphological characteristics (concavity and basin shape factor) and the mean slope distribution of drainage basins derived from a digital elevation model with a 10-m resolution. These parameters allowed for the classification of 1,069 drainage basins, which have been grouped into four different classes of proneness to disruption: low, moderate, high and very high. The map compiled in a GIS environment, as well as the linked database, can be rapidly queried.
    Description: Published
    Description: 371-387
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Volcaniclastic flow hazard ; GIS ; Vesuvian area ; Southern Campania Plain ; Slope instability ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
    Publication Date: 2017-04-04
    Description: We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO2 in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ13C of volcanic CO2 between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ13C values of Etna CO2 from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ13C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO2 emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.
    Description: In press
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Volcanic plume ; Carbon isotope ; Etna ; Magmatic degassing ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 14
    Publication Date: 2017-04-04
    Description: The Mw 5.7 earthquake that occurred on 12 May 1802 is the only one with Mw ≥ 5.5 located west of Lake Garda in the central-northern part of the Po Plain, Northern Italy, and the strongest event located in the seismic zone 907 of the ZS9 seismogenic zonation of Italy. Current parametric earthquake catalogs locate the event not far from important cities (e.g., Milan) and to sites where nuclear power plants were to be built in the 1980s or could be built in a near future. Although the earthquake parameters seemed sufficiently well constrained, a detailed investigation of documentary sources was performed, in repositories storing the documents of the Napoleonic departments to which the area affected by the earthquake belonged at that time. In the surviving archival series, we found the officers’ correspondence on all the administrative aspects raised by the earthquake. The newly collected records allowed the authors to significantly increase the number of macroseismic intensity data, including new observations in the most damaged area. The results have been then interpreted in terms of both Mercalli–Cancani–Sieberg and EMS98 macroseismic scales. The earthquake parameters were derived applying two different methods in order to get two independent estimates. Earthquake location is confirmed, although the still scarce data available in the area to the east of the epicenter do not permit to reduce the uncertainty to a minimum. According to the Boxer method, the magnitude is now slightly higher, and the source model shows a good agreement with the tectonic setting of the area.
    Description: Published
    Description: 629-651
    Description: 3.10. Storia ed archeologia applicate alle Scienze della Terra
    Description: JCR Journal
    Description: reserved
    Keywords: 1802 earthquake ; Northern Italy ; Historical seismology ; Macroseismic intensity ; Earthquake parameters ; 04. Solid Earth::04.06. Seismology::04.06.05. Historical seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publication Date: 2017-04-04
    Description: On 30 December 2002, a 25-30 × 106 m3 landslide on the NW flank of Stromboli volcano produced a tsunami that caused relevant damage to the Stromboli village and to the neighboring islands of the Aeolian archipelago. The NW flank of Stromboli has been the site of several, cubic kilometer-scale, landslides during the past 13 ka. In this paper we present sedimentological and compositional data of deep-sea cores recovered from a site located about 24 km north of the island. Our preliminary results indicate that: (i) turbidity currents were effectively generated by the large-scale failures and (ii) volcanogenic turbidity current deposits retain clues of the landslide source and slope failure dynamics. By analogy with Hawaii and the Canary islands we confirm that deep-sea sediments can be effectively used to assess the age and scale of past landslide events giving an important contribution to the tsunami hazard assessment of this region.
    Description: Published
    Description: 719-731
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: reserved
    Keywords: Landslide ; turbidite ; tsunami ; Stromboli ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: book chapter
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  • 16
    Publication Date: 2017-04-04
    Description: Recent stratigraphic studies at Vesuvius have revealed that, during the past 4,000 years, long lasting,moderate to low-intensity eruptions, associated with continuous or pulsating ash emission, have repeatedly occurred. The present work focuses on the AS1a eruption, the first of a series of ash-dominated explosive episodes which characterized the period between the two Subplinian eruptions of 472 AD and 1631 AD. The deposits of this eruption consist of an alternation of massive and thinly laminated ash layers and minor well sorted lapilli beds, reflecting the pulsatory injection into the atmosphere of variably concentrated ash-plumes alternating with Violent Strombolian stages. Despite its nearly constant chemical composition, the juvenile material shows variable external clast morphologies and groundmass textures, reflecting the fragmentation of a magma body with lateral and/or vertical gradients in both vesicularity and crystal content. Glass compositions and mineralogical assemblages indicate that the eruption was fed by rather homogeneous phonotephritic magma batches rising from a reservoir located at ~ 4 km (100 MPa) depth, with fluctuations between magma delivery and magma discharge. Using crystal size distribution (CSD) analyses of plagioclase and leucite microlites, we estimate that the transit time of the magma in the conduit was on the order of ~ 2 days, corresponding to an ascent rate of around 2× 10−2 ms−1. Accordingly, assuming a typical conduit diameter for this type of eruption, the minimum duration of the AS1a event is between about 1.5 and 6 years. Magma fragmentation occurred in an inertially driven regime that, in a magma with low viscosity and surface tension, can act also under conditions of slow ascent.
    Description: In press
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Ash emission activity ; Tephrite ; Vesuvius ; Stratigraphy ; Textural analyses ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 17
    Publication Date: 2017-04-04
    Description: Etna’s 2001 basaltic lava flow provided a good example of the distal flow segment between the flow front and stable channel, across which the flow evolves from channel-contained to dispersed. This zone was mapped with meter precision using LIDAR data collected during 2004 and 2005. These data, supported by field mapping, show that the flow front comprised eight lobes each 10 to 20 m high. The flow front appears to have advanced not as a single unit, but as a series of lobes moving forward one lobe at a time. Primary lobes were centered on the channel axis and marginal lobes were off-axis. The lobes advanced as breakouts of low-yield-strength lava from the flow core of the stalled flow front. Marginal lobes were abandoned and contributed to marginal levees flanking the transitional channel. For Etna’s 2001 flow, the transitional channel is 140 m wide, 700 m long and fed a 240-m-long zone of dispersed flow; the change from stable to transitional channel occurred at a major reduction in slope. Above this, the stable channel is 5.2 km long, 55 to 105 m wide and bounded by 15- to 25-m-high levees, and the stable channel is located over a previous channel. In a final stage of activity, lava ponding at the break-in-slope that marks the terminus of the stable channel put pressure on the eastern levee, causing it to fail. Liberated lava then fed a final break-out to the east. Similar flow front-features occur at other volcanoes, indicating that similar processes are characteristic of dispersed flow zones.
    Description: Published
    Description: 119-127
    Description: 1.10. TTC - Telerilevamento
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: reserved
    Keywords: Basalt lava ; Channelised lava flow ; Flow front ; Zone of dispersed flow ; Flow dynamics ; LIDAR ; Etna ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 18
    Publication Date: 2017-04-04
    Description: Changes of the susceptibility to lava flow invasion at Mount Etna are quantified by using lava flow simulations on four Digital Elevation Models documenting the morphostructural modifications of the volcano in the time interval 1986–2007. The probabilistic code DOWNFLOW is used to derive the areas invaded by several thousands of lava flows obtaining, for each DEM, maps of the susceptibility to lava flow invasion and of the lava flow hazard. These maps show, for the first time, the evolution of these surficial properties with time, and render a quantitative image of the effects of topographic changes on the preferential lava flow drainage paths. The results illustrate how the emplacement of new lava flows and the growth of scoria cones affect the probability of inundation by lava flows. We conclude that the persistent activity of this volcano requires a frequent updating of the topography for a reliable lava flow hazard assessment.
    Description: Published
    Description: 537-546
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Lava flow simulation ; Digital Elevation Model ; Lidar ; Time series ; Lava flow hazard maps ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.08. Risk::05.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
    Publication Date: 2021-09-03
    Description: During the past 22 ka of activity at Somma– Vesuvius, catastrophic pyroclastic density currents (PDCs) have been generated repeatedly. Examples are those that destroyed the towns of Pompeii and Ercolano in AD 79, as well as Torre del Greco and several circum-Vesuvian villages in AD 1631. Using new field data and data available from the literature, we delineate the area impacted by PDCs at Somma–Vesuvius to improve the related hazard assessment. We mainly focus on the dispersal, thickness, and extent of the PDC deposits generated during seven plinian and sub-plinian eruptions, namely, the Pomici di Base, Greenish Pumice, Pomici di Mercato, Pomici di Avellino, Pompeii Pumice, AD 472 Pollena, and AD 1631 eruptions. We present maps of the total thickness of the PDC deposits for each eruption. Five out of seven eruptions dispersed PDCs radially, sometimes showing a preferred direction controlled by the position of the vent and the paleotopography. Only the PDCs from AD 1631 eruption were influenced by the presence of the Mt Somma caldera wall which stopped their advance in a northerly direction. Most PDC deposits are located downslope of the pronounced break-in slope that marks the base of the Somma– Vesuvius cone. PDCs from the Pomici di Avellino and Pompeii Pumice eruptions have the most dispersed deposits (extending more than 20 km from the inferred vent). These deposits are relatively thin, normally graded, and stratified. In contrast, thick, massive, lithic-rich deposits are only dispersed within 7 to 8 km of the vent. Isopach maps and the deposit features reveal that PDC dispersal was strongly controlled by the intensity of the eruption (in terms of magma discharge rate), the position of the vent area with respect to the Mt Somma caldera wall, and the pre-existing topography. Facies characteristics of the PDC deposits appear to correlate with dispersal; the stratified facies are consistently dispersed more widely than the massive facies.
    Description: Published
    Description: 1021–1038
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Pyroclastic flow ; Hazard assessment ; Mt Somma ; Pyroclastic density currents ; Facies ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 20
    Publication Date: 2020-11-16
    Description: Active volcanoes characterized by open conduit conditions generate sonic and infrasonic signals, whose investigation provides useful information for both monitoring purposes and studying the dynamics of explosive processes. In this work, we discuss the automatic procedures implemented for a real-time application to the data acquired by a permanent network of five infrasound stations running at Mt. Etna volcano. The infrasound signals at Mt. Etna consist in amplitude transients, called infrasound events. The adopted procedure uses a multi-algorithm approach for event detection, counting, characterization and location. It is designed for an efficient and accurate processing of infrasound records provided by single-site and array stations. Moreover, the source mechanism of these events can be investigated off-line or in near real-time by using three different models: i) Strombolian bubble; ii) resonating conduit and iii) Helmholtz resonator. The infrasound waveforms allow us to choose the most suitable model, to get quantitative information about the source and to follow the time evolution of the source parameters.
    Description: Published
    Description: 1215–1231
    Description: 6V. Pericolosità vulcanica e contributi alla stima del rischio
    Description: JCR Journal
    Description: open
    Keywords: infrasound ; monitoring system ; Mt. Etna ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 21
    Publication Date: 2020-11-16
    Description: Earthquake catalogues for Romania supply for 11th–15th century earthquakes located in the region of Vrancea records that consist of a complete set of parameters, including magnitude and depth. Scope of this paper is to verify the reliability and consistency of these parameters with the informative background as explicitly referenced by the catalogues. After retrieving the original sources they mention, the set of data appeared to be related almost exclusively to the Russian plain and too poor to be at the very origin of the parameter assessment. Data for 19th–20th century earthquakes, such as instrumental locations and CMT solutions, added to the understanding of the macroseismic response of the Russian plain to Vrancea earthquakes. On the one hand, the investigation and analysis of historical earthquake records for the fourteen events listed by the catalogues in the 11th–15th centuries has shown that for three earthquakes (1022, 1038, 1258) no primary sources could be traced, and three more earthquakes (1091, 1170 and 1328) are attested only by scarcely reliable records and had to be classified as doubtful, and one (1473) is simply a duplication of the 1471 event. On the other hand, the availability of data on recent earthquakes that may be compared to historical ones in terms of macroseismic effects allowed the authors to agree with the previous catalogue compilers’ solution with regard to both magnitude and depth of the past earthquakes for which do exist reliable primary historical records.
    Description: Published
    Description: 575–604
    Description: 4IT. Banche dati
    Description: JCR Journal
    Description: open
    Keywords: Vrancea earthquakes ; 11th-15th earthquakes ; 04. Solid Earth::04.06. Seismology::04.06.05. Historical seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 22
    Publication Date: 2017-04-04
    Description: Methane plays an important role in the Earth’s atmospheric chemistry and radiative balance being the second most important greenhouse gas after carbon dioxide. Methane is released to the atmosphere by a wide number of sources, both natural and anthropogenic, with the latter being twice as large as the former (IPCC, 2007). It has recently been established that significant amounts of geological methane, produced within the Earth’s crust, are currently released naturally into the atmosphere (Etiope, 2004). Active or recent volcanic/geothermal areas represent one of these sources of geological methane. But due to the fact that methane flux measurements are laboratory intensive, very few data have been collected until now and the contribution of this source has been generally indirectly estimated (Etiope et al., 2007). The Greek territory is geodynamically very active and has many volcanic and geothermal areas. Here we report on methane flux measurements made at two volcanic/geothermal systems along the South Aegean volcanic arc: Sousaki and Nisyros. The former is an extinct volcanic area of Plio-Pleistocene age hosting nowadays a low enthalpy geothermal field. The latter is a currently quiescent active volcanic system with strong fumarolic activity due to the presence of a high enthalpy geothermal system. Both systems have gas manifestations that emit significant amounts of hydrothermal methane and display important diffuse carbon dioxide emissions from the soils. New data on methane isotopic composition and higher hydrocarbon contents point to an abiogenic origin of the hydrothermal methane in the studied systems. Measured methane flux values range from –48 to 29,000 (38 sites) and from –20 to 1100 mg/mˆ2/d (35 sites) at Sousaki and Nisyros respectively. At Sousaki measurement sites covered almost all the degassing area and the diffuse methane output can be estimated in about 20 t/a from a surface of about 10,000 mˆ2. At Nisyros measurements covered the Stephanos and Kaminakia areas, which represent only a part of the entire degassing area. The two areas show very different methane degassing pattern with latter showing much higher flux values. Methane output can be estimated in about 0.25 t/a from an area of about 30,000 mˆ2 at Stephanos and about 1 t/a from an area of about 20,000 mˆ2 at Kaminakia. The total output from the entire geothermal system of Nisyros probably should not exceed 2 t/a.
    Description: Published
    Description: Vienna, Austria
    Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi
    Description: open
    Keywords: methane output ; diffuse degassing ; volcanic/hydrothermal systems ; Greece ; 01. Atmosphere::01.01. Atmosphere::01.01.03. Pollution ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data ; 05. General::05.08. Risk::05.08.01. Environmental risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Poster session
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  • 23
    Publication Date: 2017-04-04
    Description: A biomonitoring survey, above tree line level, using two endemic species (Senecio aethnensis and Rumex aethnensis) was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic atmospheric emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500- 3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decrease one or two orders of magnitude with increasing distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The two different species of plants do not show significant differences in the bioaccumulation of most of the analyzed elements, except for lanthanides, which are systematically enriched in Rumex leaves. The high concentrations of many toxic elements in the leaves allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches in the Mt. Etna area.
    Description: Published
    Description: Vienna, Austria
    Description: 4.4. Scenari e mitigazione del rischio ambientale
    Description: open
    Keywords: Mt. Etna ; biomonitoring ; Trace elements ; 01. Atmosphere::01.01. Atmosphere::01.01.03. Pollution ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data ; 05. General::05.08. Risk::05.08.01. Environmental risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Poster session
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  • 24
    Publication Date: 2017-04-04
    Description: Studies on volcanic degassing have recently shown the important role of volatile release from active volcanoes in understanding magmatic processes prior to eruptions. Here we present and discuss the evolution of magmatic degassing that preceded and accompanied the 2008 Mt. Etna eruption. We tracked the ascent of magma bodies by high-temporal resolution measurements of SO2 emission rates and discrete sampling of SO2/HCl and SO2/HF molar ratios in the crater plume, as well as by periodic measurement of soil CO2 emission rates. Our data suggest that the first signs of upward migration of gas-rich magma before the 2008 eruption were observed in June 2007, indicated by a strong increase in soil CO2 efflux followed by a slow declining trend in SO2 flux and halogens. This degassing behavior preceded the mid-August 2007 summit activity culminated with the September 4th paroxysmal event. Five months later, a new increase in both soil CO2 and SO2 emission rates occurred before the November 23rd paroxysm, to drop down in late December. In the following months, geochemical parameters showed high variability, characterized by isolated sudden increases occurred in early December 2007 and late March 2008. In early May soil CO2, SO2 emission rates and S/Cl molar ratio gradually increased. Crater degassing peaked on May 13th marking the onset of the eruption. Eruptive activity was accompanied by a general steady-state of SO2 flux characterized by two main degassing cycles. These cycles preceded explosive activity at the eruptive vents, indicating terminal new-arrival of deep gas-rich magma bodies in the shallow plumbing system of Mt Etna. Conversely, halogens described a slight increasing trend till the end of 2008. These observations suggest an impulsive syn-eruptive dynamics of magma transfer from depth to the surface. Differently from the SO2 emission rates, the S/Cl ratio and the soil CO2 efflux values showed an increasing trend from mid-April to mid-July 2008, indicating steady-increasing input of deeper, gas-rich magma. Since August, geochemical parameters decreased, suggesting that new magma has not arrived from depth. According to our interpretation, both the CO2 efflux and the S/Cl ratio increases observed in early November may indicate a new input of fresh magma form depth. Finally, the estimated volume of degassing magma showed substantial equilibrium between degassed and erupted magma suggesting an “eruptive” steady-state of the volcano.
    Description: INGV, Sezione di Catania; INGV, Sezione di Pisa; University of Cambridge, Cambridge, UK
    Description: Published
    Description: Vienna, Austria
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: open
    Keywords: Mt. Etna ; plume gases ; soil CO2 ; eruption ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Abstract
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  • 25
    Publication Date: 2017-04-04
    Description: Concurrent measurement of soil radon, soil thoron and soil CO2 efflux is based on the method developed by Giammanco et al. (Geochem. Geophys. Geosys., 8(10), Q 10001, doi:10.1029/2007GC001644, 2007). An empirical relationship links the 222Rn/220Rn ratio to the CO2 efflux: deep sources of gas are characterized by high 222Rn activity and high CO2 efflux, whereas shallow sources are indicated by high 220Rn activity and relatively low CO2 efflux. This relationship is more constraining on the type and depth of the gas source than using the 222Rn/220Rn ratio alone.We studied the temporal variation of the ratio between CO2 efflux and (222Rn/220Rn), that we define as a Soil Gas Disequilibrium Index (SGDI). Since June 2006, periodical measurements of the SGDI were carried out in ten sites located on the flanks of Mt. Etna, with sampling frequency of about ten days. Remarkable variations in this parameter were recorded during the period 2006-2008 likely associated with changes in the activity level of Mt. Etna. In particular, one of the sites located in the area called Primoti (on the lower east flank of the volcano) has shown significant anomalous changes of the SGDI in time, possibly correlated with the eruptive/tectonic activity. For this reason, in this site we set up an automatic monitoring station made of a Radon/Thoron monitor (model RTM 2100, SARAD GmbH, Germany) coupled with a soil CO2 efflux station (model ACE, ADC BioScientific Ltd., UK). The sampling frequency was set at 30 minutes, in order to allow for a sufficient decay equilibration in the radon isotopes. Air temperature and barometric pressure were recorded as well, with the same sampling rate as for the soil gases. The site chosen for testing the monitoring station is located on the east flank of Mt. Etna at an altitude of about 520 a.s.l., in an area known for widespread diffuse emissions of CO2 and other gases of magmatic origin. The preliminary data acquired so far showed an average soil CO2 efflux of 10 g m􀀀2 d􀀀1 (std dev of about 7 g m􀀀2 d􀀀1) and average 222Rn and 220Rn activities of about 3.3 103 Bq/m3 (std dev of about 1140 Bq/m3) and about 2.0 103 Bq/m3 (std dev of about 620 Bq/m3), respectively. The corresponding values of the SGDI thus obtained varied in the range from about -1.5 to about 70.1, with an average of about 7 and standard deviation of about 6.3. The apparent baseline of the parameter is around the value of 3, and daily variations are clearly detected due to the combined influence of air temperature and barometric pressure. No clear influence from rainfall was observed. Some spikes were also detected, whose origin has to be studied by correlating the SGDI with other environmental parameters as well as with changes in the volcanic/tectonic activity of Mt. Etna.
    Description: INGV, Sezione di Catania
    Description: Published
    Description: Vienna, Austria
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: open
    Keywords: Mt. Etna ; soil radon ; CO2 ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Abstract
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  • 26
    Publication Date: 2017-04-04
    Description: Mt. Nyiragongo is one of the most dangerous volcanoes in the world for the risk associated with the propagation of lava flows. In 2002 several vents opened along a huge system of fractures, pouring out lava which reached and destroyed a considerable part of Goma, a town of about 500,000 inhabitants on the shore of Lake Kivu. In a companion paper (Favalli et al. in Bull Volcanol, this issue, 2008) we employed numerical simulations of probable lava flow paths to evaluate the lava flow hazard on the flanks of the volcano, including the neighbouring towns of Goma (DRC) and Gisenyi (Rwanda). In this paper we use numerical simulations to investigate the possibility of significantly reducing the lava flow hazard in the city through the construction of protective barriers. These barriers are added to the DEM of the area as additional morphological elements, and their effect is evaluated by repeating numerical simulations with and without the presence of barriers. A parametric study on barrier location, size, shape and orientation led to the identification of barriers which maximize protection while minimizing their impact. This study shows that the highest hazard area corresponding to eastern Goma, which was largely destroyed by lava flows in 2002, cannot be effectively protected from future lava flows towards Lake Kivu and should be abandoned. On the contrary, the rest of the town can be sheltered from lava flows by means of two barriers that deviate or contain the lava within the East Goma sector. A proposal for the future development of the town is formulated, whereby “new” Goma is completely safe from the arrival of lava flows originating from vents outside its boundaries. The proposal minimizes the risk of further destruction in town due to future lava flows.
    Description: Published
    Description: 375-387
    Description: 2.1. TTC - Laboratorio per le reti informatiche, GRID e calcolo avanzato
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Lava flow ; Nyiragongo ; Volcanic hazard ; Hazard mitigation ; Numerical simulations ; Lava barriers ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis ; 05. General::05.01. Computational geophysics::05.01.05. Algorithms and implementation
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  • 27
    Publication Date: 2017-04-04
    Description: On 30 December 2002, a 25-30 × 106 m3 landslide on the NW flank of Stromboli volcano produced a tsunami that caused relevant damage to the Stromboli village and to the neighboring islands of the Aeolian archipelago. The NW flank of Stromboli has been the site of several, cubic kilometer-scale, landslides during the past 13 ka. In this paper we present sedimentological and compositional data of deep-sea cores recovered from a site located about 24 km north of the island. Our preliminary results indicate that: (i) turbidity currents were effectively generated by the large-scale failures and (ii) volcanogenic turbidity current deposits retain clues of the landslide source and slope failure dynamics. By analogy with Hawaii and the Canary islands we confirm that deep-sea sediments can be effectively used to assess the age and scale of past landslide events giving an important contribution to the tsunami hazard assessment of this region.
    Description: Unpublished
    Description: -
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: reserved
    Keywords: Landslide ; turbidite ; tsunami ; Stromboli ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology ; 04. Solid Earth::04.04. Geology::04.04.08. Sediments: dating, processes, transport ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: book chapter
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  • 28
    Publication Date: 2020-02-24
    Description: A multidisciplinary geological and compositional investigation allowed us to reconstruct the occurrence of flank eruptions on the lower NE flank of Stromboli volcano since 15 ka. The oldest flank eruption recognised is Roisa, which occurred at ~15 ka during the Vancori period, and has transitional compositional characteristics between the Vancori and Neostromboli phases. Roisa was followed by the San Vincenzo eruption that took place at ~12 ka during the early stage of Neostromboli period. The eruptive fissure of San Vincenzo gave rise to a large scoria cone located below the village of Stromboli, and generated a lava flow, most of which lies below sea level. Most of the flank eruptions outside the barren Sciara del Fuoco occurred in a short time, between ~9 and 7 ka during the Neostromboli period, when six eruptive events produced scoria cones, spatter ramparts and lava flows. The Neostromboli products belong to a potassic series (KS), and cluster in two differently evolved groups. After an eruptive pause of ~5,000 years, the most recent flank eruption involving the NE sector of the island occurred during the Recent Stromboli period with the formation of the large, highly K calc-alkaline lava flow field, named San Bartolo. The trend of eruptive fissures since 15 ka ranges from N30°E to N55°E, and corresponds to the magma intrusions radiating from the main feeding system of the volcano.
    Description: The mapping of Stromboli was supported by a grant to S. Calvari (Project V2/01, 2005–2007, funded by the Istituto Nazionale di Geofisica e Vulcanologia and by the Italian Civil Protection). This work was partly supported by INGV through a research grant financed by MIUR-FIRB to G. Norini. We wish to thank the former Director of INGV-Sezione di Catania, A. Bonaccorso, for making additional funds available for field trip and datings.
    Description: In press
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: restricted
    Keywords: Stromboli ; flank fissures ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 29
    Electronic Resource
    Electronic Resource
    Springer
    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 30
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 31
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 32
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 33
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 35
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 36
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    ISSN: 1572-8943
    Keywords: cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 841-849 
    ISSN: 1572-8943
    Keywords: cobalt(II)-dothiepin ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10° C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 297-303 
    ISSN: 1572-8943
    Keywords: β-zeolite ; coke ; cumene ; kinetics ; regeneration ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An accurate description of coke burn off is obtained from a catalyst based on β-zeolite and used for benzene alkylation with propylene giving cumene by using the thermogravimetric technique. A simple empirical kinetic model was successfully applied to interpolate the data of thermogravimetric analysis performed on samples after partial burn off. Different temperatures, partial pressures of oxygen and gas flow rates were the variables studied in order to calculate the apparent rates and the activation energy for the coke oxidation reaction and to outline the best conditions for the industrial regeneration procedure of our proprietary catalyst PBE-1 for cumene synthesis. Combining the unusually long lifetime per reaction cycle with the optimized regeneration procedure leads to an outstanding overall catalyst life.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 953-958 
    ISSN: 1572-8943
    Keywords: differential scanning calorimeter ; kinetics ; oil shale ; pyrolysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this research, non-isothermal pyrolysis behavior and kinetics of three oil shales were studied by thermal analysis methods. All the thermal effects were endothermic and no exothermic region was observed in DSC curves. When oil shales are heated in nitrogen atmosphere in TG/DTG, two different mechanisms causing loss of mass were observed. The region between ambient temperature and 500 K was distillation. The second mechanism was visbreaking and cracking and it was observed between the region 500 and 800 K. Kinetic parameters of all the samples are determined by Coats and Redfern method and the results are discussed with regard to their accuracy and the ease of interpretation.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1461-1473 
    ISSN: 1572-8943
    Keywords: CaCO3 ; densification ; kinetics ; Li2CO3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressureless sintering of CaCO3 was carried out, with Li2CO3 (from 0.5 to 8 wt%) as an additive, under different pressures of CO2. Densification occurs between 600 and 700°C. Sintering above the eutectic temperature (T〉662°C) leads to the decomposition of calcium carbonate and the materials become expanded. At 620° under 1 kPa of CO2, a relative density of 96% is reached. Li2CO3 enhances the densification process and grain growth of calcium carbonate. CO2 pressure slows down densification and grain growth kinetics. These results are explained by the influence of carbonate and calcium ion vacancies on the sintering mechanisms.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 383-391 
    ISSN: 1572-8943
    Keywords: 1-aminopyrene (apyr) ; N-(2-pyridylmethylene)-1-pyrenylamine (pmpa) ; kinetics ; palladium(II)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1−aminopyrene and pmpa=N−(2−pyridylmethylene)−1−pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, Šesták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.
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  • 46
    ISSN: 1572-8943
    Keywords: first order autocatalytic reaction ; HNNC ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation $$\frac{{{\text{d}}y}} {{dt}} = - 10^{16.4} \exp \left( { - \frac{{210380}} {{RT}}} \right)y - 10^{16.7} \exp \left( { - \frac{{171205}} {{RT}}} \right)y(1 - y)$$ and that for the latter 50% mass-loss of HNNC described by the reaction equations $$\frac{{dy}} {{dy}} = - 10^{16.3} \exp \left( { - \frac{{169483}} {{RT}}} \right)y\quad (n = 1)$$ and $$\frac{{dy}} {{dt}} = - 10^{16.8} \exp \left( { - \frac{{165597}} {{RT}}} \right)y^{2.61} \quad (n \ne 1)$$
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    Journal of thermal analysis and calorimetry 55 (1999), S. 173-185 
    ISSN: 1572-8943
    Keywords: IRS ; kinetics ; mechanism ; nitro aromatic ; TA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the initial stage of thermal decomposition of 2,4,6-trinitro toluene (TNT), a widely used high explosive, have been studied, together with its morphology and evolved gaseous products using thermogravimetry (TG), differential thermal analysis (DTA), infrared spectroscopy (IR) and hot-stage microscopy. The kinetics of the thermolysis has been followed by IR after suppressing volatilisation by matrixing and by isothermal TG without suppressing volatilisation to simulate actual user conditions. The best linearity was obtained for Avrami-Erofeev equation for n=1 in isothermal IR and also in isothermal TG. The activation energy was found to be 135 kJ mol−1, with logA (in s−1) 12.5 by IR. The effect of additives on the initial thermolysis of TNT has also been studied. Evolved gas analysis by IR showed that CO2, NO2, NO and H2O are more dominant than N2O, HCN and CO. The decomposition involves the initial rupture of the C-NO2 bond, weakened by hydrogen bonding with the labile hydrogen atom of the adjacent CH3 group, followed by the abstraction of the hydrogen atom of the methyl group by NO2, generated in the initial step.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 691-698 
    ISSN: 1572-8943
    Keywords: activation energy ; kinetics ; solid-state reactions ; superconductors ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetric in situ measurements of oxygen loss from (RE)Ba2Cu3O6 samples (RE=Y, Nd, Er) heated isothermally in a relatively high dynamic vacuum were made with a Cahn RG electrobalance. Single-phase orthorhombic samples of composition (RE)Ba2Cu3O7-x (highest oxygen content) were synthesized from stoichiometric (1:2:3) mixtures of high-purity (RE)2O3, BaCO3 and CuO. The original 1:2:3 mixture was prepared by the two-stage procedure described earlier. The crystal structure of the sample in the original orthorhombic phase was controlled by the X-ray powder method (CuKα radiation) using a Stadi P Stoe diffractometer with a position-sensitive detector. The decomposition curves are described by the sum of exponential terms corresponding to rapid and slow first-order processes in which differently sized grains of the powder samples are involved. The activation energies are estimated from appropriate Arrhenius plots.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 779-788 
    ISSN: 1572-8943
    Keywords: cobalt ; dynamic and isothermal methods ; kinetics ; molybdotellurates ; nickel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Molybdotellurates [M(H2O)6]3·[TeMo6O24], with M=Ni(II) and Co(II), were synthesized and characterized by single-crystal X-ray diffraction for compound 1 and X-ray powder diffraction for compound 2, EDAX, IR, electronic spectra in the solid phase and in solution, and magnetic properties. Thermogravimetry and differential scanning calorimetry of both compounds revealed a loss of 11 water molecules through an endothermal process with ΔH=800 kJ mol−1 for the nickel compound and ΔH=833 kJ mol−1 for the cobalt compound. The residual compounds were characterized by chemical analysis, IR and XPS spectroscopy
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    Journal of thermal analysis and calorimetry 55 (1999), S. 817-831 
    ISSN: 1572-8943
    Keywords: kinetics ; Schiff-bases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of two new Schiff-bases, citronellal anthranilic acid and citronellal-5-bromoanthranilic acid have been synthesized. On the basis of spectral, magnetic and thermal data, octahedral structure was assigned to all complexes [ML2(H2O)2]. Thermal decomposition of these complexes was studied by TG. Kinetic parameters, viz activation energy, E, pre-exponential factor, A, and order of reaction, n, were calculated from the TG curves using mechanistic and non-mechanistic integral equations.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 17-26 
    ISSN: 1572-8943
    Keywords: kinetics ; reaction controlled thermal analysis ; stepwise isothermal analysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Reaction Controlled Thermal Analysis techniques, RCTA, are very useful both in thermogravimetric and dilatometric studies. In the present paper this big family of techniques is divided into three main classes: Quasi-Isothermal techniques (QIA); Controlled Reaction Rate Thermal Analysis (CRTA) and Reaction (Event) Controlled Heating Rate Adaption. After a short presentation of these techniques and the general advantages of RCTA, two examples of kinetic studies on thermal decomposition of Ba- and Ce oxalates by using Stepwise Isothermal Analysis, SIA, introduced by the author is presented and discussed.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 783-792 
    ISSN: 1572-8943
    Keywords: complex process ; DSC ; isoconversional methods ; kinetics ; model-free kinetics ; peak maximum evolution methods ; simulations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process. Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally available because of duration times or detection limits.
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  • 53
    ISSN: 1572-8943
    Keywords: cobalt ; dmit ligand ; kinetics ; non-linear method ; Zsakó method
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In this work, a cobalt complex with dmit (1,3-dithiol-2-thione-4,5-dithiolate) as ligand was prepared and its thermal stability was studied by thermogravimetric analysis and kinetics by means of the Zsakó method and a non-linear method. For both methods, numerical binomial and polynomial filters were used, where points in the central interval were utilized.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1107-1113 
    ISSN: 1572-8943
    Keywords: differential scanning calorimetry ; induction period ; kinetics ; vulcanisation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Vulcanisation of rubber compounds was studied by DSC under isothermal and non-isothermal conditions. The parameters of an Arrhenius-like equation describing the temperature dependence of induction period have been obtained both from isothermal and non-isothermal measurements. A new method for obtaining the kinetic parameters from non-isothermal measurements, based on the dependence of onset temperature of vulcanisation peak on heating rate, is presented. Also, a procedure for the evaluation of temperature difference between the furnace and sample is proposed. It has been shown that the treatment of non-isothermal DSC measurements gives the kinetic parameters free of systematic errors. The new method can also be used for studying other reactions exhibiting the induction period.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 699-705 
    ISSN: 1572-8943
    Keywords: interaction in solid phase ; lithium carbonate ; lithium orthosilicate ; kinetics ; solid electrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m2g-1 instead of aerosil with one of 175 m2g-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 755-761 
    ISSN: 1572-8943
    Keywords: crystallization ; DTA ; kinetics ; Kissinger plot ; lithium diborate glass
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystallization process of Li2B4O7 in the glass of stoichiometric composition, characterized by the crystal growth of pre-existing nuclei, was analyzed kinetically by means of DTA. Because the number of pre-existing nuclei for the subsequent growth varies depending on the cooling rate of the glass-forming melt and heating rate of the as-prepared glass, a modified Kissinger plot was applied for evaluating the apparent activation energy to the crystal growth in the glass samples with three different thermal histories, i.e., the pre-annealed, slowly quenched and quickly quenched glasses. The process was characterized by the three dimensional growth of pre-existing nuclei with the apparent activation energy of ca 340 kJ mol−1.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 603-610 
    ISSN: 1572-8943
    Keywords: coprecipitation ; ferrite ; kinetics ; sintering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors report on a non-isothermal kinetic investigation (at constant heating rate) of the sintering of manganese and nickel-zinc ferrite powders prepared by coprecipitation. The kinetic results point to the thermal compaction of the powders, which occurs mainly in the intermediate stage of sintering. A comparative study was performed in order to determine the influence of the sample characteristics (such as chemical nature, density and shape) and the heating rate on the kinetics and mechanism of the compaction.
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  • 58
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    Journal of thermal analysis and calorimetry 56 (1999), S. 843-849 
    ISSN: 1572-8943
    Keywords: adiabatic calorimetry ; kinetics ; non-parametric kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The non-parametric kinetics (NPK) method has been recently developed for the kinetic treatment of thermoanalytical data. The most significant feature of this method is its ability to provide information about the reaction kinetics without any assumptions either about the functionality of the reaction rate with the degree of conversion or the temperature. This paper presents the results of the application of the method to adiabatic calorimetry. Some data have been obtained by numerical simulation, but also the thermal decomposition of DTBP, a well known first order reaction, has been studied, being the obtained results in good agreement with literature.
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  • 59
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    Journal of thermal analysis and calorimetry 56 (1999), S. 829-833 
    ISSN: 1572-8943
    Keywords: dolomite ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition reactions of calcitic dolomite were investigated. Simultaneous TG/DTG/DTA were applied under non-isothermal conditions. From the recorded curves, the activation energies, pre-exponential factors and thermodynamic parameters of activation were calculated for the two thermal decomposition steps.
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  • 60
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    Journal of thermal analysis and calorimetry 58 (1999), S. 215-223 
    ISSN: 1572-8943
    Keywords: adiabatic calorimetry ; kinetics ; Kissinger method
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Traditionally, the kinetic treatment of adiabatic calorimetry data has been based on the results of one or more experiments, but always with the assumption of the kinetic model that the reaction follows to calculate the kinetic parameters. In this paper a method for the determination of the activation energy that uses a set of adiabatic calorimetry data is developed. To check the method, the thermal decompositions of two peroxides were studied.
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  • 61
    ISSN: 1572-8943
    Keywords: coordinationcompounds ; CRTA ; kinetics ; polymerization ; pyrolysis ; quasi-equilibrium ; TG ; thermolysis ; volatility
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Quasi-equilibrium thermogravimetry (variant of CRTA) is put to use as an express method of thermoanalytical screening for volatile compounds. During the experiments for P—T relationship calculations (running with several calibrated standard sample holders) the non-volatile (polymerized) residue is formed (and is decomposed with further temperature rising). Thermogravimetric data are used for the calculation of the kinetic parameters for the polymerization reaction, taking place (concurrently with the evaporation) in the melt of the studied volatile compound.
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  • 62
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    Journal of thermal analysis and calorimetry 58 (1999), S. 447-453 
    ISSN: 1572-8943
    Keywords: coal ; combustion reaction ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The combustion behavior of Shuangya Mountain (SYM) coal dust has been investigated by means of TG in this paper. The reaction fraction α can be obtained from isothermal TG data. The regressions of g(α), an integral function of α vs. t for different reaction mechanisms were performed. The mechanism of nucleation and nuclei growth is determined as the controlling step of the coal dust combustion reaction by the correlation coefficient of the regression, and the kinetic equation of the SYM coal dust combustion reaction has been established.
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  • 63
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    Structural chemistry 10 (1999), S. 433-437 
    ISSN: 1572-9001
    Keywords: Positronium Chemistry ; kinetics ; spin exchange reactions ; paramagnetic 3d complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constants, k CR, of ortho- into para-positronium conversion reactions promoted by paramagnetic 3d complexes are linearly correlated with the electron delocalization, β, of unpaired metal electrons caused by ligands, β being the ratio between the inter-electronic repulsion parameters in complexes and in the free gaseous ions. By applying a procedure previously described the β values of MnII, CoII, NiII complexes with dimethylurea were deduced from the mentioned correlations and compared with those of complexes with urea obtained both by the method of Ps reactions here applied and that based on UV-Vis absorption spectroscopy.
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  • 64
    ISSN: 1572-8986
    Keywords: Arc ; gliding arc ; gas temperature ; electron temperature ; ion composition ; ion bombardment ; liquid electrode ; dye oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The plasma–solution interaction processes for gliding and “point” arcs between the aqueous solution surface and the metal electrode in the gas phase are studied. The plasma, liquid, and surface zones are taken into consideration. The electric field strength is measured, and the gas and electron temperatures and ion composition are estimated for the plasma zone. The cathode fall, water vaporization rate, and active species current yield due to the radiation chemistry mechanism are determined for the surface zone. The efficiency of oxidation of iodine ions and organic dyes by different types of discharge in the liquid zone are investigated. The difference in action of the various discharge types may be connected with various influences of the plasma and surface zone on the oxidation processes.
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  • 65
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    Molecular and cellular biochemistry 197 (1999), S. 195-201 
    ISSN: 1573-4919
    Keywords: phospholipase D ; phosphatidylinositol 4,5-bisphosphate ; neomycin ; kinetics
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The kinetics of phosphatidylcholine-specific phospholipase D activated by phosphatidylinositol 4,5-bisphosphate (PIP2) and inhibition by neomycin were studied in an enzyme preparation partially purified from human hepatocarcinoma cell line. It was found that phospholipase D was marginally activated by phosphatidyl-4-phosphate (PIP) and phosphatidylethanolamine (PE). In contrast, it was considerably activated by PIP2 in different concentration of phosphatidylcholine (PC). Sphingomyelin (SM), lysophosphatidylcholine (LPC) and phosphatidylserine (PS) were neither substrates nor inhibitors of the phospholipase D. PIP2 induced an allosteric effect on phospholipase D and a negative cooperative effect with respect to phosphatidylcholine as indicated in the Lineweaver-Burk plot. In the absence of PIP2, a straight line was obtained, whereas a downward concave curve was observed in the presence of 25 μM of PIP2. The Hill coefficient and the apparent Km of phosphatidylcholine in the presence of 25 μM PIP2 were calculated to be 0.631 and 10.79 mM, respectively. PIP2 also increased the maximal velocity (Vmax) of the phospholipase D reaction, suggesting that the affinity of substrate to enzyme was decreased, and the turnover number of the enzyme (kcat) was increased by PIP2. The activation of phospholipase D by PIP2 was dose dependent up to 50 μM of PIP2. The Ka of PIP2 was 15.8 mM. Neomycin, a polycationic glycoside, was shown to be an uncompetitive inhibitor of phospholipase D, and revealed the formation of a neomycin-PIP2 complex. The Ki of neomycin was estimated to be 8.7 mM.
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    Molecular and cellular biochemistry 193 (1999), S. 19-22 
    ISSN: 1573-4919
    Keywords: poly(ADP-ribose)polymerase ; kinetics ; allosterism ; regulation
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    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Here, we describe the latest developments on the mechanistic characterization of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], a DNA-dependent enzyme that catalyzes the synthesis of protein-bound ADP-ribose polymers in eucaryotic chromatin. A detailed kinetic analysis of the automodification reaction of PARP in the presence of nicked dsDNA indicates that protein-poly(ADP-ribosyl)ation probably occurs via a sequential mechanism since enzyme-bound ADP-ribose chains are not reaction intermediates. The multiple enzymatic activities catalyzed by PARP (initiation, elongation, branching and self-modification) are the subject of a very complex regulatory mechanism that may involve allosterism. For instance, while the NAD+ concentration determines the average ADP-ribose polymer size (polymerization reaction), the frequency of DNA strand breaks determines the total number of ADP-ribose chains synthesized (initiation reaction). A general discussion of some of the mechanisms that regulate these multiple catalytic activities of PARP is presented below.
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  • 67
    ISSN: 1573-4943
    Keywords: Alkaline phosphatase ; sodium (2, 2′-bipyridine) oxodiperoxovanadate ; inhibition ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Green crab (Scylla serrata) alkaline phosphatase (EC 3.1.3.1) is a metalloenzyme, which catalyzes the nonspecific hydrolysis of phosphate monoesters. The kinetics of inhibition of the enzyme by sodium (2, 2′-bipyridine) oxodiperoxovanadate, pV(bipy), has been studied. The time course of the hydrolysis of p-nitrophenyl-phosphate catalyzed by the enzyme in the presence of different pV(bipy) concentrations showed that at each pV(bipy) concentration, the rate decreased with increasing time until a straight line was approached, the straight line slopes are the same for all concentrations. The results suggest that the inhibition of the enzyme by pV(bipy) is a slow, reversible reaction with fractional remaining activity. The microscopic rate constants are determined for the reaction of inhibitor with the enzyme.
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    Journal of sol gel science and technology 15 (1999), S. 129-136 
    ISSN: 1573-4846
    Keywords: simulation ; percolation ; aggregation ; structure ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Three-dimensional (3D) Monte Carlo simulations of diffusion limited cluster aggregation at different concentrations (φ) show a crossover from a flocculation regime at short times to a percolation regime close to the gel time (tg). Contrary to suggestions in the literature tg is independent of the system size (L) for large L. The structural and temporal crossovers between flocculation and percolation take place at characteristic values of the cluster mass (mc) and the time (tc) which depend on φ. After normalisation by these characteristic values the crossovers are independent of φ except for very small clusters and at short times. The concentration dependence of mc and tc indicates that the crossover takes place at a given cumulated volume fraction of the clusters independent of φ. At low concentrations the φ-dependence of tg is determined by the cluster growth in the flocculation regime.
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  • 69
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    Keywords: Alkaline phosphatase ; green crab ; inhibition ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The inhibition of alkaline phosphatase from green crab (Scylla serrata) by L-cysteine has been studied. The results show that L-cysteine gives a mixed-type inhibition. The progress-of-substrate-reaction method previously described by Tsou [(1988), Adv. Enzymol. Related Areas Mol. Biol. 61, 391–436] was used to study the inactivation kinetics of the enzyme by L-cysteine. The microscopic rate constants were determined for reaction of the inhibitor with the free enzyme and the enzyme–substrate complex (ES) The results show that inactivation of the enzyme by L-cysteine is a slow, reversible reaction. Comparison of the inactivation rate constants of free enzyme and ES suggests that the presence of the substrate offers marked protection of this enzyme against inactivation by L-cysteine.
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    Glycoconjugate journal 16 (1999), S. 365-373 
    ISSN: 1573-4986
    Keywords: galectin 3 ; laminin binding ; kinetics ; cooperativity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Galectin 3, a β-galactoside binding protein, contains a C-terminal carbohydrate recognition domain (CRD) and an N-terminal segment including multiple repeats of a proline/tyrosine/glycine-rich motif. Previous work has shown that galectin 3 but not the isolated CRD binds to laminin, a multivalent ligand, with positive cooperativity indicating the formation of multiple interactions although the lectin in solution is monomeric. Using surface plasmon resonance, we find that hamster galectin 3 at sub-µmolar concentrations or its isolated CRD at all concentrations binds to a laminin substratum with similar association (kass; 10 – 30 000 M−1 S−1) and dissociation (kdiss; 0.2 – 0.3 S 1 −1 ) rates and weak affinity (Ka; 1 - 3 X 105 M−1). At higher concentrations of galectin 3 the off rate decreases ten fold leading to increased affinity. Ligation of an N-terminal epitope of galectin 3 with a monoclonal Fab fragment increases association and dissociation rates ten fold. A recombinant protein obtained by deletion of the first 93 N-terminal residues binds to laminin with positive cooperativity and a slowly dissociating fraction (Kdiss; 0.002 S−1) accummulates on the substratum. The data suggest that homophilic interactions between CRD as well as N terminal domains are implicated in galectin 3 aggregation on the substratum leading to positive binding cooperativity.
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    Fish physiology and biochemistry 20 (1999), S. 279-292 
    ISSN: 1573-5168
    Keywords: heat shock proteins ; hsp70 ; kinetics ; in vitro ; salmon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The heat shock protein (hsp) response of juvenile Atlantic salmon, Salmo salar was investigated in isolated tissues subjected to various degrees of thermal shock. Distinct but overlapping arrays of proteins from the major hsp families (hsps 100, 90, 70, 60 and small hsps) were induced in branchial lamellae, hepatic tissue and erythrocytes. The two most prominent proteins induced by heat shock (MW ≅ 65 and 66 kDa) were found to be antigenic homologues of mammalian hsps72/73. A 2.6 kb transcript upregulated by the same conditions hybridized with cDNA probes to both human and salmon hsp70. Branchial lamellae exhibited the greatest degree of thermotolerance and mounted the most significant heat shock response. Moderate thermal shock induced more species of proteins in branchial lamellae than in hepatic tissue or erythrocytes, with the rate of hsp65/66 synthesis increased by as much as five fold. Thermal shock induced hsp65/66 eight fold in erythrocytes. In contrast, hepatic tissue which was least tolerant of thermal shock, lacked the inducible hsp65 and exhibited minimal induction of hsp66. Persistence of hsps was tested in erythrocytes, where elevated levels remained in the cells for at least 48 h after heat shock. The temporal pattern and magnitude of the hsp response in the stenothermal Atlantic salmon differed from that previously reported for eurythermal species. Also notable was the limited hsp response mounted by salmon tissues exposed to sodium arsenite, a known inducer of hsps. The characteristics of the hsp response to thermal shock support the significance of these proteins in adaptation of Atlantic salmon to environmental insult.
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  • 72
    ISSN: 1573-0662
    Keywords: atmosphere ; kinetics ; nitrate radical ; monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, α-phellandrene, d-limonene, terpinolene and γ-terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, α-phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and γ-terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and α-phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[−(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[−(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and γ-terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.
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  • 73
    ISSN: 1573-0662
    Keywords: δ3-carene ; chlorine atoms ; isoprene ; kinetics ; methacrolein and methyl vinyl ketone
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    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.
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  • 74
    ISSN: 1572-8943
    Keywords: adducts ; cobalt complex ; DSC ; kinetics ; nickel complex ; O,O'-dialkyldithiophosphate ; pyridine ; TG-DTG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of tri(O,O'-diisopropyldithiophosphate)cobalt(III), Co(dptp)3 and bis (O,O'-diethyldithiophosphate)nickel(II), Ni(detp)2 and its adducts with pyridine, Ni(detp)2(py)2 or 4-methylpyridine, Ni(detp)(mpy)2 in a dynamic nitrogen atmosphere was investigated by TG-DTG and DSC techniques, which showed a medium endothermic peak for the evolution process of pyridine(or 4-methylpyridine) and a strong exothermic peak for that of O,O'-diethyldithiophosphate. The thermal stability and decomposition patterns for these compounds were compared and interpreted in terms of structural features such as bond character and steric effects. The kinetic parameters and mechanisms of every decomposition stage involved for all these complexes were obtained employing the non-isothermal kinetic analysis method suggested by Malek et al., which showed the kinetics mechanism for pyrolysis of pyridine(or 4-methylpyridine) is an S-B empirical model with lower activation energy, while that of O,O'-dialkyldithiophosphate is a diffusion model. These results are in accord with the fact that two ligands are of different type.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 653-659 
    ISSN: 1572-8943
    Keywords: dehydration ; kinetics ; lanthanide complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The 2-amino-4-chlorobenzoates of Y(III), La(III), Pr(III), Sm(III), Gd(III), Dy(III), Tm(III) and Lu(III) were prepared. Their general formula is Ln(C6H3NH2ClCOO)3·H2O. X-ray analysis demonstrated that all the prepared complexes are isostructural. This indicates the same mode of coordination of water and organic ligands throughout the whole series of lanthanide(III) 2-amino-4-chlorobenzoates. The dehydrations of the complexes were studied under non-isothermal conditions in air. From the thermogravimetric data on the dehydrations, the kinetic models best fitting the experimental TG curves were selected. These models suggest that the dehydration is governed by diffusion processes. Kinetic parameters such as the activation energy and pre-exponential factor were calculated by means of the differential and integral methods.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 877-884 
    ISSN: 1572-8943
    Keywords: dehydration ; kinetics ; manganese(II) oxalate dihydrate ; mechanism ; non-isothermal ; TG-DTA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method was proposed for determining the most probable mechanism function of a solid phase reaction. According to Coats-Redfern's integral equation Eβ→0 was calculated by extrapolating β to zero using a series of TG curves with different heating rates. Similarly, Eα→0 was calculated according to Ozawa's equation. The most probable mechanism function of the solid phase dehydration of manganese(II) oxalate dihydrate was confirmed to be G(α)=(1-α)1/2 by comparing Eα→0 with Eβ→0.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 855-861 
    ISSN: 1572-8943
    Keywords: education ; kinetics ; microscopy ; solid-state reactions ; teaching materials
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In an attempt to show the importance of preparing extensively teaching materials for comprehensive education in thermal analysis at an undergraduate level, the significance of the teaching materials concerning the thermal analysis and kinetics of the solid-state reactions is discussed by reviewing our teaching activities at Hiroshima University. Application of the thermoanalytical techniques to thermal decomposition of basic copper(II) salts is appropriate for an introductory experiment to thermal analysis. Microscopic observations of the textural change during the thermal dehydration of inorganic salt hydrates are suitable for introducing the kinetics of solid-state reactions. A computer practice of drawing the experimental master plot enables students to understand the kinetic theory.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 939-946 
    ISSN: 1572-8943
    Keywords: combustion ; high pressure DSC ; kinetics ; oil shale ; pyrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressurised differential scanning calorimeter (PDSC) has been used to obtain information on the pyrolysis and combustion characteristics of oil shales. Two distinct exothermic peaks were identified in combustion experiments known as low temperature oxidation (LTO) and high temperature oxidation (HTO) reaction regions. The pyrolysis process of all studied oil shale samples showed one exothermic effect at each total pressure studied. Kinetic data were analysed by Roger & Morris and Arrhenius methods and the results are discussed.
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    Journal of thermal analysis and calorimetry 56 (1999), S. 1329-1334 
    ISSN: 1572-8943
    Keywords: cyclodextrin complexes ; dehydration ; kinetics ; TG-DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Hydrated inclusion complexes of the hosts β-CD (CD=cyclodextrin), γ-CD and permethylated β-CD with the guest clofibric acid were analysed by TG and DSC methods to characterise their dehydration behaviours. Activation energies for dehydration of the β- and γ-CD clofibric acid complexes, determined by isothermal thermogravimetry, are significantly lower (∼20-25%) than those for the corresponding uncomplexed hydrated CDs. These data can be reconciled with X-ray structural data which show that H2O molecules in the complexes occupy different crystal sites from those occupied in the parent CDs.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 607-622 
    ISSN: 1572-8943
    Keywords: Cu–3.4 At.% Sb alloy ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of solute segregation to partial dislocations in a Cu–3.4 At.% Sb alloy was studied by using a phenomenological approach with differential scanning calorimetry and isothermal calorimetry. The material, severely deformed by repeated bending, presented an excess of dissociated edge dislocations with a dislocation density amounting to about 8.5·1014 m−2, calculated using a prior model of the authors, together with calorimetric recrystallization trace analysis. The kinetics was found to be ruled by two overlapping mechanisms: diffusion of solute atoms mostly through dislocation pipes in the initial and middle stages of the reaction process, acting together with bulk solute diffusion in these stages and later. Bulk solute diffusion increases as the reaction proceeds, as shown by the increasing values of apparent activation energy in the reaction. The exponent of the Mehl-Johnson-Avrami equation used in the phenomenological description was successfully fitted to a time—temperature-dependent function, increasing in agreement with the apparent activation energy behaviour, as may be expected.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 293-299 
    ISSN: 1572-8943
    Keywords: ENR ; kinetics ; thermal degradation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Epoxidized natural rubbers (ENRs) with different extents of epoxidation (B) were prepared under various reaction conditions. The effects of the amount of H2O2 and the reaction time on B are discussed. The glass transition temperature Tg, the thermal degradation temperature and the activation energy of thermal degradation of the ENRs increase with B. The results indicate that the thermal stability of the ENRs increases with B.
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    Journal of thermal analysis and calorimetry 58 (1999), S. 317-322 
    ISSN: 1572-8943
    Keywords: chrome iron ore ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of direct reduction of artificial chrome iron ore was studied by isothermal and non-isothermal methods. In the initial, middle and final periods, the reaction is controlled by nucleation and growth, a phase boundary reaction, and diffusion, respectively. In the main reaction region, the kinetic equation is 1−(1−α)1/3=kt and the apparent activation energy is 270 kJ mol−1. The kinetic mechanisms found with the isothermal and non-isothermal methods do not differ, and the activation energy values are approximately the same. However, the non-isothermal method can demonstrate the kinetic process completely.
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    Journal of statistical physics 95 (1999), S. 949-979 
    ISSN: 1572-9613
    Keywords: numerical simulations ; interface description ; kinetics ; phase ordering ; relaxation ; dynamical scaling ; model A ; curved surface ; lipid bilayer ; dominant length scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract An interface description and numerical simulations of model A kinetics are used for the first time to investigate the intrasurface kinetics of phase ordering on corrugated surfaces. Geometrical dynamical equations are derived for the domain interfaces. The dynamics is shown to depend strongly on the local Gaussian curvature of the surface, and can be fundamentally different from that in flat systems: dynamical scaling breaks down despite the persistence of the dominant interfacial undulation mode; growth laws are slower than t 1/2 and even logarithmic; a new very-late-stage regime appears characterized by extremely slow interface motion; finally, the zero-temperature fixed point no longer exists, leading to metastable states. Criteria for the existence of the latter are derived and discussed in the context of more complex systems.
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    Biodegradation 10 (1999), S. 177-191 
    ISSN: 1572-9729
    Keywords: AQUASIM ; biodegradation ; biofilm ; growth ; kinetics ; methane ; modelling ; nitrification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This article discusses the growth of methanotrophic biofilms. Several independent biofilm growths scenarios involving different inocula were examined. Biofilm growth, substrate removal and product formation were monitored throughout the experiments. Based on the oxygen consumption it was concluded that heterotrophs and nitrifiers co-existed with methanotrophs in the biofilm. Heterotrophic biomass grew on soluble polymers formed by the hydrolysis of dead biomass entrapped in the biofilm. Nitrifier populations developed because of the presence of ammonia in the mineral medium. Based on these experimental results, the computer program AQUASIM was used to develop a biological model involving methanotrophs, heterotrophs and nitrifiers. The modelling of six independent growth experiments showed that stoichiometric and kinetic parameters were within the same order of magnitude. Parameter estimation yielded an average maximum growth rate for methanotrophs, μm, of 1.5 ± 0.5 d−1, at 20 °C, a decay rate, bm, of 0.24 ± 0.1 d−1, a half saturation constant, $${\text{K}}_{{\text{S(CH}}_{\text{4}} {\text{)}}} $$ , of 0.06 ± 0.05 mg CH4/L, and a yield coefficient, $$Y_{CH_4 } $$ , of 0.57 ±: 0.04 g X/g CH4. In addition, a sensitivity analysis was performed on this model. It indicated that the most influential parameters were those related to the biofilm (i.e. density; solid-volume fraction; thickness). This suggests that in order to improve the model, further research regarding the biofilm structure and composition is needed.
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  • 85
    ISSN: 1573-5079
    Keywords: fluorescence lifetime ; kinetics ; P680+ ; transient absorption spectroscopy ; water splitting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The PS II–LHC II supercomplex is a novel type of oxygen evolving Photosystem II (PS II) core particle that contains the light harvesting complex proteins Lhcb1/2/4/5 in addition to the PS II reaction centre, oxygen evolving complex (OEC) and inner antennae [Hankamer et al. (1997) Eur J Biochem 243: 422–429]. The 33 and 23 kDa extrinsic proteins in these particles have been localised by image analysis of electron micrographs and averaging techniques [Boekema et al. (1998) Eur J Biochem 252: 268–276]. To assay the functionality of the water splitting complex, we compared the single flash P680+ reduction kinetics in these supercomplexes with those of PS II-rich granal stack membranes (BBYs). We found that the P680+ reduction kinetics in PS II–LHC II supercomplexes were indistinguishable from those in BBYs. We also examined a number of PS II core particles lacking the Lhcb components. All of these had different P680+ reduction kinetics, which we attributed to partial loss of OEC function before and during the measurements.
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  • 86
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    Photosynthesis research 60 (1999), S. 247-256 
    ISSN: 1573-5079
    Keywords: irradiance ; kinetics ; method ; photosynthesis ; regulation ; rubisco
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract An in vivo method for the estimation of kinetic parameters of partial reactions of carboxylation of ribulose 1,5-bisphosphate (RuBP) catalyzed by ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is described. Rubisco in barley, wheat and bean is different in the ability of its active centers to bind RuBP. The rate constant of the formation of the Rubisco-RuBP complex in these plants at 25 °C is 0.414, 0.245 and 0.660 mM-1 s-1, respectively. The rate constant of the reaction of the Rubisco-bound enediol with CO2 does not differ significantly in barley and wheat, and averages 66 mM-1 s-1. Decreased irradiance inhibits Rubisco in two ways: by reducing the concentration of operating catalytic sites and by decreasing the rate constant of binding of RuBP to Rubisco. High concentrations of CO2 inhibit Rubisco by decreasing the concentration of competent carboxylation centers, without any s ignificant influence upon the rate constants of partial reactions.
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  • 87
    ISSN: 1573-3017
    Keywords: rubidium ; cesium ; kinetics ; clearance-volume model ; fish
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract We used a two-compartment, clearance volume-based model to examine rubidium and cesium pharmacokinetics in channel catfish (Ictalurus punctatus) after intravascular administration. We compared the apparent volumes of distribution in the central and peripheral compartments and the intercompartmental and whole-body clearances of both metals at 20.0 °C and 27.5 °C. Biological half-times of Rb were 15 to 16 d at both temperatures, but Cs biological half-times averaged 101 d and 85 d at 20.0 °C and 27.5 °C, respectively (5 to 7 times longer than those of Rb in the same individual). Both the intercompartmental and total body clearances of Rb were also 6 to 7 times greater than those of Cs. The apparent volumes of distribution for Rb in the central compartments were twice those of Cs and remained constant with temperature. The apparent volumes of distribution of both elements in peripheral compartments were large compared with their corresponding central compartments, and decreased by a similar extent with increased temperature. Cesium tissue to blood ratios were greatest for white muscle, with more than 85% of the Cs present in this tissue. Partitioning of Cs in peripheral tissues apparently decreased with increased temperature conditions. Our results indicate that application of pharmacokinetic modeling techniques can enhance studies of radionuclide kinetics by helping to identify rate-limiting processes within individuals that may control uptake and elimination.
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  • 88
    ISSN: 1573-2932
    Keywords: arid-zone soils ; field capacity ; fractionation ; heavy metals ; kinetics ; redistribution ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.
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  • 89
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    Hyperfine interactions 119 (1999), S. 11-21 
    ISSN: 1572-9540
    Keywords: exotic atom ; muonic hydrogen ; pionic hydrogen ; cascade ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Recent theoretical and experimental studies of the exotic atoms with Z = 1 are reviewed. An interplay between the atomic internal and external degrees of freedom is essential for a good description of the atomic cascade. The perspective of ab initio cascade calculations is outlined.
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  • 90
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    Reaction kinetics and catalysis letters 66 (1999), S. 265-272 
    ISSN: 1588-2837
    Keywords: Oxygen ; surface ; silver ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different adsorption forms of oxygen on silver are discussed. Four main types of oxygen forming at different temperatures and oxygen pressures have been distinguished. A kinetic model describing the formation and transformations of the oxygen forms and taking into account the surface amorphization has been proposed. Numerical modeling of stationary concentrations using this model gives evidence for a temperature window ΔT=500–800 K, where a quasimolecular oxygen state (E=530.5 eV, Tdes=800–900 K) can exist at high oxygen pressures.
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  • 91
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    Reaction kinetics and catalysis letters 66 (1999), S. 289-295 
    ISSN: 1588-2837
    Keywords: Resorcinol photooxidation ; kinetics ; intermediates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethanedial, butanoic acid anhydride and trihydroxybenzenes have been determined as intermediates of resorcinol photocatalytic oxidation. The photoreaction rate shows a 1st order dependence on resorcinol concentration. The calculated reaction rate constant is 2.1×10−8 mol dm−3 s−1, which is similar to the rate constant of phenol photocatalytic oxidation on TiO2 reported beore.
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  • 92
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    Reaction kinetics and catalysis letters 66 (1999), S. 55-62 
    ISSN: 1588-2837
    Keywords: Oxidation of sulfides ; kinetics ; higher Co oxide IR ; XPS ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Low-temperature heterogenous oxidation of sulfide ions on a higher Co oxide system in aqueous medium has been studied. The effects of pH, temperature and catalyst amount on the kinetic parameters as well as on the selectivity of the oxidation process were investigated. An oxidation mechanism has been proposed based on the results of kinetic investigations and on the data obtained by IR and XPS spectroscopic studies of Co oxide before and after sulfide ion oxidation.
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  • 93
    ISSN: 1588-2837
    Keywords: Silica ; monodisperse particles ; supramolecular crystallization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of supramolecular crystallization of concentrated suspensions is three-dimensional and follows the Avrami-Erofeev equation: A=1-exp[-(kt)m], where m=4. The rate constant k is proportional to the probability of the appearance of a crystallization center in unit volume in unit time and the linear crystal growth rate, which is determined experimentally.
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  • 94
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    Reaction kinetics and catalysis letters 68 (1999), S. 237-242 
    ISSN: 1588-2837
    Keywords: Diols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the oxidation of diols by ozone was investigated by a spectrophotometric method in the temperature interval of 277–304 K. The activation parameters of the reaction were determined.
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  • 95
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    Reaction kinetics and catalysis letters 68 (1999), S. 257-263 
    ISSN: 1588-2837
    Keywords: Alphatic alcohols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of oxidation of aliphatic alcohols by ozone in aqueous solutions was investigated in the temperature interval of 292–317 K. The activation parameters of the reaction were determined. The dissociation energies of CH-bonds of the studied substrates were calculated with the use of the AM1 semiempirical method.
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  • 96
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    Water, air & soil pollution 109 (1999), S. 429-442 
    ISSN: 1573-2932
    Keywords: electrochemical treatment ; kinetics ; nitrite ; stainless steel electrodes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The efficiency of nitrite removal in an electrochemical cell was investigated in this study using stainless steel electrodes. The experiments were designed to study the effects of current input, volume of the solution, initial pH, and number of electrodes on removal of nitrite at a concentration typical to aquaculture system effluents. Current variation causes opposite trends, while an increase in current would increase the oxidizing efficiency of the system, the voltage induced increase in pH due to hydrogen evolution would decrease the efficiency of the oxidizing agent formed. However, the highest nitrite removal was achieved at a current of 2 A and a complete removal was attained after a duration of ten minutes. A first order reaction model was developed to predict the effect of current on nitrite removal. The energy consumption was directly proportional to the initial pH and the solution volume, while it was inversely proportional to the number of electrodes.
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  • 97
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    Journal of inclusion phenomena and macrocyclic chemistry 35 (1999), S. 139-146 
    ISSN: 1573-1111
    Keywords: dihydropyridine ; photochromism ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermally driven reactions in a crystalline photochromic solid, 1-methyl-2,4,4,6-tetraphenyl-1,4-dihydropyridine (DHP), has been studied. The processes have been monitored by measuring the isothermal bleaching of coloured species produced upon UV irradiation of DHP, and by measuring the heat flow in non-isothermal differential scanning calorimetry experiments. Signatures of two processes were detected; a combination of quantum-chemical calculations and spectroscopic measurements allowed us to attribute them to reactions occurring in the photochromic system.
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  • 98
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    Tribology letters 7 (1999), S. 67-71 
    ISSN: 1573-2711
    Keywords: alkanethiol ; self‐assembled monolayers ; quartz crystal microbalance ; viscoelasticity ; kinetics ; ellipsometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Quartz crystal microbalance techniques and in situ spectroscopic ellipsometry are used to probe the structure‐dependent intrinsic viscoelastic properties of self‐assembled CH3(CH2)8SH alkanethiol monolayers adsorbed from the gas phase onto Au(111)‐textured substrates. Physisorbed molecules, mixed chemisorbed‐fluid/solid phases and solid‐phase domain boundaries make sequentially dominant contributions to the measured energy dissipation in the growing monolayer. Deviations from Langmuir adsorption kinetics reveal a precursor‐mediated adsorption channel. These studies reveal the impact of structural heterogeneity in tribological studies of monolayer lubricants.
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  • 99
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    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 100
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    Journal of solution chemistry 27 (1998), S. 1123-1138 
    ISSN: 1572-8927
    Keywords: Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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