Development of an Italian catalogue of potential CO2storage sites: an approach from deep wells data

Stabilize and reduce the atmospheric concentration of anthropogenic greenhouse gases is one of the principal goal that have to be accomplished in short time, in order to reduce the climate changes and the global warming, following the World Energy Outlook 2007 program by IEA. The most promising remedy, proposed for large CO2 sources like thermoelectric power plants, refineries and cement industries, is to separate the flue gas capturing the CO2 and to store it into deep sub-surface geological reservoirs, such as deep saline aquifers, depleted oil and gas fields and unminable coal beds. Among these options, deep saline aquifers are considered the reservoirs with the larger storage potentiality, as a consequence of a wide availability with respect to deep coal seems, depleted oil fields and gas reservoirs. The identification of a possible storage site necessarily passes through the demonstration that CO2 can be injected in extremely safe conditions into geological deep formations, with impermeable caprock above the aquifer/s, which physic-chemical-mineralogical conditions are useful to a better mineral and solubility trapping as well as the hydrodynamic or physical/ structural ones. In order to support the identification of potential storage reservoirs in Italy, INGV jointly with CESI RICERCA S.p.A. accomplished a detailed reworking of available geological, geophysical, geochemical and seismological data, in order to support the existing European GESTCO as well as the CO2GeoCapacity projects. Aim of this work is to establish some site selection criteria to demonstrate the possibility of the geological storage of CO2 in Italy, even if it is located in an active geodynamical domain. This research started from the study of 7575 wells drilled on Italian territory during the last 50 years for gas/oil and geothermal exploration. Among this data-set as a whole, only 1700 wells (deeper than 800 m) have been selected. Only 1290 of these wells have a public-available composite log and fit with the basic prerequisites for CO2 storage potential, mostly as deep saline aquifer/s presence. Wells data have been organized into a geodatabase containing information about the nature and the thickness of geological formations, the presence of fresh, saline or brackish water, brine, gas and oil, the underground temperature, the permeability, porosity and geochemical characteristics of the caprock and the reservoirs lithologies. Available maps, seismic and geological profiles containing or closer to the analyzed wells have been catalogued too. In order to constrain the supercritical behaviour of the CO2 and to prevent the escape of gaseous CO2 to the surface, a first evaluation of the caprock presence and quality has been done on these selected wells. Using a numerical parameterization of the caprock lithologies, a “Caprock Quality Factor” (Fbp) has been defined, which clustered the wells into 5 different classes of caprock impermeability (ranging between the lowest 1 to highest 5). The analysis shows that more than 50% of the selected wells have an Fbp Factor between 4 and 5 (good and optimal quality of caprock), and are mostly located in foredeep basins of the Alps-Apenninic Chain. The geodatabase also includes: i) the seismogenetic sources (INGV DISS 3.0.4 Database of Individual Seismogenetic Sources), ii) an elaboration of seismic events catalogues (INGV CFTI, CPTI04, NT4.1), iii) the Diffuse Degassing Structures (DDS), as part of the INGV project V5 diffuse degassing in Italy geodatabase, considered as “CO2 analogue” field-tests, iv) the distribution of the thermal anomalies on the Italian Territory, linked to the presence of volcanic CO2 emissions, in order to consider the CO2 diffuse degassing risk assessment on the Italian territory Successively it has been created a geodatabase on the nature and quality of deep aquifers for the high-ranking wells sub-dataset (where the aquifers data are available), containing the following parameters: i) presence of one or more aquifers deeper than 800 meters; ii) thickness of the aquifer/s; iii) lithology of the reservoir/s; iv) available chemical analysis; v) distance from closer power plants or other anthropogenic CO2 sources.The final aim of these work is to help to find potential areas in Italy where CO2 storage feasibility studies can be done. In these cases it is necessary to implement the knowledge by: i) better evaluation of saline aquifer quality; ii) estimation of CO2 storage capacity by 3D-modeling of deep crustal structures; iii) fluid-dynamic and geochemical modelling of water-rock-CO2 interaction paths

Simultaneous determination of the kinetics of cardiac output, systemic O2 delivery and lung O2 uptake at exercise onset in men.

We tested whether the kinetics of systemic O2 delivery (Q'aO2) at exercise start was faster than that of lung O2 uptake (V' O2), being dictated by that of cardiac output (Q'), and whether changes in Q' would explain the postulated rapid phase of the V'O2 increase. Simultaneous determinations of beat-by-beat (BBB) Q' and Q' aO2, and breath-by-breath V'O2 at the onset of constant load exercises at 50 and 100 W were obtained on six men (age 24.2 +/-3.2 years, maximal aerobic power 333 +/- 61 W). V'O2 was determined using Grønlund’s algorithm. Q' was computed from BBB stroke volume (Qst, from arterial pulse pressure profiles) and heart rate (fH, electrocardiograpy) and calibrated against a steadystate method. This, along with the time course of hemoglobin concentration and arterial O2 saturation (infrared oximetry) allowed computation of BBB Q'aO2. The Q', Q'aO2 and V'O2 kinetics were analyzed with single and double exponential models. fH, Qst, Q', and V'O2 increased upon exercise onset to reach a new steady state. The kinetics of Q'aO2 had the same time constants as that of Q'. The latter was twofold faster than that of V'O2. The V'O2 kinetics were faster than previously reported for muscle phosphocreatine decrease. Within a two-phase model, because of the Fick equation, the amplitude of phase I Q' changes fully explained the phase I of V'O2 increase. We suggest that in unsteady states, lung V' O2 is dissociated from muscle O2 consumption. The two components of Q' and Q'aO2 kinetics may reflect vagal withdrawal and sympathetic activation

The role of hole transport between dyes in solid-state dye-sensitized solar cells

In dye-sensitized solar cells (DSSCs) photogenerated positive charges are normally considered to be carried away from the dyes by a separate phase of hole-transporting material (HTM). We show that there can also be significant transport within the dye monolayer itself before the hole reaches the HTM. We quantify the fraction of dye regeneration in solid-state DSSCs that can be attributed to this process. By using cyclic voltammetry and transient anisotropy spectroscopy, we demonstrate that the rate of interdye hole transport is prevented both on micrometer and nanometer length scales by reducing the dye loading on the TiO₂ surface. The dye regeneration yield is quantified for films with high and low dye loadings (with and without hole percolation in the dye monolayer) infiltrated with varying levels of HTM. Interdye hole transport can account for >50% of the overall dye regeneration with low HTM pore filling. This is reduced to about 5% when the infiltration of the HTM in the pores is optimized in 2 μm thick films. Finally, we use hole transport in the dye monolayer to characterize the spatial distribution of the HTM phase in the pores of the dyed mesoporous TiO₂

Cardiac output by model flow method from intra-arterial and finger tip pulse pressure profiles

Modelflow®, when applied to non-invasive fingertip pulse pressure recordings, is a poor predictor of cardiac output (Q’ litre· min-1). The use of constants established from the aortic elastic characteristics, which differ from those of finger arteries, may introduce signal distortions, leading to errors in computing Q’. We therefore hypothesized that peripheral recording of pulse pressure profiles undermines the measurement of Q’ withModelflow®, so we compared Modelflow® beat-by-beat Q’ values obtained simultaneously non-invasively from the finger and invasively from the radial artery at rest and during exercise. Seven subjects (age, 24.0 + - 2.9 years; weight, 81.2 + - 12.6 kg) rested, then exercised at 50 and 100 W, carrying a catheter with a pressure head in the left radial artery and the photoplethysmographic cuff of a finger pressure device on the third and fourth fingers of the contralateral hand. Pulse pressure from both devices was recorded simultaneously and stored on a PC for subsequent Q’ computation. The mean values of systolic, diastolic and mean arterial pressure at rest and exercise steady state were significantly (P < 0.05) lower from the finger than the intra-arterial catheter. The corresponding mean steady-state Q’ obtained from the finger (Q’porta) was significantly (P < 0.05) higher than that computed from the intra-arterial recordings (Q’pia). The line relating beat-by-beat Q’porta and Q’pia was y = 1.55x - 3.02 (r2 = 0.640). The bias was 1.44 litre · min-1 and the precision was 2.84 litre · min-1.The slope of this line was significantly higher than 1, implying a systematic overestimate of Q’ by Q’porta with respect to Q’pia. Consistent with the tested hypothesis, these results demonstrate that pulse pressure profiles from the finger provide inaccurate absolute Q’ values with respect to the radial artery, and therefore cannot be used without correction with a calibration factor calculated previously by measuring Q’ with an independent method

Phase I dynamics of cardiac output, systemic O2 delivery and lung O2 uptake at exercise onset in men in acute normobaric hypoxia.

We tested the hypothesis that vagal withdrawal plays a role in the rapid (phase I) cardiopulmonary response to exercise. To this aim, in five men (24.6+/-3.4 yr, 82.1+/-13.7 kg, maximal aerobic power 330+/-67 W), we determined beat-by-beat cardiac output (Q), oxygen delivery (QaO2), and breath-by-breath lung oxygen uptake (VO2) at light exercise (50 and 100 W) in normoxia and acute hypoxia (fraction of inspired O2=0.11), because the latter reduces resting vagal activity. We computed Q from stroke volume (Qst, by model flow) and heart rate (fH, electrocardiography), and QaO2 from Q and arterial O2 concentration. Double exponentials were fitted to the data. In hypoxia compared with normoxia, steady-state fH and Q were higher, and Qst and VO2 were unchanged. QaO2 was unchanged at rest and lower at exercise. During transients, amplitude of phase I (A1) for VO2 was unchanged. For fH, Q and QaO2, A1 was lower. Phase I time constant (tau1) for QaO2 and VO2 was unchanged. The same was the case for Q at 100 W and for fH at 50 W. Qst kinetics were unaffected. In conclusion, the results do not fully support the hypothesis that vagal withdrawal determines phase I, because it was not completely suppressed. Although we can attribute the decrease in A1 of fH to a diminished degree of vagal withdrawal in hypoxia, this is not so for Qst. Thus the dual origin of the phase I of Q and QaO2, neural (vagal) and mechanical (venous return increase by muscle pump action), would rather be confirmed

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films

Charge recombination between oxidized dyes attached to mesoporous TiO2 and electrons in the TiO2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts

production and thermalization of positronium in homogeneous porous silica

Positronium yield using the "3γ method" and lifetime measurements were performed at cryogenic and room temperature by means of a variable energy positron beam in homogeneous porous silica (Aerogel). An estimation of the positronium (Ps) mean diffusion length was obtained by measuring capped samples. An efficient formation of cooled Ps atoms is a requisite for the production of antihydrogen, with the aim of a direct measurement of the Earth gravitational acceleration g of antimatter, which is the primary scientific goal of AEgIS (Antimatter Experiment: gravity, Interferometry, Spectroscopy; CERN, Geneva). Porous materials are necessary to obtain a high Ps yield as well as to thermalize Ps. Our results indicate a high Ps production, long survival time and diffusion length in Aerogel samples. It will be shown that positronium yield, lifetime and diffusion length are independent on temperature and on the effect of gas adsorption at low temperature. The results indicate that Aerogel is a good candidate for an efficient formation of cold Ps for the AEgIS experiment

The effect of lower body negative pressure on phase 1 cardiovascular responses at exercise onset in healthy humans

We tested the hypothesis that vagal withdrawal and increased venous return interact in determining the rapid cardiac output response (Phase I) at exercise onset. We used lower body negative pressure (LBNP) to increase blood dislocation to the heart by muscle pump action and simultaneously reduce resting vagal activity. At exercise start, we expected larger response amplitude for stroke volume and smaller for heart rate at progressively stronger LBNP levels, so that the cardiac output response would remain unchanged. Ten subjects performed 50 W exercise supine in Control condition and during -45 mmHg LBNP exposure. On single beat basis, we measured heart rate (HR), stroke volume (SV), and we calculated cardiac output (CO). We computed Phase I response amplitudes (A1) using an exponential model. SV A1 was higher under LBNP than in Control (p &lt; 0.05). Conversely, the A1 of HR, was 23 ± 56 % lower under LBNP than in Control (although NS). Since these changes tended to compensate each other, the A1 for CO was unaffected by LBNP. The rapid SV kinetics at exercise onset is compatible with an effect of increased venous return, whereas the vagal withdrawal conjecture cannot be dismissed for HR kinetics. The rapid CO response may indeed be the result of two independent yet parallel mechanisms, as hypothesized, one acting on SV, the other on H