"Hidden” degassing from streams: estimation of the CO2 release from the thermal springs of Sperchios Basin, Greece

Areas located at plate boundaries are characterized by the presence of seismic, volcanic, and geothermal activity, as well as ore deposition. Such processes are enhanced by the circulation of hydrothermal fluids in the crust transporting volatiles from either the deep crust or the mantle to the surface. Intense geodynamic activity is also taking place in Greece giving rise to: (i) the highest seismicity in Europe, (ii) the presence of an active volcanic arc and numerous areas of anomalously high geothermal gradient, and (iii) a widespread occurrence of thermal springs. Elevated heat flow values are concentrated in Sperchios basin, an area characterised by a system of deeply rooted extensional faults and quaternary volcanic activity. This regime favoured the formation of hydrothermal systems, the surface expression of which are thermal springs with intense bubbling of CO2-rich gases. Flux measurements in the bubbling pools were made with the floating chamber method. The highest bubbling CO2 output is found in Thermopyles and Psoroneria (1 and 2 t/d, respectively). The outgoing channels of these springs have an elevated flow (>250 l/s) of gas-charged water (>15 mmol/l of CO2). Although no bubbling is noticed along the stream, the CO2 content decreases by an order of magnitude after few hundreds of metres, indicating an intense degassing from the water. Taking into account the water flow and the amount of CO2 lost to the atmosphere, the CO2 output of the outgoing channels is quantified in >10 t/d for Thermopyles and 9 t/d for Psoroneria. An estimation is also made at Ypati, Kamena Vourla, Koniavitis and Edipsos, where the mean values reach 1 t/d of CO2 for each spring. The obtained values are always higher respect to the estimated outputs from visible bubbling, suggesting that most of the degassing is “hidden”. Furthermore, the loss of CO2 from the water determines a shift in dissolved carbonate species as demonstrated by the pH increase along the channel that leads eventually to an oversaturation in carbonate minerals and therefore travertine deposition. To sum up, the total CO2 output of the study area is estimated at 30 t/d, with the major contribution deriving from the degassing along the outflow channels of the thermal springs. Such output is comparable to that of the single active volcanic systems along the South Aegean Volcanic Arc (Sousaki, Methana, Milos, Santorini, Kos and Nisyros) and highlights the importance of “hidden” degassing along CO2-oversaturated streams

Gas Geochemistry and Fractionation Processes in Florina Basin, Greece

Florina Basin is located in northern Greece, close to Mount Voras where the volcanic activity of Late Messinian age began. In the area, many CO2-rich gas emissions are present as a bubbling free-phase in groundwater (both springs and wells) and soil gases. Volcanism along with the geological and geodynamic regime of the basin, created the ideal conditions for CO2 accumulation in vertically stacked reservoirs. One of these, industrially exploited by the company Air Liquide Greece, produces 30,000 t/a of CO2. Results show that CO2 concentrations in the gases of Florina can arrive up to 99.8% and are mostly above 90%. Moreover, C-isotope composition (-2.1 to + 0.3 h vs. VPDB) indicates a mixed mantle-limestone origin for CO2, while He isotope composition (R/RA from 0.21 to 1.20) shows a prevailing crustal origin with an up to 15% mantle contribution. Helium and methane, with concentrations spanning over three orders of magnitude, show a positive correlation and a consequent high variability of He/CO2 and CH4/CO2 ratios. This variability can be attributed to the interaction of the uprising gases with groundwater that chemically fractionates them due to their different solubility. Based on the CO2, CH4 and He concentrations, gas samples collected in the basin can be divided in 3 groups: a) deep reservoir gases, b) enriched in less soluble gases and c) depleted in less soluble gases. The first group consists of gas samples collected at the Air Liquide extraction wells, which tap a 300m deep reservoir. This group can be considered as the least affected by fractionation processes due to interaction with groundwater. The gases of the second group due to their interaction with shallower unsaturated aquifers, become progressively enriched in less soluble gases (He and CH4). Finally, the third group represents residual gas phases after extensive degassing of the groundwater during its hydrological pathway

A layering model for superconductivity in the borocarbides

We propose a superlattice model to describe superconductivity in layered materials, such as the borocarbide families with the chemical formul\ae\ $RT_2$B$_2$C and $RT$BC, with $R$ being (essentially) a rare earth, and $T$ a transition metal. We assume a single band in which electrons feel a local attractive interaction (negative Hubbard-$U$) on sites representing the $T$B layers, while U=0 on sites representing the $R$C layers; the multi-band structure is taken into account minimally through a band offset $\epsilon$. The one-dimensional model is studied numerically through the calculation of the charge gap, the Drude weight, and of the pairing correlation function. A comparison with the available information on the nature of the electronic ground state (metallic or superconducting) indicates that the model provides a systematic parametrization of the whole borocarbide family.Comment: 4 figure

Theory of the optical conductivity of (TMTSF)2_2PF6_6 in the mid-infrared range

We propose an explanation of the mid-infrared peak observed in the optical conductivity of the Bechgaard salt (TMTSF)$_2$PF$_6$ in terms of electronic excitations. It is based on a numerical calculation of the conductivity of the quarter-filled, dimerized Hubbard model. The main result is that, even for intermediate values of $U/t$ for which the charge gap is known to be very small, the first peak, and at the same time the main structure, of the optical conductivity is at an energy of the order of the dimerization gap, like in the infinite $U$ case. This surprising effect is a consequence of the optical selection rules.Comment: 10 pages, 9 uuencoded figure

Charge-density waves in the Hubbard chain: evidence for 4k_F instability

Charge density waves in the Hubbard chain are studied by means of finite-temperature Quantum Monte Carlo simulations and Lanczos diagonalizations for the ground state. We present results both for the charge susceptibilities and for the charge structure factor at densities \rho=1/6 and 1/3; for \rho=1/2 (quarter filled) we only present results for the charge structure factor. The data are consistent with a 4k_F instability dominating over the 2k_F one, at least for sufficiently large values of the Coulomb repulsion, U. This can only be reconciled with the Luttinger liquid analyses if the amplitude of the 2k_F contribution vanishes above some U^*(\rho).Comment: RevTeX, 4 two-column pages with 7 colour figures embedded in tex

Charge and spin excitations of insulating lamellar copper oxides

A consistent description of low-energy charge and spin responses of the insulating Sr_2CuO_2Cl_2 lamellar system is found in the framework of a one-band Hubbard model which besides $U$ includes hoppings up to 3^{rd} nearest-neighbors. By combining mean-field calculations, exact diagonalization (ED) results, and Quantum Monte Carlo simulations (QMC), we analyze both charge and spin degrees of freedom responses as observed by optical conductivity, ARPES, Raman and inelastic neutron scattering experiments. Within this effective model, long-range hopping processes flatten the quasiparticle band around $(0,\pi)$. We calculate also the non-resonant A_{1g} and B_{1g} Raman profiles and show that the latter is composed by two main features, which are attributed to 2- and 4-magnon scattering.Comment: 6 pages, 3 figures, To be published in PRB (july

Bond-charge Interaction in the extended Hubbard chain

We study the effects of bond-charge interaction (or correlated hopping) on the properties of the extended ({\it i.e.,} with both on-site ($U$) and nearest-neighbor ($V$) repulsions) Hubbard model in one dimension at half-filling. Energy gaps and correlation functions are calculated by Lanczos diagonalization on finite systems. We find that, irrespective of the sign of the bond-charge interaction, $X$, the charge--density-wave (CDW) state is more robust than the spin--density-wave (SDW) state. A small bond-charge interaction term is enough to make the differences between the CDW and SDW correlation functions much less dramatic than when $X=0$. For $X=t$ and fixed $V<2t$ ($t$ is the uncorrelated hopping integral), there is an intermediate phase between a charge ordered phase and a phase corresponding to singly-occupied sites, the nature of which we clarify: it is characterized by a succession of critical points, each of which corresponding to a different density of doubly-occupied sites. We also find an unusual slowly decaying staggered spin-density correlation function, which is suggestive of some degree of ordering. No enhancement of pairing correlations was found for any $X$ in the range examined.Comment: 10 pages, 7 PostScript figures, RevTeX 3; to appear in Phys Rev

Two--magnon scattering and the spin--phonon interaction beyond the adiabatic approximation

We consider a model of Raman scattering for a two--dimensional $S=1/2$ Heisenberg Anti-Ferromagnet which includes a {\it dynamical} spin--phonon interaction. We observe a broadening of the line shape due to increased coupling with excited high--energy spin states. Our results are close to a model of random static exchange interactions, first introduced in this context by Haas {\it et al.} [J. Appl. Phys. {\bf 75}, 6340, (1994)], which, when extended to large numbers of spins, explains experiments in the parent insulating compounds of high-$T_c$ superconductors.Comment: 14 pages (revtex format), 8 postscript figure

Duvalo “Volcano” (North Macedonia): A Purely Tectonic‐related CO2 Degassing System

Duvalo “volcano” is a site of anomalous geogenic degassing close to Ohrid (North Macedonia) not related to volcanic activity, despite its name. CO2 flux measurements made with the accumulation chamber (321 sites over ∼50,000 m2) showed fluxes up to nearly 60,000 g m-2 d-1, sustaining a total output of ∼67 t d-1. Soil gas samples were taken at 50 cm depth from sites with high CO2 fluxes and analyzed for their chemical and isotope composition. The gas is mainly composed by CO2 (&gt; 90%) with significant concentrations of H2S (up to 0.55 %) and CH4 (up to 0.32 %). The isotope compositions of He (R/RA 0.10) and of CO2 (δ13C ∼0‰) exclude significant mantle contribution, while δ13C-CH4 (∼ -35‰) and δ2H-CH4 (∼ -170‰) suggest a thermogenic origin for CH4. The area is characterized by intense seismic activity and Duvalo corresponds to an active tectonic structure bordering the Ohrid graben. The production of H2S within the stratigraphic sequence may be explained by thermochemical reduction of sulfate. The uprising H2S is partially oxidized to sulfuric acid that, reacting with carbonate rocks, releases CO2. The tectonic structure of the area favors fluid circulation, sustaining H2S production and oxidation, CO2 production and allowing the escape of the gases to the atmosphere. In the end, Duvalo represents a tectonic-related CO2 degassing area whose gases originate mostly, if not exclusively, in the shallowest part of the crust (&lt;10 km). This finding highlights that even systems with trivial mantle contribution may sustain intense CO2 degassing (&gt; 1000 t km-2 d-1)

Optical Spectra in the Ferromagnetic States near the Charge Ordering

The optical conductivity is studied numerically for the ferromagnetic metallic state close to the charge ordering observed in perovskite manganites.Comment: 11 pages, Latex, 6 ps figure