Massimo Guidi

Soil CO2 flux measurements in volcanic and geothermal areas

Abstract The accumulation chamber methodology allows one to obtain reliable values of the soil CO2 flux, ϕsoil CO2, in the range 0.2 to over 10 000 g m−2 d−1, as proven by both laboratory tests and field surveys in geothermal and volcanic areas. A strong negative correlation is observed between Δϕsoil CO2/Δt and ΔPatm/Δt. Maps of classes of log ϕsoil CO2 for the northern sector of Vulcano Island, Solfatara of Pozzuoli, Nea Kameni Islet and Yanbajain geothermal field evidence that active faults and fractures act as uprising channels of deep, CO2-rich geothermal or magmatic gases. The total diffuse CO2 output was evaluated for each surveyed area.

Geochemical and seismological investigations at Vulcano (Aeolian Islands) during 1978–1989

Both geochemical and geophysical evidence indicates that the activity of the fumarolic system of the Fossa crater can be divided into two periods. From 1978 to 1983, such activity has been mainly controlled by two competing processes which affect the permeability of the fumarolic system at deep levels: (1) rock fracturing induced by faulting and (2) mineral deposition-alteration. The latter, which causes a slow decrease of the permeability at deep levels through clogging of fractures and voids, prevailed at the end of this period, determining a fluid pressure increment in the deep parts of the system. From 1984 to 1989, fluid pressure at deep levels remained persistently high, triggering local microseismic swarms. Furthermore, PT conditions much higher than before were attained in the zones where hydrothermal fluids seep into the conduits from lateral aquifers, owing to an uprising of the isotherms, a deepening of these seeping zones, or both.

Chemical geothermometry and geobarometry in hydrothermal aqueous solutions: A theoretical investigation based on a mineral-solution equilibrium model

Abstract The theoretical compositions of an aqueous solution in equilibrium with a mineral assemblage made up of low-albite, K-feldspar, either a Ca-Al-silicate or calcite, clinochlore, muscovite, quartz, anhydrite, and fluorite, under varying T-PCO2-mcl conditions of geothermal interest, indicate that 1. 1) the total SO4 content as well as the Na K , K 2 Mg , and SO 4 F 2 ratios are potential geothermometers; 2. 2) the total HCO3 content as well as the K 2 Ca , Ca Mg , HCO 3 F , and (HCO 3 ) 2 SO 4 ratios are potential PCO2 indicators; 3. 3) the Na, K, Ca, and Mg total contents as well as the Na 2 Mg and Na 2 Ca ratios are mainly controlled by the total ionic salinity and are therefore hardly suitable as geoindicators. A preliminary test of the equations involving total HCO3 content as well as K 2 Ca and HCO 3 F ratios as PCO2 indicators have provided satisfactory results.

Lake Bogoria hot springs (Kenya): geochemical features and geothermal implications

Abstract Many boiling springs and fumaroles are present along the shores of Lake Bogoria, which is a closed-basin alkaline saline lake typical of African Rifts. Two different geothermal waters, both of Na-HCO3 type have been recognized. The first, discharged by the boiling springs located along the western shores of the lake, comes from a shallow steam-heated thermal aquifer. Its temperature is close to 100°C, as indicated by chalcedony solubility, while the chloride content of these waters is slightly higher than 200 mg L−1. The second, recognizable in the southernmost boiling springs, is representative of a deeper and hotter geothermal reservoir. The occurrence of mixing and boiling processes complicates the interpretation of geochemical data. Nevertheless, a chloride content of about 660 mg L−1, an equilibrium temperature close to 170°C and a high carbon dioxide partial pressure, at least 10–20 bar, have been estimated for the deep geothermal reservoir.

Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO4. Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO4 and 663 for HCO−3. Very good positive correlations are observed for the Ca2+–Mg2+–HCO−3–SO2−4–NO−3 system, indicating that dissolution of Ca (±Mg)-carbonate particles by H2SO4 and HNO3 from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na+ and Cl− in monthly precipitation derive essentially from sea spray, but the contribution of Na+ from continental sources is appreciable in a number of individual rains. NH+4 appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K+ is probably of continental origin from soil dust. The S isotopic composition of SO4 is systematically positive, with mean δ34S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO4 is estimated to have a δ34S value in the range +2.5 to +4.5‰, whereas a distinctive δ34S of −4.5‰ or lower indicates SO4 from oxidation of biogenic gases. The isotopic and chemical compositions of SO4 do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.

Water chemistry of Lake Albano (Italy)

Abstract Lake Albano was stratified at the time of our survey, in December 1997, in agreement with previous observations [Martini et al., Geochem. J. 28 (1994) 173–184; Cioni et al., Report for the Civil Protection Department (1995); Pedreschi, Accad. Lucch. Sci. Lett. Arti (1995) 39]. In the absence of phenomena induced by seismic activity, either local or regional, lake stratification may be perturbed by cooling of shallow waters below ∼8.5°C. Circulation is expected to homogenize lake waters and eventually to trigger gas exsolution when total gas pressure exceeds hydrostatic pressure. In December 1997, total gas pressure in lake water was very close to atmospheric pressure (0.9–1.3 bar) at all depths, possibly due to the occurrence of a recent episode of circulation and presumed gas exsolution. The state of saturation of Lake Albano waters and the similarity of the relative concentrations of Na, K, Mg, and Ca in lake waters, local groundwaters, and local volcanic rocks indicate that Na, K, Mg, and Ca concentrations in Lake Albano waters are mainly governed by incongruent dissolution of local volcanic rocks, coupled with minor calcite precipitation at shallow depths.

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (,14 m) oxic epilimnion overlying a ,200 m-thick anoxic hypolimnion. Dissolved CO2 concentrations reached 1000 mg/kg in the lower stratum. Loss of CO2 from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification. The Cl, SO4 and HCO3 contents of Lake Quilotoa are intermediate between those of acid‐SO4‐Cl Crater lakes and those of neutral-HCO3 Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid‐SO 4‐Cl Crater lakes. The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by ,48C or providing heat to hypolimnetic waters or by seismic activity. Although Quilotoa lake contains a huge amount of dissolved CO2O,3 £ 10 11 gU; at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO 2-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended. q 2000 Elsevier Science B.V. All rights reserved.

Fluid geochemistry of the Acqui Terme-Visone geothermal area (Piemonte, Italy)

The main geothermal reservoir of Acqui Terme-Visone hosts Na–Cl waters, which are in chemical equilibrium at 120–130°C with typical hydrothermal minerals including quartz, albite, K-feldspar, illite, chlorite (or smectite), anhydrite, calcite and an unspecified Ca-Al-silicate. In the Acqui Terme-Visone area, these geothermal waters ascend along zones of high vertical permeability and discharge at the surface almost undiluted or mixed with cold, shallow waters. To the SW of Acqui Terme, other ascending geothermal waters, either undiluted or mixed with low-salinity waters, enter relatively shallow secondary reservoirs, where they reequilibrate at 65–70°C. Both chemical and isotopic data indicate that bacterial SO4 reduction affects all these waters, especially those discharged by the secondary reservoirs. Therefore, geothermal waters must get in contact with oil, acquiring the relatively oxidized organic substances needed by SO4-reducing bacteria. This oil–water interaction process deserves further investigations, for potential economic implications.

Guagua pichincha volcano, Ecuador: fluid geochemistry in volcanic surveillance

Abstract The densely populated metropolitan area of Quito is located on the slopes of the active Guagua Pichincha volcano at only 10 km from the crater. Recently, the Italian Ministry of Foreign Affairs sponsored a project for the mitigation of volcanic hazard in this area. The geochemical study carried out as part of this project was aimed at constructing a geochemical model of the zone for use in volcanic surveillance. According to this geochemical model, a hydrothermal aquifer (T = 200–240°C), fed both by meteoric waters and by fluids released by a magma body, lies at shallow levels beneath Guagua Pichincha crater. The crater fumaroles are essentially fed by steam boiled off from the hydrothermal aquifer. The high flow rate fumaroles located in the dome area show significant SO2 contents, which suggest a relatively high contribution of magmatic fluids in the zone of the aquifer feeding them. The absence of SO2 in the fumarolic discharges near the southern crater wall indicates instead that the magmatic fluids dissolve entirely into the aquifer here. The hot springs located at the western end of the crater represent the lateral discharge of the hydrothermal aquifer. On the basis of this model, it is likely that an increment in the flux of both the magmatic fluids and the heat from a magma body produces an increase, albeit small, of the pressure-temperature conditions of the hydrothermal system and consequent changes in flow rate and fluid chemistry of the fumarolic vents. In particular, total sulphur and possibly hydrochloric acid may increase in all the vents and sulphur dioxide may appear in other fumarolic discharges. The varying thermodynamic conditions in the hydrothermal aquifer can be evaluated on the basis of the equilibria among carbon species and hydrogen. Only minor delayed changes are expected in the physical-chemical characteristics of the springs located at the western end of the crater.

Water chemistry of San Marcos area, Guatemala

Two well-equilibrated NaCl geothermal liquids are recognizable in the San Marcos area. Both have the same Cl concentration (540 mg/kg) and the same isotopic composition (δD of −66.5‰ and δ18O of −9‰) under reservoir conditions, but they come from two distinct aquifers with different temperatures, i.e. 240°C below La Cimarrona and 185°C below La Castalia. The numerous thermal NaCl to NaClHCO3 springs located in the San Marcos area originate through dilution and boiling of these two geothermal liquids and different degrees of re-equilibration at lower temperatures. Silica and K contents are useful in discriminating between dilution, boiling and re-equilibration phenomena. Thermal NaHCO3 waters, generated through conductive heat transfer or input of geothermal vapor or gases from below, delineate the extent of the geothermal reservoir(s) at depth.