Franco Tassi

Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona–Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ13C of CO2 discharged from gas vents and δ13C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher 3He/4He ratios and lower N2 contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO2 isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO2. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO2 derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220–240, 120–140 and 60–70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.

Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Abstract Since the March–April 1982 eruption of El Chichon volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na + , Cl − , Ca 2+ and SO 4 2− contents, experienced a dramatic change in 1998–1999, turning from a Na + –Cl − - to a Ca 2+ –SO 4 2− -rich composition. In June 2000, a relatively sharp increase in Na + and Cl − contents was observed. At the same time, SO 2 /H 2 S ratios and H 2 and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichon is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichon: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichon after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.

Origin and evolution of ‘intracratonic’ thermal fluids from central-western peninsular India

The chemical and isotopic composition of several thermal springs and associated gas phases in a large sector of central-western peninsular India has been investigated. Such springs have meteoric isotopic signature and emerge, after very well developed convective circulation at depth, along important tectonic structures such as the Son–Narmada–Tapti rift zone and the West Coast Fault. Chemical components in both gas and liquid phases and geothermometric estimations suggest that such springs are not related to the presence of any active hydrothermal systems at shallow depth in any of the studied areas. The hottest convective water emerges at Tattapani at near boiling point for water at atmospheric pressure (>90°C) in association with an N2-rich gas phase of clear meteoric signature. Since such fluids do not carry any corrosive components, they could be conveniently exploited for industrial purposes, such as drying processes. From a tectonic point of view, the presence of thermal emergences scattered in a wide area along geologically well defined structures, which also generate frequent moderate earthquakes, suggests that such structures are active. Although the isotopic composition of thermal springs points to a meteoric origin, their feeding aquifers are not topographically driven as in most active Alpine orogenic belts. The relative high quantity of total helium in the associated gas phase suggests also that they are really deep, old, long circulating waters. We propose for such waters the term ‘intracratonic thermal waters’ since the isotopic signature of He in the gas phase does not show any release of primordial 3He in any of the areas of spring emergence. Based on the quite low 3He/4He ratio in the gas phase we suggest also that, in spite of its morphological shape, the Narmada–Son–Tapti rift zone cutting the Indian subcontinent in two is more related to paleo-suture rather than to a mid-continental rift system.

A geochemical traverse across the Eastern Carpathians (Romania): constraints on the origin and evolution of the mineral water and gas discharges

Abstract The inner sector of the Eastern Carpathians displays a large number of Na–HCO 3 , CO 2 -rich, meteoric-originated cold springs (soda springs) and bore wells, as well as dry mofettes. They border the southern part of the Pliocene–Quaternary Calimani–Gurghiu–Harghita (CGH) calc-alkaline volcanic chain. Both volcanic rocks and CO 2 -rich emissions are situated between the eastern part of the Transylvanian Basin and the main east Carpathian Range, where active compression tectonics caused diapiric intrusions of Miocene halite deposits and associated saline, CO 2 -rich waters along active faults. The regional patterns of the distribution of CO 2 in spring waters (as calculated p CO 2 ) and the distribution pattern of the 3 He/ 4 He ratio in the free gas phases (up to 4.5 R m / R a ) show their maximum values in coincidence with both the maximum heat-flow measurements and the more recent volcanic edifices. Moving towards the eastern external foredeep areas, where oil fields and associated brines are present, natural gas emissions become CH 4 -dominated. Such a change in the composition of gas emissions at surface is also recorded by the 3 He/ 4 He ratios that, in this area, assume ‘typical’ crustal values ( R m / R a =0.02). In spite of the fact that thermal springs are rare in the Harghita volcanic area and that equilibrium temperature estimates based on geothermometric techniques on gas and liquid phases at surface do not suggest the presence of shallow active hydrothermal systems, a large circulation of fluids (gases) is likely triggered by the presence of mantle magmas stored inside the crust. If total 3 He comes from the mantle or from the degassing of magmas stored in the crust, CO 2 might be associated to both volcanic degassing and thermometamorphism of recently subducted limestones.

Fluid mixing in carbonate aquifers near Rapolano (central Italy): chemical and isotopic constraints

Chemical (major and trace elements) and isotopic compositions (dD and d 18 O in waters and d 13 Ci n CO 2 and 3 He/ 4 He in gases) of natural thermal (11) and cold (39) fluids (spring waters and gases) discharging from a tectonic window of Mesozoic limestones in central Italy, have proved to be the result of mixing processes inside the limestone formations. The limestones provide a preferential route for subsurface fluid migration and they gather both descending cold, Ca-HCO3, B-depleted groundwaters and rising convective Ca-SO4(HCO3), CO2-saturated, B-rich thermal waters. Atmospherically-derived descending gas components (N2, Ne, He), dissolved in rainfall that infiltrates the limestone system mix with N2, Ne, He-depleted hot rising waters. Boron in the liquid phase and N2 and Ne in the gas phase are the most useful elements to trace the mixing process. The deeper gas samples recognised in the area are associated with the hotter waters emerging in the area. In spite of being depleted in Ne and He and light hydrocarbons they have the higher measured 3 He/ 4 He ratios, suggesting a contribution of mantle 3 He to the gas phase. This contrasts with deep circulation in the crust which would lead to increased concentration of 4 He in the deeper gases. Paradoxically, there is more relative concentration of 4 He in the more air-contaminated gas samples than in the deeper gas samples. A similar paradox exists when the d 13 Co f CO 2 in the deeper gas samples is considered. The shallower air-contaminated gas samples, although they should be affected by the addition of soil- 13 C depleted organic C, have d 13 Ci n CO 2 more positive than the deeper gas samples recognized. Since any deep hydrothermal source of CO2 should generate CO2 with more positive values of d 13 C than those measured at surface, a multiple (single) calcite precipitation process from hydrothermal solutions, with C isotopic fractionation along the rising path inside the Mesozoic limestone formations, is proposed. # 2002 Elsevier Science Ltd. All rights reserved.

Intense magmatic degassing through the lake of Copahue volcano, 2013-2014

Here we report on the first assessment of volatile fluxes from the hyperacid crater lake hosted within the summit crater of Copahue, a very active volcano on the Argentina-Chile border. Our observations were performed using a variety of in situ and remote sensing techniques during field campaigns in March 2013, when the crater hosted an active fumarole field, and in March 2014, when an acidic volcanic lake covered the fumarole field. In the latter campaign, we found that 566 to 1373 t d−1 of SO2 were being emitted from the lake in a plume that appeared largely invisible. This, combined with our derived bulk plume composition, was converted into flux of other volcanic species (H2O ~ 10989 t d−1, CO2 ~ 638 t d−1, HCl ~ 66 t d−1, H2 ~ 3.3 t d−1, and HBr ~ 0.05 t d−1). These levels of degassing, comparable to those seen at many open-vent degassing arc volcanoes, were surprisingly high for a volcano hosting a crater lake. Copahues unusual degassing regime was also confirmed by the chemical composition of the plume that, although issuing from a hot (65°C) lake, preserves a close-to-magmatic signature. EQ3/6 models of gas-water-rock interaction in the lake were able to match observed compositions and demonstrated that magmatic gases emitted to the atmosphere were virtually unaffected by scrubbing of soluble (S and Cl) species. Finally, the derived large H2O flux (10,988 t d−1) suggested a mechanism in which magmatic gas stripping drove enhanced lake water evaporation, a process likely common to many degassing volcanic lakes worldwide.

Degradation of C2–C15 volatile organic compounds in a landfill cover soil

The composition of non-methane volatile organic compounds (hereafter VOCs) in i) the cover soil, at depths of 30, 50 and 70 cm, and ii) gas recovery wells from Case Passerini landfill site, (Florence, Italy) was determined by GC-MS. The study, based on the analysis of interstitial gases sampled along vertical profiles within the cover soil, was aimed to investigate the VOC behaviour as biogas transits from a reducing to a relatively more oxidizing environment. A total of 48 and 63 different VOCs were identified in the soil and well gases, respectively. Aromatics represent the dominant group (71.5% of total VOC) in soil gases, followed by alkanes (6.8%), ketones (5.7%), organic acids (5.2%), aldehydes (3.0%), esters (2.6%), halogenated compounds (2.1%) and terpenes (1.3%). Cyclics, heterocyclics, S-bearing compounds and phenols are <or=1%. In the wells the VOC composition is characterized by higher concentrations of cyclic (7.6%) and S-bearing compounds (2%) and lower concentrations of O-bearing compounds. The vertical distribution of VOCs in the cover soil shows significant variations: alkanes, aromatics and cyclics decrease at decreasing depth, whereas an inverse trend is displayed by the O-bearing species. Total VOC and CH(4) concentrations at a depth of 30 cm in the soil are comparable, inferring that microbial activity is likely affecting VOCs at a very minor extent with respect to CH(4). According to these considerations, to assess the biogas emission impact, usually carried out on the sole basis of CO(2) and CH(4) emission rates, the physical-chemical behaviour of VOCs in the cover soil, regulating the discharge of these highly contaminant compounds in ambient air, has to be taken into account. The soil vertical distribution of these species can be used to better evaluate the efficiency of oxidative capability of intermediate and final covers.

Gas emissions from five volcanoes in northern Chile and implications for the volatiles budget of the Central Volcanic Zone

This study performed the first assessment of the volcanic gas output from the Central Volcanic Zone (CVZ) of northern Chile. We present the fluxes and compositions of volcanic gases (H2O, CO2, H2, HCl, HF, and HBr) from five of the most actively degassing volcanoes in this region—Lascar, Lastarria, Putana, Ollague, and San Pedro—obtained during field campaigns in 2012 and 2013. The inferred gas plume compositions for Lascar and Lastarria (CO2/Stot = 0.9–2.2; Stot/HCl = 1.4–3.4) are similar to those obtained in the Southern Volcanic Zone of Chile, suggesting uniform magmatic gas fingerprint throughout the Chilean arc. Combining these compositions with our own UV spectroscopy measurements of the SO2 output (summing to ~1800 t d−1 for the CVZ), we calculate a cumulative CO2 output of 1743–1988 t d−1 and a total volatiles output of >20,200 t d−1.

Distribution of gaseous hg in the mercury mining district of mt.amiata (central italy): a geochemical survey prior the reclamation project.

The Mt. Amiata volcano is the youngest and largest volcanic edifice in Tuscany (central-northern Italy) and is characterized by a geothermal field, exploited for the production of electrical energy. In the past Mt. Amiata was also known as a world-class Hg district whose mining activity was mainly distributed in the central-eastern part of this silicic volcanic complex, and particularly in the municipality of Abbadia San Salvatore. In the present work we report a geochemical survey on Hg(0) measurements related to the former mercury mine facilities prior the reclamation project. The Hg(0) measurements were carried out by car for long distance regional surveys, and on foot for local scale surveys by using two LUMEX (915+ and M) devices. This study presents the very first Hg(0) data obtained with this analytical technique in the Mt. Amiata area. The facilities related to the mining areas and structures where cinnabar was converted to metallic Hg are characterized by high Hg values (>50,000ngm(-3)), although the urban center of Abbadia San Salvatore, few hundred meters away, does not appear to be receiving significant pollution from the calcine area and former industrial edifices, all the recorded values being below the values recommended by the issuing Tuscany Region authorities (300ngm(-3)) and in some cases approaching the Hg background levels (3-5ngm(-3)) for the Mt. Amiata area.

Origin and Distribution of Thiophenes and Furans in Gas Discharges from Active Volcanoes and Geothermal Systems

The composition of non-methane organic volatile compounds (VOCs) determined in 139 thermal gas discharges from 18 different geothermal and volcanic systems in Italy and Latin America, consists of C2–C20 species pertaining to the alkanes, alkenes, aromatics and O-, S- and N-bearing classes of compounds. Thiophenes and mono-aromatics, especially the methylated species, are strongly enriched in fluids emissions related to hydrothermal systems. Addition of hydrogen sulphide to dienes and electrophilic methylation involving halogenated radicals may be invoked for the formation of these species. On the contrary, the formation of furans, with the only exception of C4H8O, seems to be favoured at oxidizing conditions and relatively high temperatures, although mechanisms similar to those hypothesized for the production of thiophenes can be suggested. Such thermodynamic features are typical of fluid reservoirs feeding high-temperature thermal discharges of volcanoes characterised by strong degassing activity, which are likely affected by conspicuous contribution from a magmatic source. The composition of heteroaromatics in fluids naturally discharged from active volcanoes and geothermal areas can then be considered largely dependent on the interplay between hydrothermal vs. magmatic contributions. This implies that they can be used as useful geochemical tools to be successfully applied in both volcanic monitoring and geothermal prospection.