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GEOPHYSICAL RESEARCH LETTERS, VOL. 37, L11303, doi:10.1029/2010GL042858, 2010

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Nonvolcanic CO2 Earth degassing: Case of Mefite dAnsanto (southern Apennines), Italy
G. Chiodini,1 D. Granieri,2 R. Avino,1 S. Caliro,1 A. Costa,1 C. Minopoli,1 and G. Vilardo1
Received 9 February 2010; revised 27 April 2010; accepted 3 May 2010; published 8 June 2010.

[ 1] Mefite d Ansanto, southern Apennines, Italy is the largest natural emission of low temperature CO 2 rich gases, from nonvolcanic environment, ever measured in the Earth. The emission is fed by a buried reservoir, made up of permeable limestones and covered by clayey sediments. We estimated a total gas flux of 2000 tons per day. Under low wind conditions, the gas flows along a narrow natural channel producing a persistent gas river which has killed over a period of time people and animals. The application of a physical numerical model allowed us to define the zones which potentially can be affected by dangerous CO2 concentration at breathing height for humans. The geometry of the Mefite gas reservoir is similar to those designed for sequestering CO2 in geological storage projects where huge amounts of CO 2 should be injected in order to reduce atmospheric CO2 concentration. The approach which we have used at Mefite to define hazardous zones for the human health can be applied also in case of large CO 2 leakages from storage sites, a phenomena which, even if improbable, can not be ruled out. Citation: Chiodini, G.,
D. Granieri, R. Avino, S. Caliro, A. Costa, C. Minopoli, and G. Vilardo (2010), Nonvolcanic CO2 Earth degassing: Case of Mefite dAnsanto (southern Apennines), Italy, Geophys. Res. Lett., 37, L11303, doi:10.1029/2010GL042858.

1. Introduction
[2] Mefite dAnsanto (hereafter defined Mefite) is the largest nonvolcanic CO2 gas emission of Italy and probably of the Earth. Mefite is known since very long time for the danger associated to gas emissions and, in Roman age, that area was identified as the den of the harmful goddess Mefite [Sinno, 1969]. [3] Mefite offers almost the unique opportunity in the world for measuring and modeling the effects of a very large gas leakage from a buried gas reservoir similar to those involved in projects of CO2 geological sequestrations. Geologic storage of CO2 is expected to produce plumes of large areal extent and, even if it seems unlikely, it is not possible to rule out the possibility of large CO2 leakages from storage sites [Pruess, 2008].

[4] At Mefite, during periods with stable atmosphere the gas, denser than the surrounding air, is channelized at the bottom of the valley forming a lethal and invisible gas river. The effects of the gas river is visible because vegetation is absent or intensely damaged (Figure 1a). In these areas we have often found carcasses of wild and domestic animals (dogs, cats, foxes, etc.) killed by the gas. Several lethal accidents involved also humans. In particular historical chronicles of XVIIXVIII century describe the dead by gas of 9 people [Gambino, 1991, pp. 295296]. Most recently, three persons died in 1990s (register of deaths, Frigento municipality, Avellino). It is worth noting that Mefite is not the only lethal gas emission in Italy but a large list of fatal accidents for humans and animals exists for several gas emissions [Chiodini et al., 2008]. [5] In order to measure the gas flow rate at Mefite, in September 2005 we performed detailed measurements of CO2 stream velocity and CO2 air concentrations along the valley where the gas river flows. Our data show that Mefite is the largest natural emission of lowtemperature CO2 ever measured in the world [Mrner and Etiope, 2002]. [6] The field measurements were used as physical constrains for modeling the gas plume using the gas transport model TWODEE2 [Folch et al., 2009] based on the shallow layer approach [Hankin and Britter, 1999a, 1999b]. Recently, the code was satisfactorily applied to simulate the gas plume formed by the Caldara di Manziana gas emission [Costa et al., 2008], a site characterized by a relatively flat topography. Mefite, characterized by much larger gas fluxes and by an extremely uneven topography, represents a very different case where to apply the model. [7] We show that the model is able to adequately describe the gravity driven flow of CO2 flowing over the valley of Mefite and allowed us to identify the areas where air CO2 concentrations can be higher than dangerous thresholds.

2. Origin of the Gas Emission and Geological Setting


[8] From the balance of the carbon dissolved in regional aquifers, Chiodini et al. [2004] estimated about 290 kg/s of deeply derived CO2 released by the Italian Tyrrhenian side. This amount of nonvolcanic CO2 is 10% of the estimated presentday total CO2 discharge from subaerial volcanoes of the Earth [Kerrick, 2001] but it is more likely an underestimation because the contribution of the numerous CO2 vents widespread located in the Italian region is not included [Chiodini et al., 2008]. The most probable source of this regional Earth degassing process is the mantle wedge, located in the Tyrrhenian sector of Italy, which is anoma-

1 Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Napoli, Napoli, Italy. 2 Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Pisa, Pisa, Italy.

Copyright 2010 by the American Geophysical Union. 00948276/10/2010GL042858

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earthquakes, the last of which occurred in 1980 (Irpinia Earthquake, Ms = 6.9 [Del Pezzo et al., 1983]).

3. Gas Composition and Gas Flux


[12] At Mefite gas is released from an area of about 4.000 m2 covering the flank of a steepsloping hill (Figure 1a). The gas emission, sampled in September 2005, consists of CO2 (98 vol%) with minor amounts of nonatmospheric N2 (1.3 vol%, N2/Ar 1000), H2S (0.33 vol%) and CH4 (0.23 vol%). The gas flows in a street channel towards west, following the slope of the valley. Using a hotwire anemometer (Tekkal AVM 714) and an IR CO2 spectrometer (DRAGER Polytron), we measured vertical profiles of CO2 concentrations and velocities of the CO2 stream in a cross section of the channel, normal to the main direction of the flow. [13] The experiment was carried on September 7th 2005, during a day of low wind conditions. Fiftyfive measurements were made from the ground surface to 3 m height, at 0.5 m vertical interval, along eight 1.5 mspaced profiles. CO2 flux, at each measuring point, is calculated multiplying the stream velocity (m/s) by the CO2 concentration (volume fraction). A total CO2 flux of 10.7 kg/s (928 tons per day) was then estimated integrating the measurements over the crosssection of the channel (Figure 2). Considering that CO2 concentration was still relatively high (from 4 to 8 vol%) at the maximum height of our measurements (3 m), the measured value of 10.7 kg/s is a minimum estimate of the total CO2 amount that flows at Mefite.

Figure 1. (a) Location and aerial photograph of the Mefite gas emission and the associated gas river. (b) Sketch of the upper part of the gas emission feeding system and location of the Monte Forcuso 001 well. The geological sketch has been redrawn from Mostardini and Merlini [1986].

lously rich in fluids originated in the subducted Adria slab [Chiodini et al., 2004; Frezzotti et al., 2009]. [9] A deep origin of the fluids is evident at Mefite where the gases have a d13C of CO2 of 0.43 and a 3He/4He ratio (expressed as R/Ra) of 2.72 (samples of September, 2005). This isotopic signature is very similar to that of the gases emitted by the active volcanoes Vesuvio and Campi Flegrei (d 13C from 2 to 0.5, R/Ra from 2.6 to 3.4 [Caliro et al., 2007]) which are located 6080 km west of Mefite. Italiano et al. [2000], also on the basis of this similarity, suggested the presence of magmas intruded into the axial part of the southern Apennine sedimentary chain. However the presence of a deep source of fluids, common in the Earths interior for the occurrence of magmatic or methamorphic processes, is not sufficient to explain the occurrence of a so large emission of CO2 at the surface, a kind of manifestation rare in the Earth. [10] In order to understand the generation of Mefite, we need to consider the geodynamic setting of the southern Apennine chain that is an eastverging thrust belt related to the westdipping subduction of the Apulian lithosphere [Doglioni et al., 1999]. From MiddleLate Pleistocene to the present, the axial zone of the chain underwent uplift and a NESW extensional tectonics, which is responsible for the formation of up to 15 km deep seismogenetic NWSE striking faults [Cinque et al., 1993; Hippolyte et al., 1994]. Deep fluids may infiltrate upwards through the interconnected network of extensional fractures and normal faults and, during their ascent, may be trapped in crustal traps which feed the gas emissions at the surface [Chiodini et al., 1995]. In particular, Mefite is fed by a CO2 gas pocket, which has been revealed by a 1850mdeep well drilled at about 2 km east of Mefite (Figure 1b, Monte Forcuso 001 well: http://unmig. sviluppoeconomico.gov.it/unmig/pozzi/dettaglio.asp? cod=3920). The gas zone has been found from a depth of 1128 to 1600 m, at the top of a permeable carbonate formation (Piattaforma Apula Interna, Mesozoic) covered by a clay formation (Unit Lagonegresi, Miocene). [11] The gas leakage from this zone occurs at least since Roman age (2000 years ago), but it is likely that the degassing process is active since the MiddleLate Pleistocene, when the extensional tectonics began. The gas leakage is favored by faulting processes highlighted by the occurrence of large

4. Simulation of Mefite Gas River and Gas Hazard


[14] The simulation of the gas dispersion was performed with TWODEE2 code which requires the topography grid, the wind data and the source gas fluxes [Folch et al., 2009]. The topography grid, a 3m resolution digital terrain model, was created by kriging a 5 m contour lines topography map. The computation domain consisted of 400 170 cells (each of 3m 3m) covering a rectangle of 1.2 0.51 km2 (Figure 1a). The simulation was performed using the observed East to West wind with a speed of 0.1 m/s (most of the wind measurements were below the detection limit of the anemometer, i.e., 0.2 m/s with a resolution of 0.1 m/s). The atmospheric pressure was 1013 mbar, and air temperature of 15C. These conditions were assumed constant during the simulation. The computations were performed using the TWODEE2 coupled with a diagnostic wind model [Douglas and Kessler, 1990] for taking into account the topography effects on wind velocity [Folch et al., 2009].

Figure 2. CO2 flux measured in the AA crosssection of Mefite gas river (see Figure 1a).

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Figure 3. (a) Measured (dots) vs simulated (dashed lines) CO2 profiles in the central part of the AA measuring section (Figure 3b). Black line represents the profile obtained using an initial guess flux of 928 t/d. (b) Simulated cloud depth and (c) depthaveraged cloud density for a total gas flux of 2000 t/d, and a 0.1 m/s wind blowing from East to West. [15] The gas flux, from a uniform source area identified from field evidences (Figures 3b and 3c), was varied systematically in order to best fit the CO2 measured in the channel. In Figure 3a, the measured CO2 concentration profile is compared with the simulation results. As expected, simulation results obtained using the measured gas flux (10.7 kg/s) are lower than the observed values, because in our measurement we excluded the highest part of the gas plume. The best fit of the measured CO2 profile was obtained for CO2 fluxes around 23.1 kg/s (2000 tons per day) which will be considered the reference gas flux to use for modeling the plume dispersion and evaluating gas hazard. [16] Figures 3b and 3c show the location and the shape of the plume formed considering the reference CO2 flux and a East to West wind of 0.1 m/s. Figure 3b shows the gas cloud depth h, i.e. the height below which a 0.9 fraction of the buoyancy g(rm ra) is located (g is the gravity acceleration, ra the air density, rm the depthaveraged cloud density [Folch et al., 2009]). The distribution of the depthaveraged cloud density (rm) is shown in Figure 3c. Under the conditions assumed in the simulation, gas accumulation is enhanced in the bottom of the valley. From the source area to the West the density of the plume progressively decreases (Figure 3c) whereas the height of the plume gradually increases, reaching a maximum elevation of 70 m at the western border of the computational domain (Figure 3b). [17] In order to define hazardous zones for the human health at Mefite we performed numerous simulations varying wind speed and direction in order to reproduce any different meteorological conditions that can occur in the area. Considering that the most dangerous conditions occur only up to

wind velocity of 2 m/s, we simulated the effects of low wind velocities from the 8 directions of the wind rose (i.e., 32 simulations as given by the combination of 8 wind directions from N, NE, E, SE, S, SW, W, NW and 4 wind speeds of 0.1 m/s, 0.5 m/s, 1 m/s, 2 m/s). Such low wind conditions occur very frequently during the Summer season, whereas they are less frequent during the Winter season. Furthermore, in accord with historical chronicles [Gambino, 1991, p. 292], simulations show that winds blowing from North tend to enhance gas concentration in the topographic depression producing the most hazardous conditions. [18] We also computed the maximum height at which CO2 concentrations of 5%, 10% and 15% are reached during the simulations (Figures 4a, 4b, and 4c), using a specific utility of TWODEE2 code [Folch et al., 2009]. The three concentration values were selected because they represent three important thresholds for human health. At 5% air CO2 concentration, the breathing increases to twice the normal rate, humans are affected by a weak narcotic effect and headache. This value is the limit of tolerance for most people. For instance, the short time exposure limit for a CO2 concentration of 3%, has been fixed at 15 minutes by the National Institute for Occupational Safety and Health of United States [National Institute of Occupational Safety and Health, 1997]. The map of Figure 4a shows the maximum height reached by the 5% threshold in the simulation domain. Practically all the topographic depressions can be affected by 5% air CO2 concentration at elevation >1.5 m for one or more specific meteorological condition. At 10% air CO2 concentration humans are affected by respiratory distress with loss of consciousness in 1015 min. Such very dangerous concentrations are simulated at heights of 1.5 m, or higher, along the first 500 m of the gas river (Figure 4b). Finally CO2 air concentrations >15% are intolerable for humans and cause loss of consciousness after a few seconds of exposure and the subsequent death if it is not immediately given oxygen. These lethal conditions characterize the first 200 m of the valley, downhill from the gas source area, at the height

Figure 4. Maximum elevation of selected CO2 thresholds simulated by TWODEE2 code varying wind velocities and wind directions (see text). The area bounded by the dashed line is characterized by absent or damaged vegetation.

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of human breathing (Figure 4c). This is the area where we have systematically found carcasses of animals. [19] In evaluating the gas hazard at Mefite it should be considered that the effects of CO2 are enhanced by the concurrent effects of H2S. Assuming that the gas plume has the same H2S/CO2 ratio of the gas emission (H2S/CO2 0.0035), CO2 thresholds of 5%, 10% and 15% correspond to H2S air concentrations of 165 ppm, 350 ppm and 525 ppm, respectively. These are very dangerous concentrations of H2S. In fact, above a H2S concentration of 300 ppm respiratory irritation is a predominant symptom, and hyperpnoea followed by respiratory arrest is possible for concentration higher than 500 ppm [World Health Organization, 1981].

5. Conclusion
[20] Mefite represents the largest natural emission of low temperature CO2 rich gases, from nonvolcanic environment, ever measured in the Earth. By integrating measurement of gas stream velocity, analysis of CO2 air concentrations and physical numerical simulations we estimated a total gas flux of 23.1 kg/s (2000 ton/day). For low wind conditions, this huge amount of gas flows along a narrow valley producing a persistent gas river which can kill people and animals. [21] The emission is fed by a buried gas reservoir, made up of permeable limestones and covered by clayey sediments. Gas leakage at Mefite has been active for long time (at least thousands of years), probably because of both a continuous CO2 recharging of the buried reservoir and active faulting processes responsible of recurrent seismic crises. The geometry of the Mefite gas reservoir is similar to those designed for sequestering CO2 in geological storage projects where huge amounts of CO2 should be injected in order to reduce air CO2 concentration. Even if the CO2 storage sites are planned in noseismic areas, reasonable concerns regard the possibility of large CO2 leakages. In fact, massive runaway discharges of CO2 from storage sites, although unlikely, cannot be ruled out [Pruess, 2008]. For these reasons, Mefite represents a good natural analogue to be studied. [22] The use of a physical numerical model allowed us to define the most dangerous zones of Mefite area. The used method can be suitable for selecting the areas not accessible to people because recurrently affected by lethal conditions. A similar approach can be used for the mitigation of gas hazard from other natural emissions and in case of large CO2 leakages from storage sites. [23] Acknowledgments. The authors wish to thank two anonymous reviewers for their corrections and suggestions, which greatly improved the manuscript. This work was partially supported by the Research Project MIUR/PRIN2008 prot. 2008S89Y8R.

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