You are on page 1of 13

Bull Volcanol (2009) 71:171–183

DOI 10.1007/s00445-008-0216-z

RESEARCH ARTICLE

The magmatic- and hydrothermal-dominated fumarolic


system at the Active Crater of Lascar volcano,
northern Chile
F. Tassi & F. Aguilera & O. Vaselli & E. Medina &
D. Tedesco & A. Delgado Huertas & R. Poreda & S. Kojima

Received: 12 March 2008 / Accepted: 9 May 2008 / Published online: 3 June 2008
# Springer-Verlag 2008

Abstract Low-to-high temperature fumaroles discharging consisting of a general decrease of magmatic-related com-
from the Active Crater of Lascar volcano (northern Chile) pounds, i.e. SO2, have affected the fumarolic system during
have been collected in November 2002, May 2005 and the period of observation, indicating an increase of the
October 2006 for chemical and isotopic analysis to provide influence of the hydrothermal system surrounding the
the first geochemical survey on the magmatic-hydrothermal ascending deep fluids. The chemical composition of Active
system of this active volcano. Chemical and isotopic gas Crater fumaroles has been used to build up a geochemical
composition shows direct addition of high-temperature model describing the main processes that regulate the fluid
fluids from magmatic degassing, mainly testified by the circulation system of Lascar volcano to be utilized in
very high contents of SO2, HCl and HF (up to 87,800, volcanic surveillance.
29,500 and 2,900 μmol/mol) and the high R/Ra values (up
to 7.29). Contributions from a hydrothermal source, mainly Keywords Lascar volcano . Fumarolic gases .
in gas discharges of the Active Crater rim, has also been Fluid geochemistry . Isotope geochemistry . Northern Chile .
detected. Significant variations in fluid chemistry, mainly Geochemical monitoring . Volcanic hazard

Editorial responsibility: H Delgado


F. Tassi (*) : O. Vaselli D. Tedesco
Department of Earth Sciences, University of Florence, Department of Environmental Sciences, 2nd University of Naples,
Via G. La Pira 4, Via Vivaldi 43,
50121 Florence, Italy 81100 Caserta, Italy
e-mail: franco.tassi@geo.unifi.it

F. Aguilera D. Tedesco
Programa de Doctorado en Ciencias mención Geología, Institute of Environmental Geology and Geo-Engineering,
Universidad Católica del Norte, CNR-IGAG National Research Council,
Av. Angamos 0610, Pzz.e A. Moro,
1280 Antofagasta, Chile 00100 Roma, Italy
e-mail: faguilera@ucn.cl

F. Aguilera : E. Medina : S. Kojima A. Delgado Huertas


Departamento de Ciencias Geológicas, CSIS Estacion Experimental de Zaidin,
Universidad Católica del Norte, Prof. Albareda 1,
Av. Angamos 0610, 18008 Granada, Spain
1280 Antofagasta, Chile

O. Vaselli R. Poreda
CNR-IGG Institute of Geosciences and Earth Resources, Department of Earth and Environmental Sciences,
Via G. La Pira 4, 227 Hutchinson Hall,
50121 Florence, Italy Rochester, NY 14627, USA
172 Bull Volcanol (2009) 71:171–183

Introduction to the volcanic edifice. Moreover, the most important village


of the region (San Pedro de Atacama) lies at more than 70 km
Lascar (23°22′ S, 67°44′ W; 5,592 m a.s.l.) is a composite from Lascar summit, thus only exceptionally powerful
stratovolcano located in the Antofagasta Region of Chile at eruptions can represent a real hazard for local population.
about 70 km SE from San Pedro de Atacama, in the eastern In this paper, the first analytical results of the chemical and
fringe of the Atacama Basin (Fig. 1). Lascar is currently isotopic compositions of gas samples collected during three
considered the most active volcano of the Andean Central sampling campaigns (November 2002, May 2005 and
Volcanic Zone (Francis and Rothery 1987; Gardeweg et al. October 2006) from the crater fumaroles of Lascar volcano
1998). Its largest historically recorded eruption occurred on are presented and discussed in order to (1) investigate on the
19–20 April 1993 and produced a 25 km height Plinian relation between the chemical and isotopic compositional
column, whose collapse generated pyroclastic flows up to features of the fumarolic fluids and the state of activity of the
8.5 km NW from the volcano summit. The resulting tephra volcano and (2) formulate a conceptual geochemical model of
plume expanded to SSE, covering more than 850,000 km2 the magmatic-hydrothermal system.
with, at least, 0.1 mm thick layer and reached N-central
Argentina, S Paraguay, Uruguay, and S Brazil (BGVN 1994).
Despite the frequent small-to-medium size eruptions and the Geological outlines and historical and present
sporadic explosive events, which have attracted the interna- volcanic activity
tional scientific community, little is known about the
petrological features of the volcanic products (e.g. Déruelle Lascar volcano is constituted by two truncated cones with five
et al. 1996; Risacher and Alonso 2001) and only few data on ENE–WSW oriented nested craters. The present activity
the seismic activity of the area are available (e.g. Hellweg affects the so-called “Active Crater” (Fig. 2). Lascar is built
2000). Furthermore, at our best knowledge no geochemical over a pre-Cenozoic basement mainly constituted by Upper
and isotopic data have been performed on the numerous Cretaceous limestones, Tertiary continental siliciclastic sedi-
fumaroles discharging from the summit craters. The most ments and Late Tertiary to Quaternary volcanic rocks asso-
detailed information about the recent and present activity of ciated to andesitic stratocones, dacitic dome complexes and
Lascar volcano are from visual observations (e.g. Matthews large calderas. The volcanic activity of Lascar has been divid-
et al. 1997) and satellite image analysis (e.g. Oppenheimer ed by Gardeweg et al (1998) in four stages: stage I (<43 ka)
et al. 1993; Wooster and Rothery 1997). The paucity of developed in the easternmost part of the summit crater com-
volcanological investigations regarding this volcano is likely plex, presently occupied by the Active Crater, and charac-
due to its remote location, which makes difficult the access terized by pyroxene-andesite lavas and pyroclastic flows.
During the stage II (>26.5–19.22 ka) the activity shifted to
the western cone and magma composition changed to silicic
andesitic (Piedras Grandes Unit) and dacitic (Soncor Unit).
The Soncor eruption (26.45 ka) produced 10–15 km3 of
pyroclastic flow deposits and an estimated 25–30 km
eruptive column. In stage III (19.2–9.1 ka) a silicic andesitic
to dacitic stratocone was built inside the crater formed by the
Soncor eruption, and at least three andesite scoria flows were
erupted (Tumbres deposit, 9.1–9.3 ka). Eventually, in stage
IV (7.1 ka–present), marked by the Tumbres-Talabre andesite
lava flow (7.1±1.25 ka, Wörner et al 2000), the activity
shifted back to the eastern cone.
The historical reports indicate that from 1848 onward
Lascar has been characterized by fumarolic emission with
occasional explosions, notably in the eruption of 19–20
April 1933 (Gardeweg and Medina 1994). A detailed
description of Lascar volcanic activity from 1984, when a
strong thermal anomaly in the Active Crater was detected
by satellite images (Francis and Rothery 1987; Glaze et al.
1989; Oppenheimer et al. 1993), to 1996 (Matthews et al.
1997) reports that in this period a new eruptive phase, related
Fig. 1 Schematic map of the Andean Volcanic Zone and location of to the growth and collapse of lava domes, took place. This
Lascar volcano activity was marked by periodically recurrent (3–4 years)
Bull Volcanol (2009) 71:171–183 173

Fig. 2 Schematic map of the


Active Crater of Lascar volcano,
main fumarolic fields and loca-
tion of the sampling sites

explosive events, in September 1986, February 1990 and, subsidence of the crater floor was noticed and no domes, like
eventually, in April 1993, that produced eruptive columns as those characterizing the 1984–1994 activity, were observed
high 10, 8–14 and 25 km, respectively. These major events (BGVN 2006b). A platform, which lies at the depth of about
were interpreted as the result of the increasing pressure at 150 m from the crater rim, borders an inner crater, 300 m in
depth within the magmatic conduit, likely triggered by the diameter and 250 m deep (Fig. 2). From 2002 to October
subsidence of the dome that closed the inward-dipping frac- 2006, the spatial distribution of the fumarolic fields have not
ture system (Matthews et al. 1997). Several minor eruptions, been changed significantly, but the degassing activity has
generating <5 km high ash columns, typically occurred be- been shown a progressive decrease, occasionally marked by
tween the major explosive events, in response to the temporary small-to-medium eruptive events, such as that recorded on the
sealing of the pathways of the rising magmatic gases causing a 4th of May 2005 (BGVN 2005a, b; Aguilera et al. 2006a).
pressure increase at shallow depth. The April 1993 eruption that
ejected more than 0.1 km3 of volcanic material seems to have
strongly affected the geometry of the Active Crater and the Analytical methods
related sub-volcanic plumbing system (Matthews et al. 1997).
Consequently, the cyclic behaviour characterizing the eruptive During our first visit at the Active Crater, in November 2002,
style of Lascar volcano in the previous period has not been the majority of the high-flux gas vents were concentrated
repeated. Relevant eruptions were then recorded in July 1994 along the North-eastern platform border from where two
and 1995, October 1996 and July 2000, producing <10 km fumaroles (# 1 and 2; Fig. 2) were collected, while only few
high columns (BGVN 1994; 1995; 1996; 2000; Aguilera et al. fumaroles were discharging from the crater bottom and close
2003). The July 2000 ash plume extended 660 km to the E, to the crater rim. Weak gas emissions from fractures crossing
stretching from N Chile across S Bolivia and N Argentina and the eastern crater (Fig. 2) were also observed. Further fuma-
into W central Paraguay (BGVN 2000). Significant events roles vents were sampled, as follows: 1) in May 2005, three
have also occurred in May 2005, with the ejection of an ash fumaroles (# 3, 4 and 5; Table 1) discharging from a new
cloud that reached an altitude of 8–10 km (BGVN 2005a; fracture system located in the southern part of the crater rim
2006b; Aguilera et al. 2006a), and in April 2006, whose ash (Fig. 2) and likely triggered by the eruptive event occurred
plume was observed 220 km away from the volcano (BGVN only some days before (4th of May), and 2) in October 2006,
2006a; Aguilera et al 2006b; Clavero et al. 2006). the remaining nine fumaroles utilized for this work were
Presently, Lascar volcano is characterized by the presence collected within the platform (# 6, 7 and 8) and along its
of a permanent sustained plume that is fed by extensive inner North-eastern border (# 9–14; Fig. 2).
fumarolic fields consisting of hundreds of gas vents mainly Fumaroles were sampled using a 1 m long titanium tube
located in the Active Crater. The SO2 flux measured by (Ø=2.5 cm) connected, by quartz-glass dewar tubes, to pre-
correlation spectrometry (COSPEC; Andres et al. 1991) and evacuated 60 ml glass flasks equipped with a Teflon stop-
differential optical absorption spectroscopy (DOAS; Mather cock. The pre-evacuated and weighed flasks were filled
et al. 2004; Rodriguez et al. 2005) from this plume, ranged with 20 ml of a 4 N NaOH and 0.15 M Cd(OH)2 suspen-
between 500 and 2,300 tons/day. In the period from 2002 to sion to (1) condense water vapour and dissolve CO2, SO2,
2006, the morphology of the 800 m wide and 400 m deep HCl and HF, (2) precipitate elemental sulfur and (3)
Active Crater has not been significantly changed. A small combine H2S with Cd2+ to form insoluble CdS. Conse-
Table 1 Outlet temperatures (in °C) and chemical composition of the fumarolic discharges from Lascar volcano
174

Date Cord N Cord E Altitude T°C CO2 HCl HF SO2 H2S S N2 CH4 Ar O2 Ne H2 He CO H2O/ Ethane Ethane Propane Propene Iso- Furane Benzene Thiophene
CO2 butene

1 Nov. 7415800 629600 5,350 295.0 891,760 8,243 1,035 56,947 195 0.01 24,284 10.9 35.2 207 0.05 7,473 3.27 9,806 0.33 0.061 0.017 0.008 0.007 0.086 n.d. 0.031 n.d.
2002
2 Nov. 7415800 629600 5,350 385.0 855,210 12,357 2,147 87,804 145 0.02 23,245 4.27 30.5 215 0.06 8,757 3.03 10,084 0.31 0.031 0.023 0.012 0.007 0.080 n.d. 0.014 n.d.
2002
3 May 7415623 629715 5,505 76.0 753,737 5,739 966 5,995 4,440 10.1 207,209 488 1,293 464 0.71 19,269 24.0 357 19.2 5.063 0.046 0.476 0.100 1.846 0.050 1.849 0.072
2005
4 May 7415628 629716 5,514 30.0 784,999 5,061 852 6,526 4,796 10.9 179,060 734 1,225 461 0.65 15,917 23.3 326 17.8 3.907 0.048 0.420 0.083 2.387 0.045 2.205 0.073
2005
5 May 7415623 629715 5,505 76.0 755,275 8,570 1,442 7,078 5,264 14.0 200,992 689 1,416 557 0.77 18,226 28.0 438 22.5 5.334 0.053 0.391 0.102 2.237 0.043 2.117 0.070
2005
6 Oct. 7415815 629570 5,350 71.9 743,534 14,702 2,086 20,438 10,298 1.11 186,298 431 983 597 0.57 20,241 12.1 372 16.2 2.595 0.114 0.216 0.078 1.287 0.033 1.995 0.067
2006
7 Oct. 7415750 629550 5,300 73.2 768,092 29,506 2,913 24,890 8,596 1.19 144,002 267 332 285 0.19 20,683 11.9 413 14.9 2.666 0.108 0.212 0.073 1.429 0.033 1.404 0.052
2006
8 Oct. 7415760 629570 5,300 81.7 765,675 13,670 1,250 21,603 8,180 1.85 167,442 225 259 770 0.14 20,551 10.0 358 13.7 2.547 0.101 0.215 0.066 1.294 0.036 1.570 0.033
2006
9 Oct. 7415800 629585 5,300 150.8 834,908 16,522 1,277 46,074 1,977 0.60 81,114 53.1 89.2 622 0.05 16,117 7.61 1,235 5.26 1.341 0.047 0.094 0.037 0.525 0.009 0.763 0.014
2006
10 Oct. 7415800 629590 5,300 178.0 911,092 6,045 526 27,092 1,540 0.24 36,634 28.8 60.2 530 0.03 6,655 8.07 1,368 1.98 0.757 0.037 0.046 0.016 0.240 0.004 0.322 0.010
2006
11 Oct. 7415790 629630 5,300 250.0 855,579 12,513 1,971 48,617 214 0.25 68,455 17.3 77.9 654 0.04 12,146 4.86 4,141 1.40 0.144 0.015 0.006 0.002 0.124 0.014 0.188 n.d.
2006
12 Oct. 7415750 629650 5,300 154.2 841,254 12,698 1,047 42,327 1,817 0.47 92,577 44.5 91.4 677 0.05 6,286 13.3 1,165 4.70 0.819 0.041 0.026 0.011 0.612 0.003 0.567 0.018
2006
13 Oct. 7415730 629670 5,300 174.0 840,461 14,185 1,893 46,693 986 0.59 85,126 51.2 134 512 0.08 8,920 5.10 1,031 4.23 0.437 0.045 0.021 0.005 0.536 0.014 0.435 n.d.
2006
14 Oct. 7,415,710 629,670 5,300 150.0 853,908 12,795 1,682 44,835 840 0.52 75,669 43.6 132 485 0.07 8,587 6.32 1,016 3.49 0.380 0.039 0.016 0.005 0.393 0.012 0.363 n.d.
2006

Gas contents are in μmol/mol. Positions of samples referred to UTM WGS 84 coordinate system.
n.d. Not detected.
Bull Volcanol (2009) 71:171–183
Bull Volcanol (2009) 71:171–183 175

quently, the residual gases (N2, O2, CO, H2, He, Ar, Ne, and Farley (1992). The analytical error for the 3He/4He ratio
CH4 and light hydrocarbons) were concentrated in the is about 0.3%. Sensitivity for argon is about 4×10−4 Amps/torr,
head-space (Giggenbach and Gougel 1989; Montegrossi et while precision for the 40Ar/36Ar isotope ratio is 0.2%.
al. 2001). A quartz-glass water-cooled condenser was used
to obtain a suitable amount of condensate for the # 1 and 2
fumaroles (May 2005; Fig. 2) for the analysis of δ18O- and Results
δD-H2O isotopic ratios.
The inorganic residual gases were analysed with a gas Chemical composition of Lascar fumaroles
chromatographic system (Shimadzu 15a) equipped with
Thermal Conductivity Detector (TCD) and a 9 m, 5A The chemical composition of the dry gas fraction, expressed
molecular sieve column. Methane and C1–C4 hydrocarbons in μmol/mol, and the H2O/CO2 ratio of the fumaroles of
were analysed by a Shimadzu 14a gas-chromatograph equip- Lascar volcano are reported in Table 1. It is worthy to note
ped with Flame Ionization Detector (FID) and a 10 m long the very low H2O/CO2 ratios (ranging between 0.31 and
stainless steel column (ϕ =2 mm) packed with Chromosorb 5.25) of the medium-to-high temperature (≥150°C) fumar-
PAW 80/100 mesh coated with 23% SP 1700. The alkaline oles, which are completely different from those measured in
solution, separated from the solid precipitate by centrifugation the low-temperature (<82°C) gas vents (up to 22.5). Dry
at 4,000 rpm for 30 min, was used for: (1) CO2 as CO32− by gases are dominated by CO2 (up to 911,092 μmol/mol) and
titration with 0.5 N HCl solution; (2) SO2 as SO42−, after show relatively high concentrations of acidic compounds,
oxidation with H2O2, by ion-chromatography (Dionex such as SO2 (up to 87,804 μmol/mol), HCl (up to
DX100); (3) HCl and HF as Cl− and F−, respectively, by 29,506 μmol/mol), H2S (up to 10,298 μmol/mol) and HF
ion-chromatography. Successively, the solid precipitate was (up to 2,913 μmol/mol). Nitrogen, whose contents show a
oxidized by H2O2 to determine H2S as SO42− by ion- large variability, between 23,245 and 207,209 μmol/mol, is
chromatography. Finally, S0 was extracted from the final the second major component for all the gas samples, with the
residual solid with CCl4 and oxidized to S2I2 with the ad- exception of the two fumaroles with T ≥295°C (# 1, and 2).
dition of KI. Sulfur of S2I2 was oxidized to SO42− by KBrO3 Relevant concentrations of H2 and CO (up to 20,683, and
and analysed by ion-chromatography (Montegrossi et al. 2001). 10,084 μmol/mol, respectively) and minor amounts of He
Analytical error is <5% for the main gas components and (up to 28 μmol/mol) were measured. A significant air-
<10% for minor and trace gas compounds. contamination seems to affect the low-temperature fu-
The 13C/12C isotopic ratio of CO2 (expressed as δ13C ‰ maroles, as indicated by their relatively high Ar and Ne
V-PDB) was measured by using 2 ml of the soda solution concentrations (up to 1,416 and 0.77 μmol/mol, respective-
after the addition of ∼5 ml of anhydrous phosphoric acid ly), while the hottest gas vents, whose Ar and Ne contents
under vacuum. The CO2 formed by lowering the pH was are more than one order of magnitude lower, show only minor
equilibrated at 25°C in a thermal bath overnight. The ex- atmospheric contribution. Oxygen contents, varying between
solved CO2 was then analyzed with a Finningan Delta S 207 and 770 μmol/mol, are lower than those expected by
mass spectrometer. Internal (Carrara and San Vincenzo considering the atmospheric component present in the
marbles) and international (NBS18 and NBS19) standards fumaroles calculated on the basis of the Ar contents, likely
were used for the estimation of external precision. Analytical because it is at least partly consumed by oxido-reductive
error is ±0.05‰. The reproducibility of δ-values for C is reactions during gas–water–rock interactions. The contents of
±0.1‰. The 18O/16O and 2H/1H isotopic ratios (expressed as the organic gases, comprising CH4, light hydrocarbons (C2–
δ18O and δD ‰V-SMOW, respectively) in the condensates C3 alkenes–alkanes pairs, i-butene and benzene) and hetero-
were determined using a Finningan Delta Plus XL mass cyclics (furane and thiophene), in the medium-to-high temper-
spectrometer. Oxygen isotopes were analyzed by using the ature fumaroles not exceed 51, 1.34 and 0.018 μmol/mol,
CO2–H2O equilibration method of Epstein and Mayeda respectively, while in the low-temperature gases are significantly
(1953). The hydrogen isotopic measurements were carried higher, being up to 734, 5.06 and 0.073 μmol/mol, respectively.
out on H2 obtained after the reaction of 10 μl of water with
metallic zinc at 500°C according to the analytical procedure Isotopic composition of Lascar fumaroles
described by Coleman et al. (1982). The experimental error
was ±0.1‰ and ±0.1‰ for δ18O and δD values, respective- The values of R/Ra, 40Ar/36Ar and δ13C–CO2 ratios in
ly. The 3He/4He (expressed as R/Ra ratios, where R is the selected gas samples and the δ18O and the δD ratios in the
3
He/4He measured ratio and Ra is the 3He/4He ratio in the condensates collected in 2002 (# 1 and 2) are listed in
air: 1.39×10−6; Mamyrin and Tolstikhin 1984) and 40Ar/36Ar Table 2. The R/Ra values range from 6.41 to 7.29, typical of
isotopic ratios were determined using a noble gas mass mantle-related helium in subduction zones (Poreda and Craig
spectrometer (VG5400), following the procedure of Poreda 1989). Similarly, the δ13C–CO2 values, comprised in a
176 Bull Volcanol (2009) 71:171–183

Table 2 δ13C in CO2 (‰V-PDB), R/Ra and Ar/36Ar ratios for selected gas samples and δ18O and δD isotope ratios in condensates; CO2/3He,
40

N2excess/3He and CH4/3He ratios

Sample number R/Ra He/Ne 40


Ar/36Ar δ13C δ18O δD CO2/3He N2excess/3He CH4/3He

1 n.a. n.a. n.a. n.a. 2.6 −45.6 n.a. n.a. n.a.


2 n.a. n.a. n.a. n.a. 4.3 −43.7 n.a. n.a. n.a.
3 7.08 34 367 n.a. n.a. n.a. 3.19×109 4.17×108 2.07×106
6 6.4 35 296 n.a. n.a. n.a. 8.35×109 1.16×109 4.84×106
7 n.a. n.a. n.a. −3.34 n.a. n.a. n.a. n.a. n.a.
9 n.a. n.a. n.a. −2.71 n.a. n.a. n.a. n.a. n.a.
11 7.3 142 329 −1.74 n.a. n.a. 1.66×1010 1.20×109 3.36×105

n.a. Not analyzed

relatively narrow range (from −1.74‰ to −3.34‰ V-PDB), possibly due to low contribution of meteoric water to the hot
are consistent with those directly originated from the mantle circulating fluids. The hyper-arid climate, rainfall in Lascar
(e.g. Hoefs 1973; Rollinson 1993). Accordingly, the area varies from a few millimetres to some tens of
CO2/3He ratio varies between 3.19×109 and 1.66×1010 millimetres per year (Risacher and Alonso 2001), may
(Table 2), slightly exceeding those found at mid-ocean ridges explain the low rate of water recharge from precipitation to
(2×109; Marty and Jambon 1987), although in the range the local system feeding the medium-to-high temperature
measured in fumarolic discharges from Central America fumaroles. Moreover, the high temperatures of the ground in
volcanoes (between 2.55×109 and 61.7×1010), where CO2 is the northern part of the Active Crater prevent the formation
also related to contribution from subducted carbonate sedi- of any snow cap, which, on the other hand, almost perma-
ments (Patino et al. 2000; Snyder et al. 2001). The 40Ar/36Ar nently covers the southern and western external flanks of the
ratios range between 296 and 367, suggesting that Ar volcano summit, where water permeates and interacts with
is, at least partly, derived from a non-atmospheric source ascending hot fluids. This would explain how the gas vents
(Matsuda and Marty 1995). The δ18O and δD values in located in the peripheral area of the fumarolic emissions, i.e.
fumarolic condensates of #1 (+2.6‰ and −45.6‰ V-SMOW, along the southern crater rim (# 3, 4 and 5; Fig. 2) and in the
respectively) and #2 (+4.3‰ and −43.7‰ V-SMOW, western zone of the platform (# 6, 7 and 8; Fig. 2) are largely
respectively) are plotted in Fig. 3. These two fumarolic constituted by water vapor (up to 94.4% by vol.; Table 1).
condensates lie along a mixing line between the Andesitic One more peculiar chemical character of the Active Crater
water (Taran et al. 1989; Giggenbach 1992a) and the fumaroles is represented by the high contents of acidic gas
meteoric water precipitating at 5,600 m, as defined by the species, SO2, HCl and HF (Table 1). The presence of highly
meteoric water line proposed by Chaffaut et al. (1998) for acidic compounds clearly indicates that gases are affected
the Altiplano of northern Chile and southern Bolivia. by conspicuous contributions from a high-temperature
Instead, water in the fumarolic condensates may be
interpreted as deriving from mixing of Andean Cordillera
meteoric precipitation with “andesitic water”, as defined by
Taran et al. (1989) and Giggenbach (1992a).

Discussion

Origin of gases

One of the most intriguing compositional features of the


Lascar fumaroles is the strong inverse correlation between the
H2O/CO2 ratios and the outlet temperatures of the gas vents
(Fig. 4). Gases with T>150°C (closed squares and triangles)
have indeed extremely low H2O contents (Table 1), even
when compared with those measured in fumaroles with
Fig. 3 δ18O-δD diagram for the fumarolic condensates from Active
similar temperature of other volcanoes in South America, e.
Crater. The “andesitic water” field (Taran et al. 1989; Giggenbach
g. Galeras and Cumbal volcanoes, Colombia (Fischer et al. 1992a), the Local Meteoric Water Line (Chaffaut et al. 1998) and the
1997; Lewicki et al. 2000). Such a composition may be calculated composition of the local precipitation are also shown
Bull Volcanol (2009) 71:171–183 177

Fig. 4 H2O/CO2 vs. T (°C) for Active Crater fumaroles collected in


November 2002 (closed squares), May 2005 (open circles) and Fig. 6 SO2–Ar*100-H2S*10 ternary diagram for Active Crater
October 2006 (closed triangles for fumaroles with T>150°C; open fumaroles. Symbols as in Fig. 4
triangles for fumaroles with T<150°C)
ical composition of fumaroles from the Active Crater can be
source, as it should be expected considering the frequent interpreted as the result of a mixing process among three
and recent eruptive activity of this volcano and in agree- possible end-members related to (1) a magmatic source, (2)
ment with the mantle signature of the helium and carbon a hydrothermal component and (3) meteoric (air) contribu-
isotopic ratios. Nevertheless, the (H2+HCl)–(SO2)–(CO2) tion, respectively. In detail, the medium-to-high temperature
ternary diagram (Fig. 5) evidences that the low temperature (>150°C) gases, which in Fig. 6 plot closer to the SO2
fumaroles (<82°C) of the southern crater rim (open circles) corner, have the strongest magmatic signature, while hydro-
and the western sector of the platform (open triangles), thermal compounds and air contamination seem to acquire
corresponding to the periphery of the discharging area, are increasing importance for the peripheral, low-temperature
clearly distinguished from the gas vents with T>150°C, gas vents.
which are concentrated in the north-eastern border of the A clear relationship between the chemical-physical
platform (Fig. 2). The fumaroles of the former group are features of the fumaroles and their spatial distribution is also
indeed enriched in H2 and HCl, which can be ascribed to shown by the N2excess–SO2–CH4 ternary diagram (Fig. 7),
gas–water–rock interactions in magmatic-hydrothermal where N2excess, which can be defined as the portion of N2
environments (Martini 1993), while those of the latter group, content of each gas sample that cannot be related to the
having relatively higher SO2 contents, likely represents a atmospheric component, is given by: N2meas−(N2/Ar)air×
more direct contribution from a magmatic end-member. The Armeas. The low-temperature fumaroles trace a clear trend,
SO2–H2S–Ar ternary diagram (Fig. 6) shows that the chem-

Fig. 7 CH4*500-SO2–N2excess ternary diagram for Active Crater


Fig. 5 (SO2)–(CO2)/50-(H2 +HCl) ternary diagram for Active Crater fumaroles. N2excess is given by: N2meas−(N2/Ar)air×Armeas. Sym-
fumaroles. Symbols as in Fig. 4 bols as in Fig. 4
178 Bull Volcanol (2009) 71:171–183

showing a progressive increase of CH4, a compound reactions at T>150°C and prevailing reducing conditions
typically enriched in fluids from hydrothermal environ- (e.g. Capaccioni et al. 1995; 2004; Tassi 2004; Tassi et al.
ments and/or lower outlet temperatures (e.g. Giggenbach 2005a). This seems to exclude any significant contribution of
1996). This diagram also evidences a strong compositional CH4 from bacterial activity. Therefore, the source of light
difference between the gases collected in 2002 and those hydrocarbons at Lascar volcano is referred to the hydrother-
with comparable temperature (>150°C) sampled in 2006 mal environment surrounding the magmatic-related system
(samples # 9–14), the latter being marked by relatively feeding the fumaroles seeping out from the Active Crater.
lower SO2 contents likely related to a general lowering of The mixing of the hydrothermal component with the
the purely magmatic contribution. These results possibly magmatic-related oxidizing hot fluids likely promote thermal
reflect a variation in time of the fluids released from the deep cracking processes that are able to completely decompose
source that in 2002 was likely related to a less degassed long-chain saturated hydrocarbons. This may explain the
magma, enriched in the more soluble species, with respect to lack of C4+ species, with the only exception of benzene,
that feeding the fumaroles in 2006. furane and thiophene that are stable even at relatively high
The relative abundances of the non-reactive gas species, N2, temperature (e.g. Montegrossi et al. 2003; Tassi 2004;
Ar and He (Fig. 8), are typical of gas discharges associated Capaccioni et al. 2005). It has to be noted that the low
with subduction-zone andesitic magmatism (“andesite” field; values of the CH4/3He ratio (comprised between 3.36×105
Giggenbach 1992b). However, the low-temperature fumar- and 4.84×106), partly overlapping with those measured in
oles, those most affected by the meteoric component, are sediment-free mid-ocean ridge environment (between 1×105
displaced from the rest of the gas samples, plotting along the and 1×106; Snyder et al. 2003) and significantly lower than
mixing line between the andesite field and air. A deep origin those of thermogenic gases (up to 1×1012; Poreda et al.
for N2 is also identified by the N2excess/3He ratios, between 1988), seem to indicate that the presence of CH4 from
4.17×108 and 1.20×109 (Table 2), a range commonly found abiotic synthesis (i.e. forming reactions from inorganic
in gases discharging from arc volcanoes, where N2 is to be compounds) cannot be completely ruled out. Nevertheless,
related to gas extraction from subducted slab and sediments it has to be considered that there has been a long and
(Snyder et al. 2003). outstanding debate on whether CH4 can be of a pure
Concerning the organic gas fraction, the values of the CH4/ inorganic origin (e.g. Sugisaki and Mimura 1994; Kenney
(C2H6+C3H8) ratio (<170), a parameter commonly adopted 1995) and, at the present, the rare examples of abiogenic
to constrain the temperature conditions characterizing the CH4 production in natural gas emissions are only referred to
genetic process of these compounds (e.g. Oremland et al. CO2 reduction occurring at extremely reducing conditions,
1987; Whiticar and Suess 1990), suggest that the origin of related to serpentinization of olivines during the interaction
the light hydrocarbons is likely related to decomposition of of ultramafic rocks with water (e.g. Abrajano et al. 1988;
more complex organic compounds through thermocatalytic Berndt et al. 1996; Horita and Berndt 1999; Taran et al.
2002). Therefore, the low CH4/3He ratios measured at Lascar
volcano seems to indicate that the organic-rich hydrothermal
component contribute to the chemistry of the crater
fumaroles only at limited extent.

Geothermometry

A systematic thermodynamic evaluation, based on the cor-


relation of the measured contents of gas compounds with the
theoretical compositions predicted by models simulating
chemical equilibria among gas species, is considered a useful
tool to investigate on the physical-chemical conditions of the
subsurface systems controlling the reaction paths of circulat-
ing fluids in both geothermal and volcanic environments (e.g.
Giggenbach 1980; Arnorsson and Gunnlaugsson 1985;
D’Amore 1991; Chiodini and Marini 1998). The measured
H2/H2O ratio, when compared with those ratios expected for
potential buffers involving the main gas compounds, i.e. the
Fig. 8 Ar–N2/100-He*10 ternary diagram for Active Crater fumar-
oles. Air and Air Saturated Waters (ASW) compositions and
SO2–H2S redox pair, considered the major redox buffer for
convergent plate boundaries (“andesite”) field (Giggenbach 1996) magmatic gases, and/or the rock matrix, i.e. the generalized
are also reported. Symbols as in Fig. 4 FeO–FeO1.5 couple, regarded as the most suitable redox
Bull Volcanol (2009) 71:171–183 179

buffer system for hydrothermal fluids, can be used to describe


the dominating redox state for volcanic fluids at depth (e.g.
Giggenbach 1987; 1996). As shown in the log(H2/H2O) vs
temperature diagram (Fig. 9), the fumaroles with outlet
temperature >150°C do not distribute along the solid lines
representing the chemical equilibrium attained in the presence
of the two mentioned redox buffers, while the gases from the
peripheral emission sites are aligned along the FeO–FeO1.5
buffer line. However, it has to be considered that the
H2–H2O pair, although regulated by reactions characterized
by a relatively rapid kinetics (Giggenbach 1987), is likely
quenched through cooling of the hot ascending fluids
approaching the surface (e.g. Giggenbach 1991). Thus, to
obtain an evaluation of both temperature and redox potential
prevailing during the equilibration of H2, the H2–H2O redox-
Fig. 10 Log(H2/H2O) vs. log(CO/CO2) diagram for Active Crater
sensitive pair has to be combined with a geoindicator having
fumaroles. Solid lines refer to equilibria controlled by the FeO–FeO1.5
comparable kinetic characteristics, such as the CO–CO2 pair, and the SO2–H2S redox pairs. Dashed lines are the calculated
which is controlled by the following pressure-independent isotherms for the simultaneous equilibrium of the H2–H2O and the
reaction: CO–CO2 geothermometers. Symbols as in Fig. 4

CO2 þ H2 $ CO þ H2 O ð1Þ
The temperature dependence of the equilibrium constant of calculated temperatures may be lower than those at which
reaction 1 is given by (Giggenbach 1996): fumarolic gases really equilibrated. Actually, the distribution
log ðCO=CO2 Þ  log ðH2 =H2 OÞ ¼ 2:49  2; 248=T ð2Þ of gas samples in Fig. 10 clearly indicates that the SO2–H2S
buffer system is able to control the redox conditions of the
magmatic-hydrothermal environment where fumarolic gases
As shown in Fig. 10, the low-temperature gases seem to equilibrated. This suggests that the most reliable equilibrium
equilibrate at 450–550°C at the prevailing reducing con- temperatures for Lascar crater gases are those indicated in
ditions of the rock redox buffer, while the medium-to-high Fig. 9 by projecting the H2–H2O ratios on the SO2–H2S line.
temperature fumaroles attain their equilibrium at 500–600°C Among the most common chemical parameters used as
under more oxidizing conditions, likely referred to the geoindicators in geothermal and volcanic systems, a partic-
magmatic-related sulphur buffer. It is worthy of noting that ular attention is usually devoted to the CH4/CO2 ratio (e.g.
some CO loss due to formiate production in the soda sam- Giggenbach 1980; 1987; 1997; Taran and Giggenbach 2003;
pling flasks could have occurred. Therefore, the CO–CO2 Fiebig et al. 2004). The main reaction involving these two C-
bearing gases is given by:
CO2 þ 4H2 $ CH4 þ 2H2 O ð3Þ

In liquid-dominated geothermal systems, with temperature


above 160°C and large availability of catalysts, such as free
transition metals (Mango 1996) and Fe-bearing phases
(Berndt et al. 1996), reaction 3 tends to approach equilibrium
under the control of the FeO–FeO1.5 redox pair (e.g.
Giggenbach 1997), in agreement with the behavior of the
Fischer-Tropsch synthesis for the industrial production of
various C–H–O-chemicals (Storch et al. 1951; Anderson
1984). Differently, in volcanic environment, where fluid cir-
culation is rapid and redox conditions also depend on
oxidizing magmatic gases, the CH4–CO2 pair shows no
tendency to re-equilibrate (e.g. Taran and Giggenbach 2003).
This behavior is likely due to (1) the slow kinetics of reaction 3
Fig. 9 Log(H2/H2O) vs. outlet temperature (°C) diagram for Active
Crater fumaroles. Solid lines refer to equilibria controlled by the FeO– (Giggenbach 1997) and (2) the coexistence of different redox
FeO1.5 and the SO2–H2S redox pairs. Black symbols as in Fig. 4 buffer systems controlling fH2. However, in the log(CH4/
180 Bull Volcanol (2009) 71:171–183

Fig. 11 Log(C2H4/C2H6) vs. log(CO/CO2) for Active Crater fumar- Fig. 12 Log(C2H4/C2H6) vs. temperature for Active Crater fumaroles.
oles. Solid lines refer to equilibria controlled by the FeO–FeO1.5 and Temperatures are those calculated by using the H2–H2O geothermom-
the SO2–H2S redox pairs. Dashed lines are the calculated isotherms eter. Solid lines refer to equilibria controlled by the FeO–FeO1.5 and
for the simultaneous equilibrium of the CH4–CO2 and the CO–CO2 the SO2–H2S redox pairs. Symbols as in Fig. 4
geothermometers. Symbols as in Fig. 4

whose temperature dependence of the equilibrium constant is


CO2) vs. log(CO/CO2) diagram (Fig. 11), Lascar gases seem given by (Capaccioni et al. 2004):
to equilibrate at temperatures (up to 860°C), consistent with 7:15  6; 600=T ¼ logðC3 H6 =C3 H8 Þ þ log f H2 ð7Þ
those evaluated on the basis of the H2/H2O ratios by con-
sidering that redox conditions are governed by the SO2–H2S In the log(C3H6/C3H8) vs. calculated temperature diagram
buffer system (Fig. 9). (Fig. 13), all the fumaroles are clustered in an area that
The chemical features of the C2 and C3 alkenes–alkanes corresponds to more reducing conditions and/or low equi-
redox pairs, which have been revealed particularly suitable librium temperatures than those of the C2–C2 redox pair. The
to investigate the thermal and redox conditions dominating lack of simultaneous equilibration of the C2 and C3 alkanes–
at depth the hydrothermal-magmatic fluids (e.g. Seewald alkenes pairs may be due to the different kinetics of reactions
1994; Capaccioni and Mangani 2001; Taran and Giggenbach in which they are respectively involved. In fact, reaction 6 is
2003; Tassi et al. 2005a; 2005b), can be used to highlights characterized by a significantly lower activation energy com-
the physical-chemical features of the source region of the pared to that of reaction 4 (Lide 2001). During the rising of
Lascar fumarolic fluids provided by the classical geoindicators. fumarolic fluids the C2H4/C2H6 ratio, which is governed by
De-hydrogenation reaction involving the C2 alkene–
alkane pair is given by:
C2 H6 $ C2 H4 þ H2 ð4Þ
The temperature dependence of the equilibrium constant
for reaction 4 is described by the following equation
(Capaccioni et al. 2004):
7:43  8; 809=T ¼ logðC2 H4 =C2 H6 Þ þ log f H2 ð5Þ
The distribution of Lascar gases in Fig. 12, where the log-
values of the C2H4/C2H6 ratio vs. temperature calculated on
the basis of the H2/H2O ratios are plotted, seems to indicate
that this alkene–alkane pair tends to equilibrate at redox
conditions strongly influenced by the presence of magmatic
fluids.
De-hydrogenation reaction involving the C3 alkene–alkane
pair given by: Fig. 13 Log(C3H6/C3H8) vs. temperature for Active Crater fumaroles.
Temperatures are those calculated by using the H2–H2O geothermom-
eter. Solid lines refer to equilibria controlled by the FeO–FeO1.5 and
C3 H8 $ C3 H6 þ H2 ð6Þ the SO2–H2S redox pairs. Symbols as in Fig. 4
Bull Volcanol (2009) 71:171–183 181

Fig. 14 Schematic N–S section


and conceptual geochemical
model of the summit portion of
the Active Crater at Lascar
volcano

the slow reaction 4, is quenched at relatively high temper- reducing (hydrothermal fluids). The compositional variability
ature and/or oxidizing conditions, while the C3H6/C3H8 ratio, characterizing the Active Crater fumaroles is related to both
controlled by the more rapid reaction 6, is able to readjust at the position of the gas vents and the temporal evolution, from
shallower depth. November 2002 to October 2006, of the gas chemistry that
shows decreasing inputs of magmatic fluids. This can be
ascribed to either a progressive depletion of the highly-soluble
Conclusions species (i.e. SO2) in the magmatic reservoir feeding the gas
exhalations at surface due to its continuous degassing or the
Chemical and isotopic features of the fumaroles at the Active enhancing influence of an immature hydrothermal system
Crater of Lascar volcano result by the mixing of at least three after the volcanic activity of Lascar volcano up to 2005.
different components: (1) magmatic, (2) hydrothermal and (3) Accordingly, a general weakening of the fumarolic output
meteoric. The gas chemistry of the vents discharging in the rate from the Active Crater has been observed during this
northern part of the platform bordering the bottom of the period. The flux decrease of the highly oxidizing fluids can
Active Crater, which represent the main fumarolic field, also explain the contemporary increase of the gas species
strongly differs from that located in the western sector and produced by secondary gas–water–rock interactions at high
along the crater rim. The former are more affected by a direct temperature (i.e. H2 and HCl). The chemical variations to
magmatic contribution, mainly reflected by the low H2O/CO2 more hydrothermal conditions suggest that in the observation
ratios and the high concentrations of SO2, whereas the latter period no magma have reached the shallow environment
also depends on the influence of a shallower hydrothermal- below the crater bottom.
meteoric system confined the periphery of the magmatic Our results may have also important implications in terms
system, as supported by the relatively high contents of H2, of volcanic hazard, since crater fumaroles seem to be par-
CH4, C2–C6 hydrocarbons and atmospheric-related species. ticularly sensitive to even minor modifications of the ther-
A chemical transition between these two groups is recorded. modynamic conditions acting on the magmatic-hydrothermal
In Fig. 14, a schematic N–S section of the Active Crater is system beneath the Active Crater. Thus, it is reasonable to
reported along with a conceptual geochemical model to point suggest that a periodic geochemical monitoring on the high-
out the various sources feeding the gas exhalations. temperature fluid discharges could be able to trace the future
Gas geothermometry, based on chemical reactions relating evolution of the Lascar volcanic activity.
both organic and inorganic species, indicates equilibrium
temperatures up to 860°C under variable redox conditions
Acknowledgements This research was partially financed by Dirección
progressively changing, from the centre to the outer part of the General de Investigación y Postgrado (UCN-Chile) and by D-21050592
fumarolic area, from highly oxidizing (magmatic fluids), to CONICYT grant (Government of Chile). The authors wish to express
182 Bull Volcanol (2009) 71:171–183

their gratitude to Jaime Llanos (Inorganic Chemical Laboratory-UCN- D’Amore F (1991) Gas geochemistry as a link between geothermal
Chile) for facilities in the samples preparation, to José G. Viramonte and exploration and exploitation. In: D’Amore F (ed) Application of
Mariano Poods (UNSA-Argentina) for their help during the first sampling geochemistry in geothermal reservoir development. UNITAR, New
campaign, and Victor Gaete, Karen Guzman and Valeria Ortega (UCN- York, pp 93–117
Chile) for their help during the second and third sampling campaigns. Dèruelle B, Figueroa O, Medina E, Viramonte J, Maragaño C (1996)
Special thanks to Steffen Welsch, our field guide up to the top of the Petrology of pumices of April 1993 eruption of Lascar (Atacama,
volcano. We thank BW Christenson and an anonymous reviewer for their Chile). Terra Nova 8:191–199
useful suggestions and reviews. Epstein S, Mayeda TK (1953) Variation of the 18O/16O ratio in natural
waters. Geochim Cosmochim Acta 4:213–224
Fiebig J, Chiodini G, Caliro S, Rizzo A, Spangenberg J, Hunziker JC
(2004) Chemical and isotopic equilibrium between CO2 and CH4
References in fumarolic gas discharges: Generation of CH4 in arc magmatic-
hydrothermal systems. Geochim Cosmochim Acta 68:2321–2334
Abrajano TA, Sturchio NC, Bohlke JK, Lyon GL, Poreda RJ, Stevens Fischer TP, Sturchio NC, Stix J, Arehart GB, Counce D, Williams SN
CM (1988) Methane-hydrogen gas seeps, Zambales ophiolite, (1997) The chemical and isotopic composition of fumarolic gases
Philippines: deep or shallow origin? Chem Geol 7:211–222 and spring discharges from Galeras Volcano, Colombia. J Volcanol
Aguilera F, Martínez C, Tassi F, Viramonte J, Medina E, Vargas H Geoth Res 77:229–253
(2003) Actividad del Volcán Lascar en el periodo 2000–2002. In: Francis PW, Rothery DA (1987) Using the Landsat thematic mapper
Abstracts of the 10th Chilean Geological Congress, Universidad to detect and monitor active volcanoes: an example from Lascar
de Concepción, Concepción, 6–10 October 2003 volcano, northern Chile. Geology 15:614–617
Aguilera F, Viramonte J, Medina E, Guzmán K, Becchio R, Delgado H, Gardeweg MC, Medina E (1994) La erupcion subpliniana del 19–20 de
Arnosio M (2006a) Eruptive activity from Lascar Volcano (2003– Abril de 1993 del Volcan Lascar, N. de Chile. In: Abstracts of the
2005). In: Abstracts of the 11th Chilean Geological Congress, 7th Chilean Geological Congress, Universidad de Concepción,
Universidad Católica del Norte, Antofagasta, 7–11August 2006 Concepción, 17–21 October 1994
Aguilera F, Viramonte J, Medina E, Guzmán K, Becchio R, Delgado H, Gardeweg MC, Spark RSJ, Matthews SJ (1998) Evolution of Lascar
Arnosio M (2006b) Recent eruptive activity from lascar volcano Volcano, northern Chile. J Geol Soc London 155:89–104
(2006). In: Abstracts of the 11th Chilean Geological Congress, Giggenbach WF (1980) Geothermal gas equilibria. Geochim Cosmo-
Universidad Católica del Norte, Antofagasta, 7–11August 2006 chim Acta 44:2021–2032
Anderson RB (1984) The Fischer-Tropsch synthesis. Academic, New Giggenbach WF (1987) Redox processes governing the chemistry of
York fumarolic gas discharges from White Island, New Zealand. Appl
Andres R, Rose W, Kyle P, de Silva S, Francis P, Gardeweg M, Moreno H Geochem 2:143–161
(1991) Excessive sulfur dioxide emissions from Chilean volcanoes. Giggenbach WF (1991) Chemical techniques in geothermal exploration.
J Volcanol Geoth Res 46:183–198 In: D’Amore F (ed) Application of Geochemistry in Geothermal
Arnorsson S, Gunnlaugsson E (1985) New gas geothermometers for Reservoir Development. UNITAR, New York, pp 253–273
geothermal exploration—Calibration and application. Geochim Giggenbach WF (1992a) Isotopic shifts in waters from geothermal and
Cosmochim Acta 49:1307–1325 volcanic systems along convergent plate boundaries and their
Berndt ME, Allen DE, Seyfried WE (1996) Reduction of CO2 during ser- origin. Earth Planet Sci Lett 113:495–510
pentinization of olivine at 300°C and 500 bar. Geology 24:351–354 Giggenbach WF (1992b) The composition of gases in geothermal and
Capaccioni B, Mangani F (2001) Monitoring of active but quiescent volcanic systems as a function of tectonic setting. In: Kharaka YK,
volcanoes using light hydrocarbon distribution in volcanic gases: Maest AS (eds) Water–Rock Interaction. Balkema, Rotterdam,
the results of 4 years of discontinuous monitoring in the Campi pp 873–878
Flegrei (Italy). Earth Planet Sci Lett 188:543–555 Giggenbach WF (1996) Chemical composition of volcanic gases. In:
Capaccioni B, Martini M, Mangani F (1995) Light hydrocarbons in Scarpa M, Tilling RJ (eds) Monitoring and mitigation of Volcanic
hydrothermal and magmatic fumaroles: hints of catalytic and Hazards. Springer, Heidelberg, pp 221–256
thermal reactions. Bull Volcanol 56:593–600 Giggenbach WF (1997) Relative importance of thermodynamic and
Capaccioni B, Taran Y, Tassi F, Vaselli O, Mangani F, Macias JL (2004) kinetic processes in governing the chemical and isotopic composi-
Source conditions and degradation processes of light hydrocarbons tion of carbon gases in high-heat flow sedimentary basins. Geochim
in volcanic gases: an example from El Chichón volcano (Chiapas Cosmochim Acta 61:3763–3785
State, Mexico). Chem Geol 206:81–96 Giggenbach WF, Gougel RL (1989) Method for the collection and
Capaccioni B, Tassi F, Maione M, Mangani F, and Vaselli O (2005) analysis of geothermal and volcanic water and gas samples. NZ-
Organics in volcanic gases: a review on their distribution and DSIR Report, CD 2387, 53
applications to volcanic surveillance. In: Abstracts of the AGU Fall Glaze LS, Francis PW, Rothery DA (1989) Measuring thermal budgets of
Meeting, San Francisco, 5–9 December 2005 active volcanoes by satellite remote sensing. Nature 338:144–146
Chaffaut I, Coudrain-Ribstein A, Michelot JL, Pouyaud B (1998) Global Volcanism Program (1994) Lascar, Volcanic Activity Reports,
Précipitations d’altitude du Nord-Chile, origine des sources de vapeur BGVN 18:04. http://www.volcano.si.edu
et données isotopiques. Bull Inst Fr Etudes Andines 27:367–384 Global Volcanism Program (1995) Lascar, Volcanic Activity Reports,
Chiodini G, Marini L (1998) Hydrothermal gas equilibria: The H2O–H2– BGVN 20:06. http://www.volcano.si.edu
CO2–CO–CH4 system. Geochim Cosmochim Acta 62:2673–2687 Global Volcanism Program (1996) Lascar, Volcanic Activity Reports,
Clavero J, Naranjo J, Cayupi J (2006) El ciclo eruptivo del 18 al 25 de BGVN 21:07. http://www.volcano.si.edu
abril de 2006 del Volcán Láscar, Andes Centrales. In: Abstracts Global Volcanism Program (2000) Lascar, Volcanic Activity Reports,
of the 11th Chilean Geological Congress, Universidad Católica BGVN 25:06. http://www.volcano.si.edu
del Norte, Antofagasta, 7–11August 2006 Global Volcanism Program (2005a) Lascar, Volcanic Activity Reports,
Coleman ML, Shepherd TJ, Durham JJ, Rouse JE, Moore GR (1982) BGVN 30:04. http://www.volcano.si.edu
Reduction of water with zinc for hydrogen isotope analysis. Anal Global Volcanism Program (2005b) Lascar, Volcanic Activity Reports,
Chem 54:993–995 BGVN 30:05. http://www.volcano.si.edu
Bull Volcanol (2009) 71:171–183 183

Global Volcanism Program (2006a) Lascar, Volcanic Activity Reports, Risacher F, Alonso H (2001) Geochemistry of ash leachates from the
BGVN 31:04. http://www.volcano.si.edu 1993 Lascar eruption, northern Chile. Implication for recycling
Global Volcanism Program (2006b) Lascar, Volcanic Activity Reports, of ancient evaporites. J Volcanol Geoth Res 109:319–337
BGVN 31:11. http://www.volcano.si.edu Rodriguez LA, Watson IM, Viramonte J, Hards V, Edmonds M,
Hellweg M (2000) Physical models for the source of Lascar’s Cabrera, A, Oppenheimer C, Rose WI, Bluth GJS (2005) SO2
harmonic tremor. J Volcanol Geoth Res 101:183–198 conversion rates at Lascar and Soufriere Hills volcanoes. In:
Hoefs J (1973) Stable isotope geochemistry. Springer, Berlin Abstracts of the 9th Gas Workshop, Palermo, 1–10 May 2005
Horita J, Berndt ME (1999) Abiogenic methane formation and isotopic Rollinson HR (1993) Using geochemical data: evaluation, presenta-
fractionation under hydrothermal conditions. Science 285:1055– tion, interpretation. Longman, London
1057 Seewald JS (1994) Evidence for metastable equilibrium between
Kenney JK (1995) Comment on Mantle hydrocarbons: Abiotic or hydrocarbons under hydrothermal conditions. Nature 370:285–
biotic? By R. Sugisaki and K. Mimura. Geochim Cosmochim 287
Acta 59:3857–3858 Snyder G, Poreda R, Hunt A, Fehn U (2001) Regional variations in
Lewicki JL, Fischer TP, Williams SN (2000) Chemical and isotopic volatile composition: Isotopic evidence for carbonate recycling in
compositions of fluids at Cumbal Volcano, Colombia: evidence the Central American volcanic arc. Geochem Geophys Geosyst 2.
for magmatic contribution. Bull Volcanol 62:347–361 DOI 10.1029/2001GC000163
Lide DR (2001) Handbook of chemistry and physics, 82th edn. CRC, Snyder G, Poreda R, Fehn U, Hunt A (2003) Sources of nitrogen and
Boca Raton, Florida methane in Central American geothermal settings: Noble gas and
129
Mamyrin BA, Tolstikhin IN (1984) Helium isotopes in nature. In: I evidence for crustal and magmatic volatile components.
Fyfe WS (ed) Development in geochemistry. Elsevier, Amster- Geochem Geophys Geosyst 4. DOI 10.1029/2002GC000363
dam, pp 1–273 Storch HH, Golumbic N, Anderson RB (1951) The Fischer-Tropsch
Mango FD (1996) Transition metal catalysis in the generation of and related synthesis. Wiley, New York
natural gases. Org Geochem 24:977–984 Sugisaki R, Mimura K (1994) Mantle hydrocarbons: abiotic or biotic?
Martini M (1993) Water and fire: Vulcano island from 1977–1991. Geochim Cosmochim Acta 58:2527–2542
Geochem J 27:297–303 Taran YA, Giggenbach WF (2003) Geochemistry of light hydro-
Marty B, Jambon A (1987) C/3He in volatile fluxes from the solid carbons in subduction-related volcanic and hydrothermal fluids.
Earth—implications for carbon geodynamics. Earth Planet Sci In: Simmons SF, Graham IJ (eds) Volcanic, geothermal, and ore-
Lett 83:16–26 forming fluids: rulers and witnesses of processes within the
Mather TA, Tsanev VI, Pyle DM, McGonigle AJS, Oppenheimer C, Earth. Littleton, Colo Soc Econ Geol Spec Issue 10:61–74
Allen AG (2004) Characterization and evolution of tropospheric Taran YA, Pokrovsky BG, Esikov AD (1989) Deuterium and oxygen-
plumes from Lascar and Villarica volcanoes, Chile. J Geophys 18 in fumarolic steam and amphiboles from some Kamchatka
Res 59:72–82 volcanoes: “andesitic waters”. Doklady Akademii nauk SSSR
Matsuda J, Marty B (1995) The 40Ar/36Ar ratio of the undepleted 304:440–443
mantle; a reevaluation. Gephys Res Lett 22:1937–1940 Taran Y, Fisher TP, Cienfuegos E, Morales P (2002) Geochemistry of
Matthews SJ, Gardeweg MC, Sparks RSJ (1997) The 1984 to 1996 hydrothermal fluids from an intraplate ocean island: Everman
cyclic activity of Lascar Volcano, northern Chile: cycles of dome volcano, Socorro Island, Mexico. Chem Geol 188:51–63
growth, dome subsidence, degassing and explosive eruptions. Tassi F (2004) Fluidi in ambiente vulcanico: Evoluzione temporale dei
Bull Volcanol 59:72–82 parametri composizionali e distribuzione degli idrocarburi leggeri
Montegrossi G, Tassi F, Vaselli O, Buccianti A, Garofalo K (2001) in fase gassosa. Ph.D. thesis, University of Florence, Italy
Sulfur species in volcanic gases. Anal Chem 73:3709–3715 Tassi F, Vaselli O, Capaccioni B, Giolito C, Duarte E, Fernandez E,
Montegrossi G, Tassi F, Vaselli O, Minissale A (2003) Heterocyclic Minissale A, Magro G (2005a) The hydrothermal-volcanic
compounds in volcanic and geothermal systems: case studied from system of Rincon de la Vieja volcano (Costa Rica): a combined
Vulcano Island (Sicily, Italy) and Larderello (Central-Northern (inorganic and organic) geochemical approach to understanding
Italy). In: Abstracts of the 4th FIST Congress, Bellaria, 16–18 the origin of the fluid discharges and its possible application to
September 2003 volcanic surveillance. J Volcanol Geoth Res 148:315–333
Oppenheimer C, Francis PW, Rothery DA, Carlton RWT (1993) Tassi F, Martinez C, Vaselli O, Capaccioni B, Viramonte J (2005b)
Infrared image analysis of volcanic thermal features: Lascar The light hydrocarbons as new geoindicators of equilibrium
volcano, Chile 1984 1992. J Geophys Res 98:4269–4286 temperatures and redox conditions of geothermal fields: evidence
Oremland RS, Miller LG, Whiticar MJ (1987) Sources and flux of from El Tatio (northern Chile). Appl Geochem 20:2049–2062
natural gases from Mono Lake, California. Geochim Cosmochim Whiticar MJ, Suess E (1990) Hydrothermal hydrocarbon gases in the
Acta 51:2915–2929 sediments of the King-George Basin, Bransfield Strait, Antarc-
Patino LC, Carr MJ, Feigenson MD (2000) Local and regional tica. Appl Geochem 5:135–147
variations in Central American arc lavas controlled by variations Wooster M, Rothery D (1997) Thermal monitoring of Lascar volcano,
in subducted sediment input. Contrib Mineral Petrol 138:265–283 Chile, using infrared data from the along - track scanning
Poreda R, Craig H (1989) Helium isotope ratios in circum-Pacific radiometer: a 1992–1995 time series. Bull Volcanol 38:566–579
volcanic arcs. Nature 338:473–478 Wörner G, Hammerschmidt K, Henjes-Kunst F, Lezaun J, Wilke H
Poreda RJ, Farley KA (1992) Rare-gases in Samoan xenoliths. Earth (2000) Geochronology (Ar–Ar, K–Ar and He-exposure ages) of
Planet Sci Lett 113:129–144 Cenozoic magmatic rocks from northern Chile (18–22°S):
Poreda RJ, Jeffrey AWA, Kaplan LR, Craig H (1988) Magmatic Implications for magmatism and tectonic evolution of the Central
helium in subduction-zone natural gases. Chem Geol 71:199–210 Andes. Rev Geol Chile 27:205–240

You might also like