International Journal of Mass Spectrometry 415 (2017) 44–54

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International Journal of Mass Spectrometry

journal homepage: www.elsevier.com/locate/ijms

Real-time quadrupole mass spectrometry of hydrothermal gases from

the unstable Pisciarelli fumaroles (Campi Flegrei): Trends, challenges
and processes
Alessandro Fedele a,∗ , Maria Pedone a , Roberto Moretti b , Thomas Wiersberg c ,
Renato Somma a , Claudia Troise a , Giuseppe De Natale a
a
Istituto Nazionale di Geofisica e Vulcanologia, Sez. di Napoli – Osservatorio Vesuviano, Italy
b
Università degli Studi della Campania “Luigi Vanvitelli”, Dipartimento di Ingegneria Civile, Design. Edilizia e Ambiente, Aversa, CE, Italy
c
Helmholtz-Zentrum Potsdam – Deutsches GeoForschungsZentrum GFZ, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Volcanic gas sampling and post-collection chemical determination in a laboratory may preclude any
Received 9 September 2016 real-time continuous monitoring of volcanic activity. We describe the development, and show the advan-
Received in revised form 7 February 2017 tages, of a system used for the continuous monitoring of fumarolic gases discharged from the Pisciarelli
Accepted 16 February 2017
site (Campi Flegrei, Southern Italy) based on a commercial quadrupole mass spectrometer (QMS-301
Available online 24 February 2017
OmnistarTM ). Although numerous technical problems were addressed due to the ephemeral nature of
the emission point and the harsh environment, we also report measurements of the chemical composi-
Keywords:
tion of the major gas species emitted from the fumarole for two different periods (in 2009 and 2012). The
Quadrupole mass spectrometer
Fumarolic gases
CO2 /H2 S, H2 S/H2 , He/CO2 and CH4 /CO2 molar ratios were investigated in order to detect magmatic and/or
Hydrothermal systems hydrothermal components in the system, while the N2 /O2 ratio was adopted to infer other non-volcanic
Continuous geochemical monitoring processes, such as air contamination and mixing with polluted surface waters. The presented method-
Campi Flegrei ology allows continuous gas sampling and provides the first evidence of short-term gas variations not
available by direct sampling, which is often impractical and hazardous. Compared to the current tech-
niques that are used worldwide for the full characterization of gaseous emissions, i.e. chemical analysis of
traditional soda-filled under-vacuum bottles and MultiGAS surveys (laboratory-based and in situ, respec-
tively), QMS-based monitoring is complementary and, in prospect, an alternative. With our method, the
geochemical monitoring benefits of the real-time analysis for high sampling rates that can be made com-
parable to the continuous measurements of geophysical networks. This allows a better understanding
of hydrothermal features, particularly of chemical fluctuations occurring on the very short-term, which
is fundamental for the evaluation of the evolution of unrest episodes at Campi Flegrei, one of the most
hazardous volcanic areas in the world.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction sequent laboratory analysis, thermal profiling in boreholes), or

Several efforts have been made in geophysical and geochemi-
cal monitoring to interpret, and possibly predict, the evolution of
volcanic activity. Typically, geophysical methods target the depth
and size of the magmatic/hydrothermal source by inverting seismic
features and ground deformation data from widespread acquisi-
tion ground networks, such as the seismic and GPS ones, in some
cases integrated by satellite interferometry for ground displace-
ments over wide areas; geochemistry can be either based on in situ
site-specific measurements (e.g. fumarolic gases sampling and sub-
∗ Corresponding author.
E-mail address: alessandro.fedele@ingv.it (A. Fedele).
widespread data acquisition covering wide surfaces (e.g. soil diffuse
degassing).
Isolated point measurements, and subsequent laboratory anal-
yses, yield the full concentration of fluids discharged at specific
peculiar sites (fumaroles) and allow interpretation of the pressure
and temperature conditions of actively degassing hydrothermal
reservoirs by identifying the conditions yielding the last gas re-
equilibration prior to the outlet discharge. Such an approach to the
measurement of intensive parameters of the hydrothermal sys-
tem must be necessarily complemented by the measurements of
extensive quantities, such as the extension of the anomalous (i.e.
exceeding the background value) degassing areas, and the fluxes of
mass discharged at surface.

http://dx.doi.org/10.1016/j.ijms.2017.02.006
1387-3806/© 2017 Elsevier B.V. All rights reserved.
 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54 45

Volcanic eruptions are frequently preceded by variations in trometer, Toutain et al. [20] monitored CO2 , He and 222 Rn in gases
the chemical and isotopic composition of fluids discharged from from a well located at the base of the active cone on Vulcano Island
fumaroles, hot springs and also from diffuse soil emissions mak- (Italy). Shimoike and Notsu [21] reported on a system to moni-
ing observations of waters and gases basic tools to understand the tor volcanic gases extracted from an observation well located 3 km
magmatic-hydrothermal systems beneath active volcanoes [1–4]. north of the summit of the Izu-Oshima Volcano (Japan) using IR
In particular, diffuse CO2 emissions have been quantified by soil- sensors.
gas surveys of hydrothermal systems at volcanoes in a quiescent In this paper we extend results and possibilities offered by an
condition and, recently, more information have been obtained on our preliminary approach to continuous hydrothermal/volcanic gas
fumarolic CO2 emissions [5]. monitoring [22] and demonstrate the usefulness of a quadrupole
However, high-precision geochemical discrete sampling and mass spectrometer, deployed at the Pisciarelli fumarolic field
measurements suffer limitations, essentially due to the necessity of (Campi Flegrei, Southern Italy) to improve present-day strategies
accessing the point source of gas emission, avoiding any secondary of geochemical monitoring. Considering that data processing and
phenomena (such as component removal, particularly water, or interpretation are relevant part of the monitoring strategy, this
contamination). Collection of fumarolic gases is – depending on paper shows how the described data acquisition and treatment
logistics and the state of volcanic activity – mostly performed brings advancements in our understanding of the investigated
discontinuously with time intervals between consecutive sample fumarolic system, included at one of the most dangerous volcanic
collections ranging from days to weeks or even months between areas on Earth.
consecutive sample collections [6]. Sampling frequencies are too
low to allow an efficient comparison between gas data and geodetic
2. Campi Flegrei setting
and seismic information from continuous geophysical monitoring.
Furthermore, direct sampling poses dangers when getting close
2.1. Generalities
to active fumarolic sites. Steam, from both magmatic and superficial
heated up sources (such as overlying lakes or groundwaters), is the
The restless Campi Flegrei caldera (CFc), often referred to as a
most common volcanic gas, but other gases, often very toxic, are
‘supervolcano’ [23] was formed by two major events: the Cam-
emitted during eruptive events and may impact on human health.
panian Ignimbrite eruption, 39 ka ago [24,25], and the Neapolitan
CO2 and H2 S, particularly, are heavier than air and may pool at
Yellow Tuff eruption, 15 ka ago [26]. More than 1.5 million peo-
ground level and result in asphyxia [7]. Another disadvantage of
ple live within the CFc and surrounding areas, including the city
the direct sampling is that it requires instrumental analysis in the
of Naples. Volcanic risk has enormously increased through time
laboratory, which is often performed many days later making it
as a consequence of rapid population expansion and strong, often
unsuitable for tracking real-time variations on site.
irregular, urbanization. The previous eruption occurred in 1538
Because of these difficulties, the volcanic CO2 flux inventory
AD and was preceded by uplift episodes lasting decades [27]. The
(claimed as one of the most reliable gas precursors to an eruption
caldera resurgence is typically characterized by phases of uplift
[8]) remains sparse and incomplete for most of the active volca-
and subsidence over a range of timescales [28–31], not necessar-
noes on Earth [9]. Moreover, its estimate is further complicated
ily culminating in an eruption. The last important strong ground
by the high background atmospheric concentration, which, inex-
uplift (∼3.8 m) occurred from 1969 to 1984, followed by a period
orably, can affect all measurements carried out by remote-sensing
of relatively slow subsidence, interrupted by minor uplifts in 1989,
techniques [8].
1994 and 2000 [32]. Since 2005 a renewed uplift phase affects the
High-frequency measurements of volcanic gases are a priority
area, at a much smaller rate [33,34], resulting in a ground uplift of
for obtaining a better understanding of the precursors of eruptive
38 cm in the last ten years [35]. Together with a moderate seismic-
activity and unrest, but because increasing the frequency of on-site
ity [34], such a ground deformation is accompanied by other signs
discrete sampling in such environments entails high risks and costs,
of potential reawakening, particularly variations in the chemical
in the last decades, automatic systems have been developed (Multi-
composition of fumarolic emission, and flux gases degassing from
GAS) [10–13] and several novel techniques are still in experimental
soils [11,36–38]. These geochemical anomalies reveal a progressive
phase (Tunable Diode Laser TDL [5]; Differential Absorption Lidar
increase in the CO2 -rich magmatic contribution to fumarolic flu-
DIAL [8]) to become a strong tool in geochemical monitoring.
ids since 2000, largely prevailing over the meteoric/hydrothermal
Few applications of continuous fumarolic gas monitoring sys-
contribution [37,39,36]. The area is affected by intense, diffuse
tems based on quadrupole mass spectrometer have been so far
degassing and fumarolic activity in both Solfatara crater and Pis-
discussed in literature. Continuous measurement of dissolved gas
ciarelli fault [5], placed close to the town of Pozzuoli. Detailed
concentrations using a quadrupole mass spectrometer (QMS) was
geochemical analyses of the fumaroles [37–39,36,40], coupled with
described by Takahata et al. [14]. Faber et al. [15] reported on a sys-
the measurements of soil diffuse degassing [39–41] and with
tem which analyzed fumarolic gases pumped through a pipe to a
physical numerical simulations of the hydrothermal system [42],
remote station where several instruments (e.g. gas chromatograph
suggests that magma degassing episodes have a relevant role
and mass spectrometer) monitored various physical and chemical
in triggering the volcanic unrest periods that periodically affect
parameters. In situ mass spectrometer measurements of volcanic
the area [37,43,44], as strongly supported by temporal coherence
gaseous emission were conducted at several fumarolic sites using
between changes in gas composition and uplift [11,45]. In January
a commercial quadrupole mass spectrometer by Diaz et al. [16] at
2013, based on persistence of ground uplift and gas chemistry data,
Poas (Nicaragua) and Hawaii Volcanoes. It is worth noting that QMS
the Dipartimento della Protezione Civile (Italian Government) raised
represented an important advancement compared to other tech-
the state of the CFc from the green level (quiet) to the yellow level
niques for continuous gas monitoring which have been applied on
(scientific attention) [46].
several volcanoes. Earlier attempts by Le Guern [17] were based
on a portable gas-chromatograph to determine in real-time the full
gas speciation at Vulcano Island (Italy), Kilauea (Hawaii, U.S.A.), and 2.2. The fumarolic activity and state of art in geochemical
Merapi (Java, Indonesia) volcanoes. Similarly, Zimmer and Erzinger monitoring at the Pisciarelli site
[18] and Zimmer et al. [19] showed data from a gas chromatograph-
based system operating continuously at the summit of Merapi The Pisciarelli area is a fault-related fumarolic field located a few
Volcano. By means of specific infrared analysers and mass spec- hundred meters east of Solfatara crater (Fig. 1). This area, the most
46 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
Fig. 1. The Campi Flegrei caldera (CFc), Southern Italy. The unsteady Pisciarelli fumarolic field is located a few hundred meters east of the Solfatara crater. Both fumarolic
fields display vigorous hydrothermal activity within a densely populated area.
Fig. 2. The Pisciarelli fumarolic field. In the foreground the main fumarolic vent and
the bubbling mud pool. Our investigated, and ephemeral, emission points (in 2009
and 2012 campaigns) are shown.
active fumarolic vent aea in the entire Mediterranean volcanic dis-
trict [8], is characterized by the presence of fractures and is affected
by a consistent soil degassing and fluid emission (Fig. 2) from vents,
mostly ephemeral and pools. Chiodini et al. [41] first identified a
large diffuse degassing structure (DDS) with an anomalously high
CO2 flux release, which also includes the Solfatara crater, a tuff cone
near Pozzuoli that formed ∼3.9 ka BP [29]. The bulk CO2 flux from
the Pisciarelli and Solfatara sites attains 50,000 g/m2 d, over an area
of ∼1 km2 [44]. Fumarole discharges are mainly composed by H2 O
(>70%) followed by CO2 and H2 S and have surface temperatures
between 100 and 110 ◦ C [47].
A strong increase in fumarolic flow rate was reported to occur
from 2005 to 2013 [40], also testified by continuous measurements
of soil CO2 flux at the FLXOV3 station [35]. This degassing activity
was episodically accompanied by local seismic activity [48] and by
some macroscopic changes such as (1) the appearance of a vig-
orous degassing vent (March 2009), which is currently the main
active gas source at this site (T > 110 ◦ C), (2) a mud bubbling pool
(T ∼ 90 ◦ C). These changes were probably accompanied by a small
explosion [49] and the onset of a small active fumarolic field in the
southern part of the area. In March 2009, CO2 flux was evaluated
at only ∼18 tons/day; but, from 2012 to 2014 fumarolic emissions
increased, ranging from ∼170 [5] to ∼380 tons/day [8]. During the
recent ongoing unrest (in January 2013), a new vent appeared,
emitting for few days high-pressure steam and liquid water up to
3–4 meters at least, partly linked to heavy rainfall during the last
week of January. Aiuppa et al. [11] reported an increase of fumarolic
CO2 output during the campaign carried out at the end of January
2013, with an unusually strong high (>3 m) jet of gas and hot water.
In our experience at Pisciarelli, we never observed a constant
pressure of gas discharged from investigated vents, but a pulsating
behaviour. We observed many times, but never quantified, pres-
sure increases at some vents and pressure drops at others, such that
in some cases it was not possible to attain the minimal flow rates
which are necessary for the “traditional” gas sampling by using the
technique of Giggenbach and Goguel [50]. Consistent with these
field observations, a nearly linear trend of the peak temperatures,
oscillating from about 95 ◦ C up to around 115 ◦ C, has been recorded
from 2003 to date [40]. Fig. 3 shows such temperature fluctuations
at the main fumarolic outlet during the periods of QMS deployment.
These testify to the unsteady nature of the fumarole, likely related
to a still transient balance between the evolving and heating up
reservoir conditions and the filtration of gravitative waters in the
unsaturated subsoil of the fumarole. Such a behaviour, for exam-
ple, is not observed at the two main nearby Solfatara fumaroles,
which display stable temperatures (∼160 ◦ C at Bocca Grande and
∼145 ◦ C at Bocca Nuova; [40]), hence dynamically stable pathways
of ascent fluids. We relate such a strong pulsating behaviour to the
immaturity of the fumarolic ascent paths, and propose that strong
fluctuations in the mass and energy balances of the fumarole are
produced by the variable interaction of ascending fluids with the
percolating surface waters, which are formed by a mix of rainwaters
and condensed steam.
In summary, the emission of gases and fluids at Pisciarelli
is affected by near-surface secondary processes, probably of a
seasonal nature that may mask the deep signals related to the
temperature-pressure changes occurring in the hydrothermal sys-
tem [49,51].
Most of the volcanic monitoring at the Pisciarelli fumarolic field
has been so far carried out discontinuously. In particular, discontin-
 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
Fig. 3. Temporal evolution of outlet temperatures. Chronogram of the Pisciarelli outlet temperatures during the 2009 and 2012 sampling campaigns. Also reported are
temperature data taken from INGV-OV bulletins.
uous gas analysis at Pisciarelli started in 1999 [52] with a sampling
frequency of less than one per month [35]. The flux of carbon
dioxide dissipated in diffuse form via the soil has been character-
ized by Chiodini et al. [41]. In contrast, the gas output sustained
by fumarolic activity was unconstrained (before the campaigns
carried out from Aiuppa et al. [11] and Pedone et al. [5]), which
reflects current technical inability to make gas flux estimates at
low-temperature fumarolic fields. At these sites, where sulphur
dioxide (SO2 ) is typically absent, conventional ultraviolet sensing
techniques (e.g. [53]) are therefore useless, and a direct but chal-
lenging measurement of the CO2 emission rate is required [5,11].
The present-day status in the continuous monitoring of
geochemical parameters at Pisciarelli is quite poor. The afore men-
tioned automatic station (FLXOV3) for the measurement of soil CO2
fluxes was installed for the first time in March 2002, but it was
seriously and repeatedly damaged during the period 2002–2005;
therefore, the data set for this period is largely incomplete [45]. The
only attempt to determine automatically the composition of emit-
ted gases from the fumaroles was carried by Aiuppa et al. [11] by
means of a MultiGAS analyzer.
Considering the visible, but not systematically quantified,
increasing activity at the Pisciarelli site in the last decade, including
small events of dark mud expulsion [11,45,49] and together with
the highly pulsating behaviour in flow rates, it is now more impor-
tant than ever to pursue continuous gas monitoring of such an
unsteady and evolving fumarolic field in order to better understand
precursors of the whole area unrest. Consequently, at the begin-
ning of 2009, we started evaluating the feasibility of a continuous
gas monitoring station, mainly equipped with a quadrupole mass
spectrometer (QMS Pfeiffer OmnistarTM ), installed at the Pisciarelli
site.
3. Gas mass spectrometry based on QMS: experimental field
set-up
3.1. Instrument
During the surveys, carried out in 2009 and 2012, at the Piscia-
relli site, a quadrupole analyser was used in dynamic mode, i.e. the
gas was continuously pumped to the mass spectrometer, which was
left to acquire (at 1 Hz), measuring the concentrations of gases (H2 ,
H2 S, He, Ar, CH4 , CO2 , N2 , O2 ) discharging from the vent. The ana-
lyzed species have different detection limits (e.g. <0.2 ppmv for He,
<1 ppmv for H2 , CH4 , and Ar, and <10 ppmv for O2 , N2 , and CO2 [22]).
47
Moreover, the detection limit for H2 S (increasing to 200 ppmv) is
due to the isobaric interferences with oxygen.
The analyser of the qms is capable to record ion currents in the
mass range 0–100 amu. Multiple gas concentrations detection was
performed by analysing ion currents on peak maxima of eleven
channels with the following mass over charge ratios m/z: 2, 4, 14, 15,
28, 32, 33, 36, 40, 44 and 84. The number of channels was reduced
to eight in 2012 m/z: 2, 4, 14, 15, 32, 34, 40, 44. The detection time
for each channel was set to 1 s, resulting in 11 respectively 8 s a
complete record of all gases. Data were recorded minutely in order
to reduce the data volume.
The gas entrance into the quadrupole is ensured by its work-
ing pressure (lower than the atmospheric one); when the pressure
is reduced, through a capillary (GSD 320 OmniStar, 2 m length), to
∼7 × 10−8 mbar, the gas can be pumped at ∼4 × 10−6 mbar value.
In our study, the acceleration voltage was set to 90 eV in order to
achieve an acceptable ion yield at a relatively low yield of multi-
ply charged ions [22]. Multiple charged ions may cause significant
isobaric interferences on mass-to-charge ratio m/z 20 (20 Ne and
40 Ar2+ ), m/z 22 (22 Ne and CO 2+ ). The resolution of the QMS does not
2
allow discriminating between 20 Ne and 40 Ar2+ respectively 22 Ne
and CO2 2+ ; we therefore do not report neon concentrations here.
The amount of hydrocarbons is generally low in volcanic gases with
methane concentration in the water-free gas phase of Pisciarelli
volcanic gases in the range of 10–100 ppmv. Isotopic gas equilib-
ria studies suggest that CH4 is formed by reduction of CO2 [39]
rather than by thermal degradation of organic matter. The amount
of C2+ (ethane, propane, butane) in Pisciarelli volcanic gases is so
low [54] that formation of fragmented and/or multiple charged
ions is negligible. Methane was determined on m/z 15, with 85%
yield, compared to m/z 16 to circumvent the problem of isobaric
interferences with O2 2+ .
3.2. Calibration
Prior to fumarole gas monitoring, the mass spectrometer has
been calibrated for shifts of the mass scale (mass scale calibration)
and for multiple concentration detection.
The mass scale was calibrated to ensure that ion currents were
determined on their respective peak maxima. The peak maxima
were identified by measuring air on m/z 2, 4, 7, 8, 14, 15, 16, 18,
28, 32, 34, 36, 38, 40 and 44. Masses were shifted according to the
newly found peak maxima. The shift of channels not analyzed in air,
e.g. m/z 33, were interpolated from neighboring channels 32 and
34. The concentrations of gases are determined by multiplying ion
48 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
current intensities measured on certain masses with a calibration
factors stored in a library and solving the resulting equation system
based on a matrix comprising up to 64 × 64 elements. The mathe-
matical solution of the resulting equations is based on the process
of elimination according to Givens [55]. The calibration factors are
calculated from analysis of air and calibration gases with a defined
composition, similar to what could be expected in fumarolic gases.
The accuracy of the gas concentration detection has been checked
in regular intervals with air and calibration gases (once a week).
The calibration measurements, performed under the same condi-
tions as the monitoring, delivered the following relative standard
deviation values: ±0.1% for concentration range 1–100 vol.%, ±0.5%
for concentration range 1000 ppmv – 1 vol.%, ±1% for concentration
range 1000 – 100 ppmv, ±3% for concentration range 100 – 10 ppmv
and ±5% for concentrations below 10 ppmv.
Isobaric interferences between H2 S and O2 on the diagnostic
m/z ratios 32, 33, 34, and 36 lowers the detection accuracy. If both
gases are present in the gas sample, we assume an analytical error
of ±5% for both species. The long-term stability of this gas concen-
tration detection technique has been proven in several long-term
gas monitoring projects, e.g. [56,57].
After turning on, the QMS takes about 30 min to achieve the
required vacuum in the recipient. However, several more hours are
needed to achieve a stable electron emission from the filament and
thus a stable signal. During the operations, a set of gases (H2 , H2 S,
He, Ar, CH4 , CO2 , N2 , O2 ) was detected every minute (about 1400
values per day) and controlled by using the Quadstar software.
3.3. Field set-up
The investigated fumarolic field can be easily reached by car, so
transportation of equipment was not a limiting factor. During the
field operations, we used a quadrupole mass spectrometer (QMS)
OmnistarTM (Pfeiffer Vacuum, Germany) for the gas analysis and a
laptop for data storage assembled inside a small container (Fig. 4)
close to the investigated fumarole (80 m of distance). In detail, a
titanium tube was inserted into the fumarolic vent and connected
to a 100 m of teflon tube (4 mm internal diameter and 6 mm exter-
nal) to divert the gas in the QMS. Our sampling apparatus was
assembled in order to satisfy two main criteria: (i) temperature
does not drop while the gas flows through it, and (ii) no condensa-
tion processes occur before the gas reaches the QMS. In our method
the latter problem was overcome by using two traps, one located
10 m of distance from the fumarolic vent and another one placed
inside the container before the QMS inlet. Each trap consists of a
flagon placed inside an ice cooler (at T = 4 ◦ C) and a peristaltic pump
which was used to remove the condensing steam water in the trap
closer to the vent. The components of the gas monitoring system
are shown schematically in Fig. 4. Air conditioning was used to sta-
bilize the temperature of the station and a UPS (Uninterruptible
Power Supply) was used for data retrieval in case of power cut off.
The behaviour of the fumarole and also its water content was
changed in the time and for this reason the gas-sampling system
has been improved several times. Often, the main difficulty was
represented by steam condensation, suggesting to us, the future
implementation of a heated pipeline and also a Peltier cell before
the traps, to better remove the pure water at the fluid entrance
in the line. We recognize in fact that our present system is such
that removed water dissolves small amounts of other components,
particularly CO2 and H2 S [58].
Moreover, power supply components can be damaged because
of the high corrosion due to volcanic fluids. Both, water entrance
and power supply corrosion are fundamental issues to be planned
and addressed for each kind of fixed installation aimed at con-
tinuous measurements. This evidently applies to all developed
techniques worldwide, and not only to ours. Because of the above
limitations, we have so far recorded two limited datasets, working
under ideal conditions in two different periods, in 2009 and 2012.
4. Results and discussion
4.1. Geochemical ratios and their significance
The sampling and QMS analysis of the gas discharges from
the fumarolic field (Fig. 2) were carried out from January to April
2009, and subsequently during twenty days among the months of
May–June 2012. Gaps of some days (10 days at most, in 2009) in our
dataset are due to interruption of measurements for re-calibration
and maintenance of the instrument.
Since the QMS has been set to acquire one measurement each
60 s, an average of about 1400 acquisitions per day was obtained.
The large amount of data obtained allowed us to observe short-
term variations (daily/weekly variations) which are typically not
returned by the discontinuous (discrete) sampling (see Electronic
Annex).
Our choice was then using daily averages of measured species
concentrations, in order to investigate the compositional fluc-
tuation in terms of ratio between species of interest during a
short-term period (a day). This choice allows us to have a set
of data that can be immediately compared to other geochemical
measurements, such as chemical ratios from daily-averaged suc-
cessive discrete sampling [59] and MultiGAS acquisition [60]. The
significance of acquired data can be appreciated in Fig. 5, in which
standard deviation is given by the distance separating the hori-
zontal bars crossing symbol and is normally within the size of the
symbol itself.
In Fig. 6, the CO2 /H2 S, H2 S/H2 , He/CO2 and CH4 /CO2 molar ratios
were plotted, and used to track the relative contribution and evo-
lution of magmatic and hydrothermal components to the analyzed
gases. Also N2 -based indicators were investigated, particularly to
detect possible secondary effects, such as external (e.g. air) contam-
ination (see next paragraph). In detail, in the 2009 measurement
campaign the CO2 /H2 S, H2 S/H2 , He/CO2 and CH4 /CO2 molar ratios
ranged from 337 to 408, 1.8 to 2.8, 7.4 × 10−6 to 1.5 × 10−5 and
6.2 × 10−5 to 1.8 × 10−4 , respectively (Fig. 6). For the same ratios,
values measured in 2012 ranged from 391 to 501, 0.17 to 0.33,
2.3 × 10−5 to 2.9 × 10−5 and 2 × 10−4 to 3 × 10−4 , respectively.
He/CO2 and CH4 /CO2 are good tracers of the injection of mag-
matic gases into hydrothermal systems [40,47,61]. These are in
fact conservative components little involved in the subsequent
hydrothermal processes (e.g. [62]). The He/CO2 ratio reflects the
different solubility of these two gas species in a magma: because at
the same pressure solubility is higher for He, an ascending gas-
saturated magma, subject to a decreasing lithostatic load, will
release gases showing an increasing He/CO2 ratio [61]. At same
time, the enhanced supply of magmatic fluids released from a ris-
ing batch of magma will result in a decrease of CH4 /CO2 , due to the
injection of hot oxidized and CO2 -rich gases into the hydrother-
mal system [47]. However, joint consideration of these two ratios
shows different behaviours for the 2009 and 2012 periods: a rapid
injection of oxidized magmatic gases, likely related to magma
ascent, might be suggested in 2012 (both ratios show higher val-
ues), whilst in 2009 the increasing trend of He/CO2 is accompanied
by an increase of CH4 /CO2 , which instead supports an increase of
the hydrothermal component, rather than of the magmatic one.
The rapid decrease of the H2 S/H2 ratio, after an initial peak in
February 2009 may suggest that either the S-input lowered in time,
or that the redox state decreased: considering the water disso-
ciation equilibrium, H2 O ⇔ H2 + 1/2O2 , a decrease in the oxygen
potential necessarily implies increasing H2 values based on the Le
Chatelier principle. For the 2009 period, this would also be con-
 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54 49

Fig. 4. Scheme of the gas monitoring system installed close to the main fumarolic vent. Fluids are driven by a membrane pump, through the two water traps, to the QMS
inlet.

Fig. 5. One day chronograms of the concentrations of gaseous species (left side), and chronograms reporting a selection of corresponding daily concentrations in the periods
of acquisition (right side).
50 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
Fig. 6. Temporal evolution of geochemical ratios involving measured gas species.
Top to bottom panel: chronograms (for the periods of data acquisition), of CO2 /H2 S,
H2 S/H2 , He/CO2 , CH4 /CO2 , N2 /O2 and N2 ,corr /H2 daily-based ratios. The thick solid
grey line goes through a short living feature discussed in the text. Thin dashed grey
lines go through potentially similar, but significantly smaller, features. See text.
sistent with increasing CH4 /CO2 , whereas invoking this process to
explain low H2 S/H2 values in 2012 would be incompatible with
dropping CH4 /CO2 values. Finally, in 2009, CO2 /H2 S values are sta-
ble during the decreasing trend of H2 S/H2 ones and then start
decreasing when H2 S/H2 values attain stable values around 2. This
is a clear evidence of decreasing CO2 content in March–April 2009,
that also explains the relative increase of He/CO2 and which can-
not be related to the arrival of a fresh S-rich shallow magmatic gas,
because any input of fresh and oxidized magmatic gas would not
be compatible with increasing CH4 /CO2 and decreasing H2 S/H2 val-
ues. In 2012, the CO2 /H2 S ratio has a constant value around ∼420,
with the exception of one datum in May.
Therefore, we may assert that monitored geochemical ratios
reveal a removal of CO2 accompanied by a trend of reduction in
the surveyed 2009 time interval. Such a removal is not compatible
with the ongoing episode of magmatic gas injection enlightened by
discrete gas sampling [40], and likely reflects a second-order fluc-
tuation not catched by classical discrete sampling carried out on a
monthly basis (see Electronic Annex and [35]).
The shorter interval, surveyed in 2012, bears the same inter-
pretation as for year 2009, in light of (a) higher CH4 /CO2 values
(although dropping in time, likely due to an ongoing oxidation),
(b) higher He/CO2 and (c) lower H2 S/H2 ratios, which seem to
expand the 2009 trend for the same indicators (Fig. 6). However, the
CO2 /H2 S ratio, rather than further decreasing shows values even a
little larger than those measured in the initial phase of the 2009
campaign. This can be due to the arrival of a deep derived CO2 and
He-rich, but S-poor, gas, which enters and oxidizes the hydrother-
mal system [38], thus yielding the H2 S/H2 even lower than in 2009
and the decreasing CH4 /CO2 . Therefore, the injected magmatic gas
should not be released by a shallow magma source (which would
supply a lot of the more soluble sulphur upward), but would have
a deep provenance, likely from the huge regional magma reservoir
located at 8 km depth [11,37].
In terms of hydrothermal versus magmatic contributions to
sampled fluids, we cannot push further our analysis, because any
interpretative effort is hampered by intrinsic limits of data qual-
ity inherited by sampling conditions and determined by local
time-space variations of investigated point of emissions. In fact,
Pisciarelli’s fumarolic field is still under evolution, not having yet
reached a definite configuration of discharging vents, unlike the
Solfatara ones.
For future studies, a better choice of sampling points, and also
an improved fluid collection set-up, are expected to reduce prob-
lems related to condensation as well as air contamination due to
a mixture of ambient air with fumarolic gas close to the vent. The
latter is likely to occur (as testified by presence of O2 ) at the outlet
point where the sampling probe is inserted.
Steam condensation, instead, would be the partial responsible
of decreasing CO2 and especially H2 S concentrations in time, due
to the high solubilities of these components in water [58]. How-
ever, water condensation cannot be responsible of the decreasing
CO2 /H2 S ratio in 2009, because the solubility of H2 S is larger than
that CO2 [58]. For the same reason, water condensation in the
sampling line can have a role on our 2012 measurements, (a) deter-
mining the relatively higher CO2 /H2 S ratio, (b) doubling the He/CO2
values and (c) depressing the H2 S/H2 ones with respect to the 2009
measurements (Fig. 6). The CH4 /CO2 ratio, which during the 2009
campaign displayed an increasing trend determined by the removal
of CO2 , in 2012 shows a behaviour likely related to a strong oxida-
tion event, largely overcoming the CO2 dissolution in the condensed
water. The fact that such an oxidation event does not affect the 2012
H2 S/H2 ratio can be explained by the continuous pressure relax-
ation within the hydrothermal system, which tends to increase H2
contents, despite any oxidation due to CO2 , which instead strongly
affects the CH4 /CO2 ratio [38]. We then see that consideration of
potential secondary effects, such as steam condensation prior to
measurement, enlarges the interpretative possibilities offered by
data, by including alternative processes other than the mixing of
magmatic and hydrothermal components.
Our results are in line with those reported in the literature from
discontinuous sampling and lab-analysis, which showed, in case of
the CO2 /H2 S (molar) ratio, an average of 296 [49]. Also our H2 S/H2
values (ranged from ∼2 to ∼3, Fig. 6) are similar to the average
(∼2.4) reported by the monitoring bulletins from INGV. The He/CO2
molar ratio (Fig. 5), from March 2009, shows in time departures
from our earlier results, which are instead in line with the dis-
crete INGV monitoring data [22]. The CH4 /CO2 ratio too shows in
time departures from earlier results in line with the discrete INGV
monitoring (∼4.9 × 10−5 ).
In 2012, our data seem to diverge from the 2009 measurements.
This is likely caused by the aforesaid instability of the emission
point (Fig. 2), which contains more liquid water respect to the past
 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54 51

years. The average of the ratios analyzed is 445 for CO2 /H2 S, 0.26 reservoir, and FeS2(py) is the pyrite component in its pure phase.
for H2 S/H2 , 2.6 × 10−5 for He/CO2 and 2.44 × 10−4 for CH4 /CO2 . We By combining reactions (1) and (2) to remove water, we obtain:
conclude therefore that, during the 2012 campaign, the new sam-
4H2 S + CH4 + 2FeO ⇔ 2FeS2 + 6H2 + CO2 (3)
pling point (Fig. 2) was not really appropriate, probably worsening
the problem of water condensation and leading to a removal of whose equilibrium constant, considering a fixed value for the activ-
other species, particularly CO2 and H2 S, occurring at the point of ity ratio of FeS2(py) and FeO(r) , can be written for partial pressures
probe insertion. Other external processes (see below) cannot be of gaseous species and then take the form:
excluded, testifying for the need of a more appropriate selection of
representative gas outlets and evidencing all the challenges related PCO2 · PH2 6 [CO2 ] · [H2 ]6
log K3 = 4
= log + 2 log P + const (4)
to the immaturity and the unsteady nature of Pisciarelli fumarolic PCH4 · PH2 S [CH4 ] · [H2 S]4
field.
in which P is the total pressure of the fluid system. From Eq. (4) we
see that, for a given temperature, pressure build-up yields at equi-
4.2. Minor fluctuations and secondary processes, other than librium a decrease of CO2 and H2 and an increase of CH4 and H2 S,
steam condensation, affecting measurements thus producing the feature observed in Fig. 5. If we now consider
the reaction of ammonia interconversion in N2 and H2 , i.e.:
We have already qualitatively analyzed the effects on measured
and selected geochemical indicators played by water condensa- 2NH3 ⇔ N2 + 3H2 (5)
tion along the sampling line. Such a secondary process may offer whose equilibrium constant, written for partial pressures, is:
an alternative explanation to the arrival, in 2012, of fresh, oxi-
dized, CO2 - and He-rich, but S-poor, magmatic gases which mix [N2 ] · [H2 ]3
log K5 = log + 2 log P (6)
with the hydrothermal component (essentially H2 O). Other pro- [NH3 ]2
cesses are related to the contamination by atmospheric air, while
we see that the pressure build-up and H2 decrease must produce
sampling, right at the inlet. This is demonstrated by the presence
an increase of [N2 ], thus yielding the positive peak shown by the
of molecular oxygen in the final analysis and cannot be easily
N2(corr) /H2 indicator for the same feature (Fig. 6). Therefore, very
solved at an unsteady fumarole like Pisciarelli, which is charac-
short living pressure pulses within the hydrothermal system may
terized by thermal and baric fluctuations within the subsoil where
be further recognized which represent fluctuations of even higher
the sampling probe is inserted. However, we can apply a simple
order with respect to variations described in the above paragraph. It
correction to analytical data (N2 /O2 ratio in Fig. 6), by recomput-
is evident that only the QMS methodology could detect such subtle
ing normalized concentrations after having recalculated N2,corr as
fluctuations, due to its high sampling frequency, which allow us to
N2 -N2,atmospheric = N2 -3.71·O2 , being 3.71 the value of atmospheric
listen to the “breath” of the hydrothermal system and improve our
N2 /O2 ratio, and attributing all the detected oxygen content to the
monitoring and forecasting capabilities.
atmospheric contamination. The returned N2,corr values are, how-
ever, positive only for samples collected in year 2009, suggesting
4.3. CO2 /Stot in the western Mediterranean region
that, in 2012 campaign, a different kind of sample contamination
occurred. In Fig. 6, N2 /O2 values plot at a value slightly above 2.
At the Pisciarelli site we obtained a mean, QMS-based CO2 /H2 S
This strongly suggests that minor contents of magmatic N2 mixes
(corresponding to CO2 /St for this emission, with St = SO2 + H2 S)
with abundant nitrous oxide (N2 O), whose presence is likely due
plume ratio of ∼380–445 (molar) from the analysis of the main
to seasonal use of fertilizers in the surrounding farming areas
jet-water degassing vent carried out in 2009 and 2012. Our results
located on the crater rim. In fact, the 2012 campaign was carried
(Fig. 7) are consistent with literature data based on direct fumarole
out during spring-summer time, so the presence of N2 O due to
sampling (CO2 /St ratio average of 286, [49]) and on MultiGAS sur-
agricultural drainage water following field fertilization might be
veys (CO2 /St ratio ranged 210–410, [11]). The latter is, at present,
expected. Moreover, at Pisciarelli, N2 O can easily form by combi-
one of the most widely used techniques to detect in situ the chem-
nation of ammonium (NH4 + ), naturally abundant in the fumarolic
ical composition of plumes and fumaroles from volcanoes in the
field, with the nitrates (NO3 − ) present in surface waters due to fer-
world.
tilization. Therefore, for 2012 data we apply a correction such that
Fig. 7 compares the characteristic CO2 /St ratios of Pisciarelli
N2,corr = N2 -N2,N2O = N2 -2·O2 (see Electronic Annex).
fumaroles from this study, against the chemical signature of vol-
On this basis it was possible to plot the N2,corr /H2 chronogram
canic/hydrothermal fluids from a number of volcanoes in the
(Fig. 6), which shows decreasing values (from 3.9 to 6.1) in 2009,
Western Mediterranean region, covering a temperature range from
dropping to ∼0.1 in 2012. We ascribe the drop of values observed in
<100 ◦ C to >1000 ◦ C (i.e. 1/T ranging from 0.0007 and 0.003 K−1 ,
2012 to the same oxidation event already discussed in the previous
Fig. 7). In detail, the CO2 /St ratio detected by QMS at Piscia-
paragraph, and likely related to nitrates.
relli (383–445) is close to that quoted by Ferreira and Oskarsson
An interesting, short-living feature, appears around 26–29
[63] and Pedone et al. [64] at the hydrothermal system of Furnas
March 2009 (solid grey line in Fig. 6), represented by positive peaks
Lake (Azores) and by Chiodini et al. [65] for Vesuvius fumaroles
on the H2 S/H2 , CH4 /CO2 and N2,corr /H2 chronograms and by nega-
(CO2 /St = 342).
tive inflections on He/CO2 and CO2 /H2 S chronograms. Considering
In Fig. 7, our QMS-based CO2 /St ratio detected at “Bocca Nuova”
solubilities of gas species in water, because of the positive peaks of
(BN) fumarolic vent, at the nearby Solfatara crater (Fig. 1), in 2016
H2 S/H2 and the negative CO2 /H2 S one, the nature of such a feature
(average of 247) is also shown. Our result is comparable with com-
is not related to increased water condensation in the flowline. We
positions found in previous surveys carried out to analyze the gas
then consider the following chemical equilibria:
discharged (1) at the BN vent (CO2 /St ratio of 182, [40]), or (2) from
2H2 S + FeO(r) ⇔ FeS2(py) + H2 + H2 O (1) the total fumarolic field at Solfatara crater (CO2 /St ratio of 130,
range 120–152; [11]), and (3) Ischia island (CO2 /St ratio of 119;
CH4 + 2H2 O ⇔ 4H2 + CO2 (2) [66]) (Fig. 7).
Fig. 7 also shows that, in contrast with the high-temperature
In Eq. (1) FeO(r) is a generic iron oxide component with constant (SO2 dominated) magmatic gas discharges of Etna and Strom-
composition in the volcanic rocks making up the hydrothermal boli active volcanoes in Sicily, both characterized by CO2 /St = 8
52 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54

Fig. 7. Plot of molar CO2 /St ratios volcanic/hydrothermal gases emissions versus the reciprocal of absolute discharge temperatures (in K) in the western Mediterranean
region. For Etna and Stromboli, we used best-guess estimates [11] of magmatic temperatures. Sources: Etna, Stromboli, time-averaged compositions of the summit crater
plumes during 2005–2013, from the permanent MultiGAS network [11]; Vesuvius [65]; Ischia [66]; Vulcano Island [67]; Campi Flegrei (Pisciarelli and Solfatara, [11]); Bocca
Nuova (Solfatara, [40]); Pisciarelli [49]; Furnas Village and Furnas Lake (VG and LK, red coloured symbols, [64], by using MultiGAS); Furnas Village and Furnas Lake (VG and
LK, grey coloured symbols, [63], in situ sampling). Empty circles: QMS-based CO2 /St mean ratios at Pisciarelli of this study. Empty black square: QMS-based CO2 /St mean
ratio at Solfatara (in 2016 campaigns). Campi Flegrei (in particular Pisciarelli fumarolic site) is characterized by a lower S levels (with dominance of H2 S), in contrast with
high temperature magmatic gas discharges of Etna and Stromboli (instead characterized by dominance of SO2 ). At low temperature, the hydrothermal systems’ S levels are
dominated by local scrubbing processes. See text.

(permanent MultiGAS network, [11]), the CO2 /St ratios (with H2 S approximation taken as representative of the enhanced injection
dominance) of “low” temperature (1/T > 0.002 K) manifestations are of magmatic gases.
more scattered, ranging from ∼100 at the Furnas Village fumarolic
site, up to ∼450 at Pisciarelli. It is worth noting that our CO2 /St ratio
5. Perspectives and conclusions
calculated in the 2012 campaign (445), is akin to the value of 410
returned by the MultiGAS [11], thus reflecting a variable extent of
By using a commercial portable QMS-301 our experiments, car-
(1) S scrubbing operated by the hydrothermal system on the mag-
ried out in 2009 and 2012 at Pisciarelli fumarolic site, demonstrate
matic fluids injected at its bottom and (2) on H2 S dissolution by
the usefulness of in situ gas mass spectrometry for the continuous
the hydrothermal system. Furthermore, the results shown in Fig. 7,
monitoring of hydrothermal/fumarolic systems. A major prob-
possibly suggest that, at Pisciarelli, S scrubbing is more emphasized
lem we have faced is steam-to-water condensation, due to the
rather than the Solfatara crater. This is likely due to shallower pro-
large amount of water vapour discharged from the investigated
cesses, even if the Pisciarelli site and the Solfatara fumarolic field
fumarolic field. Water has in fact to be removed completely imme-
are relatively close inside the active Campi Flegrei caldera. In light
diately, right after the vent inlet. In perspective, this can be done
of arguments previously reported we infer that this difference can
by introducing a Peltier cell, in order to kinetically remove pure
be due to the interaction with percolating surface waters at the Pis-
water and prevent the (in any case limited) dissolution of the other
ciarelli site. At parity of source, this effect is of course related to the
components. Typical traps so far adopted cannot prevent such a
lower thermal regime of Pisciarelli with respect to the Solfatara, as
dissolution, and do not guarantee full water removal. Indeed, in
shown by the points within the low-T red box in Fig. 7.
present conditions, further condensation may take place after the
The example of the two main fumarolic fields at Furnas volcano
traps along the flow line to the QMS. This may result in the depar-
(Lake and Village, [63]) is emblematic, because at same discharge
tures displayed by recomputed gas indicators with respect to the
temperature conditions (96–98 ◦ C, or 1/T ∼ 0.0027 K) Furnas Lake
early days of measurements. Regardless of such present limitations,
exhibits lower S contents than Furnas Village (Fig. 7), suggesting
results showed in this work encourage us toward the develop-
that scrubbing is more intense in the former site than in the latter.
ment of a fixed quadrupole mass spectrometer installation, adapted
Similarly to the Pisciarelli case, this can be seen as an effect deter-
for fumarolic measurements and functional to short-medium term
mined by secondary water addition due to the seepage of surface
geochemical monitoring of volcanoes such as CFc. This instrumen-
waters.
tation, of course, is characterized by optimized features for in situ
Finally, the data plotted in Fig. 7 show a power law distribu-
measurements in volcanic environments: resistance to harsh cor-
tion (R2 = 0.80) connecting two end members (an hydrothermal
rosive conditions and high discharge temperatures, low power
one of low temperature and a magmatic one of high tempera-
consumption, small weight, and a reasonable price. These require-
ture), passing through intermediate composition and temperature
ments yield to an informative and practical method to monitor
values that characterize Vulcano (Aeolian archipelago) emissions
volcanic gas emissions continuously, at the same level of other
[67]. In association with the widespread release of deep gases
(few) techniques that make possible the real-time characteriza-
investing the whole area (e.g. [66]), pointing to a common deep
tion of a volcanic system in its evolution. Compared to MultiGAS,
source likely located in the mantle, the magmatic high temperature
whose sensors have to be immersed in the gas plume and thus be
end-member can be considered as representative of the original
most exposed to hostile conditions, QMS analyses need a sampling
signature of magmatic gases injected upward in hydrothermal
line inserted in the ground, very similar to that of discrete sam-
systems. Depending on their thermal condition, such hydrother-
pling. A major advantage of both discrete sampling and MultiGAS
mal systems differentially scrub SO2 and dissolve H2 S. Decreasing
is that they allow also the estimation of water (by weight analyses of
CO2 /St values at investigated hydrothermal systems may be at first
sampled fluids and by using an IR detector, respectively), the major
 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
component of investigated emissions. With QMS, water removal at
the entrance of the pipeline can be estimated, and coupled with
flow measurements of pumped gas may be used to estimate the
relative amount of water, at least on a daily basis. Furthermore, for
all the other analyzed gas species, the QMS allows an internally
consistent analysis on a large number of species, whereas Multi-
GAS return results based on the post-processing of signals from
different sensors, each calibrated on a specific gas species [11,67].
The different trends in geochemical indicators between 2009
and 2012 are partly due to the condensation of water in the
sampling-line as well as the sampling point, and to other secondary
processes, such as air contamination and the vaporization of likely
contaminated surface waters.
Advantage of QMS is certainly the high sampling rate, so that, in
the future, geochemical measurements can be made more com-
parable with the geophysical acquisition. This would represent
an essential step forward in our understanding of the evolution
of the unstable Pisciarelli hydrothermal system. The QMS-based
methodology of continuous and real-time monitoring provides the
requested geochemical information on the short-term gas varia-
tions in safe conditions, allowing us to listen to the “breath” of
all investigable hydrothermal systems of the world, in order to
catch subtle variations and better interpret unrest phenomena on
the short-term. Further gain of information can also be derived by
application of a modified membrane inlet technique [68], particu-
larly with the aim of extending measurements to the volcanogenic
volatile organic compounds (VOCs) [69]. In addition, our technique
can be implemented for downhole measurements in order to pro-
vide direct in situ sampling and analysis of hydrothermal gases at
their reservoir equilibrium conditions. Finally, in Fig. 7, the com-
patibility of QMS measurements with other techniques is shown.
The same figure compares the characteristic CO2 /St ratios of Pis-
ciarelli fumaroles from this study, against the chemical signature
of volcanic/hydrothermal fluids from a number of volcanoes in
the Western Mediterranean region. The results suggest that, at
local and regional scale, QMS measurements allow evaluation of
the compositional changes of the shallow hydrothermal reservoirs
associated with major volcanic systems.
Acknowledgements
The research leading to these results has received funding from
PON-MON.I.C.A. and ITEMS projects. The authors would also like
to thank technical assistance and scientific support from Dr. Mar-
tin Zimmer and Prof. Dr. Joerg Erzinger (from Helmholtz-Zentrum,
Potsdam, Germany), who were essential in setting up the QMS-
based field acquisitions. The authors wish to express their gratitude
to the Editor Prof. P.E. Barran and two anonymous reviewers for
their revision of the manuscript and providing constructive com-
ments and suggestions.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ijms.2017.02.006.
References
[1] W.F. Giggenbach, P.N. Garcia, C.A. Londono, V.L.A. Rodriguez, G.N. Rojas,
V.M.L. Calvache, The chemistry of fumarolic vapor and thermal-spring
discharges from the Nevado del Ruiz volcanic magmatic-hydrothermal
system, Colombia, J. Volcanol. Geotherm. Res. 42 (1990) 13–39.
[2] D. Rouwet, S. Inguaggiato, Y. Taran, N. Varley, S.J.A. Santiago, Chemical and
isotopic compositions of thermal springs, fumaroles and bubbling gases at
Tacana Volcano (Mexico–Guatemala): implications for volcanic surveillance,
Bull. Volcanol. 71 (2009) 319–335.
[3] F. Tassi, F. Aguilera, O. Vaselli, E. Medina, D. Tedesco, A. Delgado Huertas, R.
Poreda, S. Kojima, The magmatic- and hydrothermal dominated fumarolic
53
system at the active crater of Lascar volcano, northern Chile, Bull. Volcanol. 71
(2009) 71–183.
[4] G. Chiodini, S. Caliro, A. Aiuppa, R. Avino, D. Granier, R. Moretti, F. Parello, First
13
C/12 C isotopic characterisation of volcanic plume CO2 , Bull. Volcanol. 73
(2011) 531–542.
[5] M. Pedone, A. Aiuppa, G. Giudice, F. Grassa, C. Cardellini, G. Chiodini, M.
Valenza, Volcanic CO2 flux measurement at Campi Flegrei by tunable diode
laser absorption spectroscopy, Bull. Volcanol. 76 (2014) 1–13, http://dx.doi.
org/10.1007/s00445-014-0812-z.
[6] G. Pecoraino, S. Giammanco, Geochemical characterization and temporal
changes in parietal gas emissions at Mt. Etna (Italy) during the period July
2000–July 2003, Terr. Atmos. Ocean. Sci. 16 (2005) 805–841.
[7] P. Weinstein, C.J. Horwell, A. Cook, Volcanic Emissions and Health, in:
Essentials of Medical Geology, 2012, pp. 217–238.
[8] A. Aiuppa, L. Fiorani, S. Santoro, S. Parracino, M. Nuvoli, G. Chiodini, C.
Minopoli, G. Tamburello, New ground-based lidar enables volcanic CO2 flux
measurements, Sci. Rep. (2015).
[9] M.R. Burton, G.M. Sawyer, D. Granieri, Deep carbon emissions from volcanoes,
Rev. Miner. Geochem. 75 (2013) 323–354.
[10] A. Aiuppa, R. Moretti, C. Federico, G. Giudice, S. Gurrieri, M. Liuzzo, P. Papale,
H. Shinohara, M. Valenza, Forecasting Etna eruptions by real-time observation
of volcanic gas, Geology 35 (2007) 1115–1118.
[11] A. Aiuppa, G. Tamburello, R. Di Napoli, C. Cardellini, G. Chiodini, G. Giudice, F.
Grassa, M. Pedone, First observations of the fumarolic gas out-put from a
restless caldera: implications for the current period of unrest (2005–2013) at
Campi Flegrei, Geochem. Geophys. Geosyst. 14 (2013) 4153–4169.
[12] H. Shinohara, A new technique to estimate volcanic gas composition: plume
measurements with a portable multi-sensor system, J. Volcanol. Geotherm.
Res. 143 (2005) 319–333.
[13] A. Aiuppa, H. Shinoara, G. Tamburello, G. Giudice, M. Liuzzo, R. Moretti,
Hydrogen in the gas plume of an open-vent volcano, Mount Etna, Italy, J.
Geophys. Res. Solid Earth 116 (2011) B10204.
[14] N. Takahata, G. Igarashi, Y. Sano, Continuous monitoring of dissolved gas
concentrations in groundwater using a quadrupole mass spectrometer, Appl.
Geochem. 12 (1997) 337–382.
[15] E. Faber, S. Inguaggiato, G. Garzòn-Valencia, D. Seidl, Continuous gas
measurements at volcanic fumaroles, Mitt. Dtsch. Geophysik. Ges. e.V. DGG
Spec. 3 (1998) 83–87.
[16] J.A. Diaz, C.F. Giese, W.R. Gentry, Mass spectrometry for in-situ volcanic gas
monitoring, Trends Anal. Chem. 21 (2002) 498–514.
[17] F. Le Guern, A. Nohl, P. Bicocchi, Field measurements of volcanic gases.
Vulcano Island (Italy), Kilauea. (Hawaii, U.S.A.), Merapi (Java, Indonesia), Bull.
Volcanol. 45 (1982) 229–233, http://dx.doi.org/10.1007/BF02597735.
[18] M. Zimmer, J. Erzinger, Geochemical monitoring on Merapi volcano,
Indonesia, Mitt. Dtsch. Geophysik. Ges. e.V. (1998) 89–92, DGG Special Issue
III/1998, ISSN-Nr. 0947-1944.
[19] M. Zimmer, J. Erzinger, Y. Sulistiyo, Continuous chromatographic gas
measurements on Merapi volcano, Indonesia, Mitt. Dtsch. Geophysik. Ges. e.V.
(2000) 87–91, DGG Special Volume IV/, ISSN-Nr. 0947-1944.
[20] J.P. Toutain, J. Baubron, J. Le Bronec, P. Allard, P. Briole, B. Marty, G. Miele, D.
Tedesco, G. Luongo, Continuous monitoring of distal gas emanations at
Vulcano, southern Italy, Bull. Volcanol. 54 (1992) 147–155.
[21] Y. Shimoike, K. Notsu, Continuous chemical monitoring of volcanic gases in
Izu-Oshima volcano, Japan, J. Volcanol. Geotherm. Res. 101 (2000) 211–221.
[22] A. Fedele, M. Pedone, R. Moretti, R. Somma, T. Wiersberg, C. Troise, G. De
Natale, Continuous gas sampling and analysis at the Pisciarelli fumarolic field
(Campi Flegrei) by using a quadrupole mass spectrometer (QMS), Tech. Rep.
Issue 344 (2016), ISSN 2039-7941.
[23] P. Marianelli, A. Sbrana, M. Proto, Magma chamber of the Campi Flegrei
supervolcano at the time of eruption of the Campanian Ignimbrite, Geology
34 (2006) 937–940.
[24] B. De Vivo, G. Rolandi, P.B. Gans, A. Calvert, W.A. Bohrson, F.J. Spera, H.E.
Belkin, New constraints on the pyroclastic eruptive history of the Campanian
volcanic Plain (Italy), Mineral. Petrol. 73 (2001) 47–65, http://dx.doi.org/10.
1007/s007100170010.
[25] L. Fedele, D.D. Insinga, A.T. Calvert, V. Morra, A. Perrotta, C. Scarpati, 40 Ar/39 Ar
dating of tuff vents in the Campi Flegrei caldera (southern Italy): toward a
new chronostratigraphic reconstruction of the Holocene volcanic activity,
Bull. Volcanol. 73 (2011) 1323–1336, http://dx.doi.org/10.1007/s00445-011-
0478-8.
[26] A.L. Deino, G. Orsi, S. de Vita, M. Piochi, The age of the Neapolitan Yellow Tuff
caldera-forming eruption (Campi Flegrei caldera–Italy) assessed by 40 Ar/39 Ar
dating method, J. Volcanol Geoth. Res. 133 (2004) 157–170.
[27] J.J. Dvorak, G. Mastrolorenzo, The mechanisms of recent vertical crustal
movements in Campi Flegrei Caldera, southern Italy, Spec. Pap. Geol. Soc. Am.
263 (1991) 47.
[28] M. Rosi, A. Sbrana, C. Principe, The Phlegrean fields: structural evolution,
volcanic history and eruptive mechanisms, J. Volcanol. Geotherm. Res. 17
(1983) 273–288.
[29] M.A. Di Vito, R. Isaia, G. Orsi, J. Southon, S. de Vita, M. D’Antonio, L.
Pappalardo, M. Piochi, Volcanism and deformation since 12,000 years at the
Campi Flegrei caldera (Italy), J. Volcanol. Geotherm. Res. 91 (1999) 221–246.
[30] G. Orsi, M.A. Di Vito, R. Isaia, Volcanic hazard assessment at the restless Campi
Flegrei caldera, Bull. Volcanol. 66 (2004) 514–530.
54 A. Fedele et al. / International Journal of Mass Spectrometry 415 (2017) 44–54
[31] C. Morhange, J. Marriner, T. Laborel, T. Micol, C. Oberlin, Rapid sea-level
movements and noneruptive crustal deformations in the Phlegrean Fields
caldera, Italy, Geology 43 (2006) 93–96.
[32] C. Del Gaudio, I. Aquino, G.P. Ricciardi, C. Ricco, R. Scandone, Unrest episodes
at Campi Flegrei: a reconstruction of vertical ground movements during
1905–2009, J. Volcanol. Geotherm. Res. 195 (2010) 48–56, http://dx.doi.org/
10.1016/j.jvolgeores.2010.05.014.
[33] C. Troise, G. De Natale, F. Pingue, F. Obrizzo, P. De Martino, U. Tammaro, E.
Boschi, Renewed ground uplift at Campi Flegrei caldera (Italy): new insight on
magmatic processes and forecast, Geophys. Res. Lett. (2007) 34.
[34] L. D’Auria, S. Pepe, R. Castaldo, F. Giudicepietro, G. Macedonio, P. Ricciolino, P.
Tizzani, F. Casu, R. Lanari, M. Manzo, M. Martini, E. Sansosti, I. Zinno, Magma
injection beneath the urban area of Naples: a new mechanism for the
2012-2013 volcanic unrest at Campi Flegrei caldera, Sci. Rep. 5 (2015) 13100,
http://dx.doi.org/10.1038/srep13100.
[35] INGV-Osservatorio, Vesuviano’s bulletins, 2017, Retrieved from http://www.
ov.ingv.it/ov/it/bollettini/275.html, Campi Flegrei.
[36] G. Chiodini, S. Caliro, P. De Martino, R. Avino, F. Ghepardi, Early signals of new
volcanic unrest at Campi Flegrei caldera? Insights from geochemical data and
physical simulations, Geology 40 (2012) 943–946.
[37] R. Moretti, I. Arienzo, L. Civetta, G. Orsi, P. Papale, Multiple magma degassing
sources at an explosive volcano, Earth Planet. Sci. Lett. 367 (2013) 95–104.
[38] R. Moretti, G. De Natale, C. Troise, A geochemical and geophysical reappraisal
to the significance of the recent unrest at Campi Flegrei caldera (Southern
Italy), Geochem. Geophys. Geosyst. (2016) (submitted for publication).
[39] S. Caliro, G. Chiodini, R. Moretti, R. Avino, D. Granieri, M. Russo, J. Fiebig, The
origin of the fumaroles of La Solfatara (Campi Flegrei, South Italy), Geochim.
Cosmochim. Acta 71 (2007) 3040–3055.
[40] G. Chiodini, J. Vandemeulebrouck, S. Caliro, L. D’Auria, P. De Martino, A.
Mangiacapra, Z. Petrillo, Evidence of thermal-driven processes triggering the
2005–2014 unrest at Campi Flegrei caldera, Earth Planet. Sci. Lett. 414 (2015)
58–67.
[41] G. Chiodini, F. Frondini, C. Cardellini, D. Granieri, L. Marini, G. Ventura, CO2
degassing and energy release at Solfatara Volcano, Campi Flegrei, Italy, J.
Geophys. Res. 106 (2001) 16213–16221.
[42] M. Todesco, G. Chiodini, G. Macedonio, Monitoring and modelling
hydrothermal fluid emission at La Solfatara (Phlegrean Fields, Italy); an
interdisciplinary approach to the study of diffuse degassing, J. Volcanol.
Geotherm. Res. 125 (2003) 57–79.
[43] G. Chiodini, M. Todesco, S. Caliro, C. Del Gaudio, G. Macedonio, M. Russo,
Magma degassing as a trigger of bradyseismic events: the case of Phlegrean
Fields (Italy), Geophys. Res. Lett. 30 (2003) 1434.
[44] R. Bodnar, C. Cannatelli, B. De Vivo, A. Lima, H.E. Belkin, A. Milia, Quantitative
model for magma degassing and ground deformation (bradyseism) at Campi
Flegrei, Italy: implications for future eruptions, Geology 35 (2007) 791–794,
http://dx.doi.org/10.1130/G23653A.1.
[45] G. Chiodini, S. Caliro, C. Cardellini, D. Granieri, R. Avino, A. Baldini, M. Donnini,
C. Minopoli, Long-term variations of the Campi Flegrei, Italy, volcanic system
as revealed by the monitoring of hydrothermal activity, J. Geophys. Res. 115
(2010) B03205.
[46] M. Pistolesi, R. Isaia, P. Marianelli, A. Bertagnini, C. Fourmentraux, P.G. Albert,
E.L. Tomlinson, M.A. Menzies, M. Rosi, A. Sbrana, Simultaneous eruptions
from multiple vents at Campi Flegrei (Italy) highlight new eruption processes
at calderas, Geology 44 (2016) 487–490.
[47] G. Chiodini, CO2 /CH4 ratio in fumaroles a powerful tool to detect magma
degassing episodes at quiescent volcanoes, Geophys. Res. Lett. 36 (2009)
L02302.
[48] L. D’Auria, F. Giudicepietro, I. Aquino, G. Borriello, C. Del Gaudio, D. Lo Bascio,
M. Martini, G.P. Ricciardi, P. Ricciolino, C. Ricco, Repeated fluid-transfer
episodes as a mechanism for the recent dynamics of Campi Flegrei Caldera
(1989–2010), J. Geophys. Res. 116 (2011) B04313.
[49] G. Chiodini, R. Avino, S. Caliro, C. Minopoli, Temperature and pressure gas
geoindicators at the Solfatara fumaroles (Campi Flegrei), Ann. Geophys. 54
(2011).
[50] W.F. Giggenbach, R.L. Goguel, Collection and Analysis of Geothermal and
Volcanic Water and Gas Discharges. Report No. CD 2401, Department of
Scientific and Industrial Research. Chemistry Division, Petone, New Zealand,
2017.
[51] A. Troiano, M.G. Di Giuseppe, D. Patella, C. Troise, G. De Natale,
Electromagnetic outline of the Solfatara–Pisciarelli hydrothermal system,
Campi Flegrei (Southern Italy), J. Volcanol. Geotherm. Res. 277 (2014) 9–21.
[52] G. Chiodini, P. Allard, S. Caliro, F. Parello, 18 O exchange between steam and
carbon dioxide in volcanic and hydrothermal gases: implications for the
source of water, Geochim. Cosmochim. Acta 64 (2000) 2479–2488.
[53] C. Oppenheimer, Ultraviolet sensing of volcanic sulfur emissions, Elements 6
(2010) 87–92.
[54] J. Fiebig, F. Tassi, W. D’Alessandro, O. Vaselli, A.B. Woodland, Carbon-bearing
gas geothermometers for volcanic-hydrothermal systems, Chem. Geol. 351
(2013) 66–75.
[55] W. Givens, Computation of plain unitary rotations transforming a general
matrix to triangular form, J. Soc. Ind. Appl. Math. 6 (1958) 26–50, http://dx.
doi.org/10.1137/0106004.
[56] T. Wiersberg, J. Erzinger, On the origin and spatial distribution of gas at
seismogenic depths of the San Andreas Fault from drill-mud gas analysis,
Appl. Geochem. 23 (1998) 1675–1690, http://dx.doi.org/10.1016/j.
apgeochem.2008.01.012.
[57] S. Süer, T. Wiersberg, N. Güleç, J. Erzinger, M. Parlaktuna, Real-time gas
monitoring experiment in a tectonically active region: Tekke Hamam
Geothermal Field, Western Anatolia, Turkey, Geochem. J. (2016) (submitted
for publication).
[58] W.F. Giggenbach, Geothermal gas equilibria, Geochim. Cosmochim. Acta 44
(1980) 2021–2032.
[59] G. Saito, H. Shinohara, K. Kazahaya, Successive sampling of fumarolic gases at
Satsuma-Iwojima and Kuju volcanoes, southwest Japan: Evaluation of
short-term variations and precision of the gas sampling and analytical
techniques, Geochem. J. 36 (2002) 1–20.
[60] A. Aiuppa, C. Federico, G. Giudice, G. Giuffrida, R. Guida, S. Gurrieri, M. Liuzzo,
R. Moretti, P. Papale, The 2007 eruption of Stromboli volcano: insights from
real-time measurement of the volcanic gas plume CO2 /SO2 ratio, J. Volcanol.
Geotherm. Res. 182 (2009) 221–230.
[61] S. Caliro, G. Chiodini, A. Paonita, Geochemical evidences of magma dynamics
at Campi Flegrei (Italy), Geochim. Cosmochim. Acta 132 (2014) 1–15.
[62] W.F. Giggenbach, Chemical composition of volcanic gases, in: R. Scarpa, R.I.
Tilling (Eds.), Monitoring and Mitigation of Volcano Hazards, 1996, pp.
221–256, http://dx.doi.org/10.1007/978-3-642-80087-0.
[63] T. Ferreira, N. Oskarsson, Chemistry and isotopic composition of fumarole
discharges of Furnas caldera, J. Volcanol. Geotherm. Res. 92 (1999) 169–179.
[64] M. Pedone, F. Viveiros, A. Aiuppa, G. Giudice, F. Grassa, A.L. Gagliano, V.
Francofonte, T. Ferreira, Total (fumarolic + diffuse soil) CO2 output from
Furnas volcano, Earth Planets Space 67 (2015) 174, http://dx.doi.org/10.1186/
s40623-015-0345-5.
[65] G. Chiodini, L. Marini, M. Russo, Geochemical evidence for the existence of
high-temperature hydrothermal brines at Vesuvio Volcano, Italy, Geochim.
Cosmochim. Acta 65 (2001) 2129–2147.
[66] G. Chiodini, R. Avino, T. Brombach, S. Caliro, C. Cardellini, S. de Vita, F.
Frondini, D. Granieri, E. Marotta, G. Ventura, Fumarolic and diffuse soil
degassing west of Mount Epomeo, Ischia, Italy, J. Volcanol. Geotherm. Res. 133
(2004) 291–309, http://dx.doi.org/10.1016/j.jvolgeores.2003.02.00.
[67] A. Aiuppa, S. Inguaggiato, A.J.S. McGonigle, M. O’Dwyer, C. Oppenheimer, M.J.
Padgett, D. Rouwet, M. Valenza, H2 S fluxes from Mt. Etna, Stromboli and
Vulcano (Italy) and implications for the global volcanic sulfur budget,
Geochim. Cosmochim. Acta 69 (2005) 1861–1871, http://dx.doi.org/10.1016/j.
gca.2004.09.018.
[68] S. Giannoukos, B. Brkic, S. Taylor, N. France, Membrane inlet mass
spectrometry for homeland security and forensic applications, J. Am. Soc.
Mass Spectrom. 26 (2015) 231–239.
[69] F. Tassi, S. Venturi, J. Cabassi, F. Cappecchiacci, B. Nisi, O. Vaselli, Volatile
organic compounds (VOCs) in soil gases from Solfatara crater (Campi Flegrei,
southern Italy): geogenic source(s) vs. biogeochemical processes, Appl.
Geochem. 56 (2015) 37–49.