Carbon dioxide in the urban area of Naples: Contribution and effects of

the volcanic source
Domenico Granieri
a,
⁎, Antonio Costa
b
, Giovanni Macedonio
c
, Marina Bisson
a
, Giovanni Chiodini
c
a
Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Pisa, Via della Faggiola 32, 56126 Pisa, Italy
b
Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Bologna, via Donato Creti 12, 40128 Bologna, Italy
c
Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Napoli, via Diocleziano 328, 80124 Napoli, Italy
a b s t r a c t a r t i c l e i n f o
Article history:
Received 8 January 2013
Accepted 6 May 2013
Available online 26 May 2013
Keywords:
CO
2
dispersion
Solfatara
Gas hazard
Campi Flegrei
Naples is a large city located betweentwo active volcanic areas: Campi Flegrei to the Wand Vesuvius to the SE. The
Solfatara crater, inside the caldera of the Campi Flegrei and nearest to the western quarters of the city, is a prodi-
gious source of natural CO
2
with a mean emission rate of 1067 ton/d, i.e. seven times higher than that of Vesuvius
(151 ton/d).
This study shows that the area around the Solfatara and part of the urban area of Naples are affected by the
volcanic plume when atmospheric circulatory patterns are dominated by the locally frequent sea breezes.
Under these conditions the CO
2
content in the air increases above normal values, reaching more than
1000 ppm in proximity to the Solfatara crater to a few tens of ppm several kilometres from the source. Al-
though these values do not indicate a health risk even under the most unfavourable atmospheric conditions,
the volcanic source contributes to the total CO
2
burden from all urban emissions and hence to overall air
quality. An emission rate ten times higher than the present one would lead to an air CO
2
concentration in ex-
cess of recommended health protection thresholds.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
Human activity is concentrated in urban areas, where the massive
use of fossil fuels, mainly for domestic heating and transport, produces
a significant amount of anthropogenic carbon dioxide. The buildup of
CO
2
over an urban area has been called an “urban CO
2
dome” by Idso
et al. (1998), by analogy with the more well-known “urban heat island”
(Goward, 1981; Oke, 1982). Several studies have documented its
presence in the urban environment of large-sized cities such as London,
UK (Derwent et al., 1995), Vancouver, Canada (Reid and Steyn, 1997),
Phoenix, USA (Idso et al., 1998), Karachi, Pakistan (Ghauri et al., 1994)
and Nottingham, UK (Berry and Colls, 1990). None of these studies
were undertaken in cities located near active volcanoes, where the natu-
ral source can increase urban CO
2
levels. In this study we describe the
dispersion of CO
2
discharged from the Solfatara volcanic area near the
city of Naples. Naples is the most densely-populated city in Italy and
one of the most densely-populated metropolitan areas in Europe, with
a density of 8566 inh/km
2
downtown and 2612 inh/km
2
in the suburbs
(ISTAT, 2001). The urban area lies between two volcanoes: its western
quarters are located inside the Campi Flegrei (CF) caldera, whereas the
southeastern side of the city extends up to the slopes of Vesuvius. The
city centre is surrounded by fairly high hills on three sides such that
the dominant sea breeze from the SW is channelled over the urban
area. A large part of the city lies downwind of the CF volcanic area. The
most active volcanic site in the CF is the Solfatara crater; within just a
few hundred square metres the crater hosts two high-temperature fu-
maroles (140–160 °C), a few low-temperature fumaroles (95.0–
97.5 °C) and one large degassing mud pool. The bottom of the crater
andthe external easternslope of the cone are affectedby widespreaddif-
fuse CO
2
degassing. Carbon dioxide has a molecular weight greater than
that of air (44 g/mol vs 29 g/mol of air) and therefore tends to accumu-
late in low-lying areas, forming potentially lethal invisible traps
(Carapezza et al., 2003; Costa et al., 2008; Chiodini et al., 2010a). This is
not the case of the Solfatara because the discharged gas is warmer than
the surrounding air, so that the greater molecular weight of CO
2
is com-
pensated by the decrease in density due to its higher temperature (Costa
et al., 2005). Under such conditions the CO
2
plume is dispersed mainly
under the effect of wind and atmospheric turbulence (so-called passive
dispersion) and, depending on the wind direction, it can move towards
the densely populated quarters of the city or its suburbs.
Toinvestigate the dispersionof the CO
2
cloud we applied the DISGAS
code (an improved version of the model presented in Costa et al., 2005,
see the Appendix), coupled with a mass-consistent wind model
(Douglas and Kessler, 1990). Simulations were performed for the
most significant local-scale wind and hydrodynamic conditions of the
atmosphere derived from the analysis of micrometeorological observa-
tions. Results agree satisfactorily with field data collected in the Solfata-
ra area by two automated stations that continuously measure the CO
2
content in air. In the following we discuss the spatial and temporal
Journal of Volcanology and Geothermal Research 260 (2013) 52–61
⁎ Corresponding author. Tel.: +39 0508311958; fax: +39 0508311942.
E-mail address: granieri@pi.ingv.it (D. Granieri).
0377-0273/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jvolgeores.2013.05.003
Contents lists available at SciVerse ScienceDirect
Journal of Volcanology and Geothermal Research
j our nal homepage: www. el sevi er . com/ l ocat e/ j vol geor es
evolutionof the gas plume for the meanand maximumCO
2
output rates
measuredinthe current quiescent periodof the volcano. Lastly, we used
the model to define the potential hazard to human health by increasing
the flow rate to ten times the current one.
2. Carbon dioxide source
An impressive amount of CO
2
is released continuously at the
Solfatara crater through diffusion from the soil (Chiodini et al.,
2001, 2010b). From 1998 to 2008 twelve extensive field surveys
were performed in order to monitor CO
2
emission rates. Each survey
covers roughly the same area of ~1 km
2
centred over the Solfatara
crater and includes about 400 carbon dioxide soil diffusion measure-
ments (Chiodini et al., 2010b). The average CO
2
emission (ACE) of all
the surveys is 1067 ton/d (Fig. 1) and the maximum CO
2
emission
(MCE) is ~1800 ton/d (Chiodini et al., 2010b). For comparison, note
that the average discharge of CO
2
through diffuse degassing at Vesuvius
is seven times smaller than that at the Solfatara crater (i.e., 151 ton/d
(Frondini et al., 2004) vs 1067 ton/d).
3. Micrometeorological measurements and experiment design
at Solfatara
The surface boundary layer (SBL), the lowest layer of the tropo-
sphere, is almost always turbulent and is influenced by surface friction
due to vegetation and topography (Stull, 1988). Within the SBL, atmo-
spheric trace gases are rapidly diffused to (or from) the surface by irreg-
ular or random motions generated by wind shear and buoyancy forces
(Baldocchi et al., 1988; Stull, 1988). Micrometeorology is based on the
high-frequency acquisition of these turbulent fluctuations generated
by small short-lived eddies. The high-frequency acquisition of data
over a time frame provides a means for splitting variables such as
wind into a mean part and a turbulent part. For example, the turbulent
component of wind in the longitudinal direction (u′) is:
u

¼ u−u

ð1Þ
where u is the instantaneous value of wind along the x axis and ū is the
mean longitudinal velocity over the period of time chosen to average
the raw measurements. We can likewise divide the latitudinal (v) and
vertical (w) components of wind into their mean and turbulent parts:
v

¼ v−v

ð2Þ
w

¼ w−w

ð3Þ
where the overbar indicates the mean and (′) a deviation from the
mean of the instantaneous measurement. High-frequency acquisition
allows us to resolve small-scale wind features and hydrodynamic con-
ditions at the surface such as friction velocity (u
*
) and Monin–Obukhov
length (L). Friction velocity, an index of the “drag” which the Earth's
surface exerts on atmospheric flows, is defined as follows:
u
Ã
2
¼ u

w

ð Þ
2
þ v

w

ð Þ
2
: ð4Þ
The magnitude of u
*
is a function of the roughness and slope of the
site, as well as the wind speed.
The Monin–Obukhov length relates the turbulent energy generated
by the mechanical mixing of gas in the atmosphere with the buoyancy-
induced turbulent energy:
L ¼ −T
v
u
Ã
3
=kg F
b0
ð5Þ
where k is the dimensionless von Karman constant, T
v
is the virtual po-
tential air temperature and F
b0
is the virtual potential temperature flux
at the surface due to air density differences determined by temperature
and humidity fluctuations. L is zero for neutral stratifications (L values
of around zero typically occur during day–night transitions, under over-
cast skies or with strong winds), negative for unstable stratifications
(small negative values indicate a highly unstable atmosphere, large
negative ones a slightly unstable atmosphere) and is positive for stable
stratifications.
Our micrometeorological measurements were performed inside the
Solfatara crater using a 3.3 m high tower (Fig. 2) equipped with a
three-axis sonic anemometer (Campbell Scientific, Model CSAT3-3D),
one barometer (Campbell Scientific, Model CS106) and one fine-wire
thermocouple (Campbell Scientific, Model FW05). An ancillary
open-path gas analyser was used to derive H
2
O and CO
2
fluxes (Licor,
Model LI-7500).
The micrometeorological survey lasted 2 years, from June 2004 to
June 2006, and valid data were collected approximately every three
days (207 days over a two-year period). The three components of
wind speed, atmospheric pressure and air temperature were sampled
at a 10-Hz rate and averaged over 10-min intervals. We calculated
more than 12,700 10-min averages, corresponding to about 76 million
observational readings.
The micrometeorological survey allowed us to resolve in great de-
tail the dominant wind conditions and hydrodynamic features of the
atmospheric surface layer at the Solfatara crater. Acquired data re-
vealed the following features: 1) onshore breezes (westerly and
southwesterly) are present more than 50% of the year, mainly during
spring and summer (Fig. 3); 2) typical spring/summer meteorological
Fig. 1. Soil CO
2
flux measured in the Solfatara area during 12 extensive field surveys in the 1998–2008 period (Chiodini et al., 2010b). Vertical bars represent the variation in each
survey value (95% confidence interval). The horizontal dashed line is the average CO
2
emission (ACE, 1067 ton/d) of all the surveys, whose variation is represented by the grey area
(790–1600 ton/d, 95% confidence interval). MCE is the maximum CO
2
emission rate (MCE, 1800 ton/d in the range 1260–2900 ton/d) measured in the ten-year period. Vertical
dashed lines indicate the days used in the procedure of the code validation (see Section 4.1).
53 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
conditions are characterised by a weak synoptic circulation (mainly
in summertime due to the presence of the Azores anticyclone over
Europe) and a well developed breeze regime controlled by the daily
thermally-induced sea–land air circulation; 3) diurnal breeze cycles
are characterised by very weak air circulation during the night (land
breeze) and an increase in wind intensity in the day (sea breeze). In
summer/spring, the sea breeze cycle starts at around 9:00–10:00
Local Time, LT (about 3–4 h after sunrise) and ends in the evening
at about 21:00 LT, with the maximum intensity during the warmer
hours of the day (about 3–3.5 m/s at 15:00 LT, Fig. 4a). Diurnal sea
breezes initially blow from ~270° (W) and then veer to ~190° (SSW)
in broad daylight (Fig. 4b). Wind measurements suggest that air circu-
lation is quite weak at night (mean speed of 0.45 m/s, Fig. 4a), so that
the expected land breeze (winds from the NE and NNE) is often
overpowered by the synoptic SW wind; 4) in summer/spring, the
values of the Monin–Obukhov length (L) at Solfatara reveal that atmo-
spheric conditions range from highly unstable (small negative L from
9:00 to 18:00 LT) to weakly unstable (from 19:00 to 22:00 LT),
Fig. 2. Micrometeorological station at Solfatara. The tower is 3.3 mhigh. Inset: red dot indicates the location of the micrometeorological station inside the crater facing the mud pool
(Fangaia). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 3. Wind rose plot for the Solfatara crater (data refer to 207 days ina two-year period).
The scale of the axes is from 0 to 15% (frequency).
54 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
indicating that during the daytime the turbulence induced by buoyancy
exceeds mechanical mixing (Fig. 5). During nighttime the atmosphere
is stable (positive L from 23:00 to 8:00), implying low turbulence
effects.
4. The numerical model: validation and applications
The numerical simulations presented in this study were performed
using the DISGAS code (Costa et al., 2005), an Eulerian model based
on advection–diffusion equations, coupled with the mass-consistent di-
agnostic wind model (DWM, Douglas and Kessler, 1990), which can de-
scribe wind fields over complex terrains such as those surrounding
Solfatara. The DWM generates wind components (U, V, W) in a
terrain-following coordinate system. The model needs topographic
data, average wind on the computational domain, atmospheric stability
information within the scale of the domain (i.e. the temperature gradi-
ent dT/dz), and, when available, local surface and upper-air wind mea-
surements. In a first step the domain-mean wind is adjusted for the
kinematic effects of terrain (lifting and acceleration of the airflow over
terrain obstacles), thermodynamically generated slope flows, and
blocking effects. In a second step, wind observations, when available,
are added to the first step field, and an objective analysis scheme is
used to produce a new gridded field (U, V, W). The scheme is designed
so that the observations are used to define the wind field within a
user-specified radius of influence while the first step (U, V, W) field is
used in sub-regions in which observations are unavailable. Finally, a
divergence-minimization procedure is iteratively applied until velocity
divergence is smaller thanan arbitrarily user defined small number. The
final product of DWM is an approximately null-divergence wind field
consistent with the observations. Dispersion is assumed to be governed
by the wind and atmospheric turbulence, since the passive plume con-
dition (Mohan et al., 1995):
Δρ ¼
M
CO
2
M
air
−1
_ _
à C ≈
44
29
−1
_ _
à C ¼
15
29
à C b 0:001 kg m
−3
ð1Þ
is legitimate for diluted and warm gases (up to 162 °C) of Solfatara at
few centimetres above the ground level (Δρ is the density contrast be-
tween gas plume and air, M
CO
2
and M
air
are the molecular weights of
CO
2
and air and C is the CO
2
concentration, expressed in kgm
−3
).
DISGAS inputs include topography, roughness length, meteorological
data (wind velocity and direction, air temperature), atmospheric stabil-
ity information(Monin–Obukhov length, frictionvelocity), and gas flow
rates from the source. The model yields CO
2
concentrations expressed
as values in excess of background CO
2
levels in the air at heights select-
ed by the user. For all simulations, the computational domain extended
over an area of 27 × 27 km
2
that was discretised using a square grid
with180 × 180 cells inthe x and y directions. Vertical grid steps ranged
fromΔz = 10 m in the uppermost level (100 m) to Δz = 0.5 m in the
lowermost ground level so as to better detect near-surface gradients. A
preliminary test demonstratedthe results of the simulations donot vary
substantially when reproducing the wind field over a thicker domain
(e.g., assigning the altitude of 500 mat the topof the domain). The tran-
sition sea–land is associated with the change of the roughness height
from 0.01 m for the sea (relative to the marine surface in coastal
areas) to 0.5 m for land (typical for rolling or moderate relief covered
by shrubs, rare tree and thin buildings).
4.1. Model validation
In order to validate the model, simulated concentrations were
compared with CO
2
concentrations in the air measured directly inside
the Solfatara crater. We chose to simulate the daily cycles (1:00–
24:00 LT) recorded by the micrometeorological station on 29 June
2004 and 24 December 2004, which are considered to be representa-
tive of summertime and wintertime cycles respectively. Meteorolog-
ical data and parameters relative to the hydrodynamic conditions of
the atmosphere employed in the validation of numerical simulations
are reported in Table 1.
The carbon dioxide flow rate was assumed to be the mean be-
tween the ACE (1067 ton/d) and the August 2004 survey value
(684 ton/d) in the summer (Fig. 1) and the March 2005 survey
value (572 ton/d) in the winter. Simulated values were compared
with CO
2
concentrations measured at the station #1 (3.3 m above
soil level) and station #2 (0.5 m a.s.l.), located in two different
areas of the Solfatara crater and with an acquisition periodicity of
1 h and 2 h respectively. There is less correlation between modelled
and observed CO
2
concentrations at the beginning of the series
(Fig. 6), when the day/night transition produces abrupt changes in
wind direction and intensity. In the middle and at the end of the con-
sidered period the two series are remarkably similar, both in order of
magnitude and in the trend over time. As a whole, the correlation co-
efficients (Table 2) suggest that the correlation is higher for station
#1, and lower but significant at the 95% confidence level for station
#2. Correlation is better in the summer, when the wind regime is
dominated by breezes, than in the winter.
Fig. 4. Wind in the Solfatara crater during summer 2004. (a) wind speed; (b) wind direction
with respect to the north. Each dot represents a 10-min interval.
Fig. 5. Variations in the Monin–Obukhov length (L) at Solfatara in summer 2004 (about
2400 10-min intervals); grey areas define the theoretical range of L over a daily cycle in
fair weather conditions over land (Stull, 1988).
55 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
Despite the limitations of using the Eulerian approach to reproduce
dispersion in the proximity of the gas source (Boybeyi and Raman,
1995), the numerical simulations we performed provide a satisfactory
representation of the natural system. Furthermore, the average CO
2
concentration for 28 gas plume samples collected inside the Solfatara
on 7 July 2008 is 1606 (±947) ppm (Chiodini et al., 2011). This value
is similar to the simulated value inside the crater during a typical sum-
mer day (about 1100 ppm) at a height of 0.5 m to 3.3 m.
4.2. Model applications
Having described the evolution of the wind field through the prog-
nostic DWM, we nowreport the results of two scenarios during a typical
spring/summer period accounting for two different CO
2
emission rates.
In the first scenario the carbon dioxide flow rate is assumed to be
1067 ton/d (ACE), i.e. the average of 12 surveys in the 1998–2008 peri-
od (Chiodini et al., 2010b). In terms of mean value and range of varia-
tion, the most representative survey is the October 2005 survey
(Fig. 1). The secondscenario assesses the consequences of a CO
2
feeding
rate equal to the maximumvalue actually measured in the ten-year pe-
riod (MCE ~1800 ton/d inJuly 2000, Fig. 1). Fig. 7 reports the spatial dis-
tribution of the CO
2
source in the Solfatara area for the ACE value
(Fig. 7a) and the MCE value (Fig. 7b). CO
2
flux values (about 400 CO
2
soil flux measurements for each survey) were mapped using the se-
quential Gaussian simulation approach (Cardellini et al., 2003;
Deutsch and Journel, 1998). The resulting maps highlight strong CO
2
degassing in the Solfatara crater and in the neighbouring areas;
degassing is mainly controlled by the NW–SE trending fractures
(Chiodini et al., 2001; Granieri et al., 2010). Meteorological data and pa-
rameters relative to the hydrodynamic conditions of the atmosphere
are reported in Table 1 (summer column). Simulated CO
2
concentrations
were calculated at a height of 1.5 m, this being the typical breathing
height of humans.
5. Results and discussion
The wind field was reproduced using the diagnostic wind model
(Douglas and Kessler, 1990); data from two meteorological stations lo-
cated in different sites of the computational domain were used as
input. The results of the diagnostic wind model indicate that during
the night (Fig 8a) the wind regime in the lower layers is characterised
Table 1
Input data for the numerical simulation.
Hour Wind speed
(m/s)
Wind
direction
a
(°)
u*
b
(m/s)
L
c
(m)
T
d
(°C)
Summer/
winter
Summer/
winter
Summer/
winter
Summer/
winter
Summer/
winter
1 0.36/0.35 213/246 0.06/0.06 −4.36/2.12 18.6/3.8
2 0.36/0.22 215/273 0.04/0.10 9.13/3.93 18.4/3.8
3 0.40/0.25 216/248 0.03/0.11 1.76/10.73 18.3/4.1
4 0.37/0.36 220/234 0.05/0.13 4.12/−3.30 18.1/4.5
5 0.35/0.24 218/150 0.04/0.15 3.78/7.76 17.9/4.2
6 0.27/0.32 189/188 0.05/0.15 −1.88/0.54 17.8/3.9
7 0.27/0.08 179/260 0.05/0.08 7.87/17.89 18.3/4.9
8 0.60/0.11 195/297 0.11/0.11 4.56/−1.94 18.9/5.9
9 1.09/0.53 232/38 0.19/0.15 −11.32/0.41 21.8/7.6
10 1.37/0.58 278/53 0.11/0.11 −1.05/−11.54 25.9/9.4
11 1.83/1.43 273/48 0.18/0.14 −3.68/−8.20 28.2/10.5
12 1.72/0.75 273/46 0.19/0.23 −3.17/−46.15 29.0/11.7
13 1.69/0.64 244/305 0.25/0.21 −7.9/−57.39 28.9/12.2
14 2.42/1.30 228/237 0.26/0.19 −6.91/−47.33 28.7/12.6
15 2.68/0.90 217/214 0.26/0.16 −8.36/−142.62 29.0/12.3
16 1.75/1.13 256/192 0.19/0.20 −4.05/27.80 29.1/11.8
17 1.90/0.78 277/178 0.16/0.12 −1.94/45.13 29.4/11.7
18 2.46/1.09 263/174 0.20/0.19 −3.14/84.64 29.8/11.6
19 2.21/1.18 211/166 0.25/0.14 −20.95/38.74 29.2/11.7
20 1.65/1.16 217/185 0.22/0.19 −18.85/64.89 27.8/11.7
21 0.79/0.93 206/193 0.18/0.28 −36.98/128.05 25.1/11.7
22 1.15/1.03 175/193 0.14/0.27 −191.18/184.48 22.6/11.6
23 0.93/0.70 172/188 0.13/0.27 29.09/149.43 21.3/11.9
24 0.45/0.24 181/52 0.05/0.27 6.43/189.24 20.6/12.2
a
Wind direction is the direction from which the wind blows, reported in degrees
from the north.
b
u
*
is the friction velocity.
c
L is the Monin–Obukhov length.
d
T is the air temperature measured 3.3 m above ground level.
Fig. 6. CO
2
concentrations measured at stations #1 (a–b) and #2 (c–d) compared with DISGAS code simulation values. The stations are equipped with IR non-dispersive gas ana-
lyzers (Licor LI-7500 at station #1 and Dräger Polytron IR-CO
2
at station #2 with 1% and 3% accuracy respectively). The local background CO
2
concentration (380 ppm, Chiodini et
al., 2011) was added to the simulated values.
Table 2
Correlation coefficient (R) between measured and simulated CO
2
concentrations.
Season Station #1
(3.3 m)
a
Station #2
(0.5 m)
a
Summer +0.86 +0.55
Winter +0.68 +0.29
a
The value in brackets is the height at which CO
2
concentrations were measured.
56 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
by a dominant circulation from the W, with weak winds (mean
velocity = 0.27 m/s) that flow around the main morphological obsta-
cles in the domain. During the day, the winds pick up (mean
velocity = 2.33 m/s), shift from the W to the SW and penetrate deep
inland (Fig 8b). These results agree with the considerations of Barone
et al. (2000) on wind circulation patterns over the city of Naples during
summer: “During the early morning a shift in the wind direction (from
westerly to southerly) is observed at the Naples monitoring station,
where the wind direction changes by about 90°; the transition between
the night and day circulation is due to the sea breeze, which develops
in the morning hours and lasts until late afternoon.”
Assuming an ACE rate, the CO
2
dispersion model suggests that car-
bon dioxide reaches higher concentrations during the night, when
winds are weak and the atmosphere is very stable. In this situation
the gas accumulates and CO
2
concentrations at breathing level in the
source area reach up to 1400 ppm(Fig. 9) in excess of local background
values (380 ppm, Chiodini et al., 2011). Values decrease to a fewtens of
ppm 2–3 km from the source. Daytime atmospheric conditions are un-
stable and wind circulation is more intense, so that the gas is rapidly di-
luted in proximity to the source (Solfatara), where maximum values of
300–350 ppm in excess are estimated. The gas plume stretches more
than 3 km from the source in a SW–NE direction (Fig. 9); CO
2
Fig. 7. Maps of the soil CO
2
flux measured in a) October 2005 and b) July 2000. CO
2
degassing from soil is controlled by the first-order NW–SE fractures affecting the Solfatara crater
and the surrounding areas. Pisciarelli is an area of intense fumarolic activity on the external NE flank of the crater.
Fig. 8. Simulated wind fields in the first layer of the computational grid (2 mabove the ground) at a) 3:00 and b) 13:00 LT on 29 June 2004. The reference vector is the wind velocity,
solid (blue) dots indicate the position of the meteorological stations. The background layer is a high-resolution orthophoto from the 2000 Italy flight (Bisson et al., 2007).
57 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
concentrations in the northwesterly quarters of Naples reach up to a
few tens of ppm. The map of CO
2
concentrations averaged over a com-
plete 24-h cycle shows a roughly circular pattern, with maximum
values of about 500 ppm above background levels inside the Solfatara
crater (Fig. 10a). The plume is slightly elongated toward the NE, proba-
bly due to the effect of the SW–NE marine breezes during daytime
hours. This tongue of gas covers the northwestern area of Naples, in
which the ‘residential areas’ of Agnano (10,000 residents) and Bagnoli
(28,600 residents) are found. At the lowest wind speeds and under con-
ditions of atmospheric stability (2:00–7:00, LT), excess concentrations
of CO
2
in air ranging from 200 ppm to 1100 ppm were estimated in
the populated area around Solfatara (Fig. 10b).
Considering the MCE rate measured in the last ten years
(~1800 ton/d in July 2000, Fig. 1), the model predicts that CO
2
concen-
trations at a height of 1.5 mincrease by 100% compared to the previous
case, reaching maximum values of about 1300 ppm in an area near to
the gas source (Fig. 11a) and values of up to 300–400 ppm in the area
NE of the Solfatara crater. In this area the model calculates values rang-
ing from300 ppmto 2400 ppmduring nighttime, when gas accumula-
tion is favoured by stagnant atmospheric conditions (Fig. 11b).
Fig. 9. Typical nighttime (3:00, LT) and daytime (13:00, LT) CO
2
concentrations 1.5 m above the ground. Concentrations are expressed as values in excess of background CO
2
con-
centrations in air. The urban area of Naples, affected by volcanic CO
2
dispersion, has the highest population density in Italy (8566 inh/km
2
in the city vs 189 inh/km
2
in Italy, ISTAT,
2001). The shaded relief with cell size of 10 m is shown in the background (Tarquini et al., 2007).
Fig. 10. Air CO
2
concentration maps assuming an ACE rate (1067 ton/d). a) Map averaged over a complete diurnal cycle (24 h) and b) nocturnal map (2:00–7:00, LT).
58 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
Even considering the maximum CO
2
emission rate measured in
the last ten years and the most unfavourable atmospheric conditions
(i.e. onshore wind and atmospheric stability), results indicate that
there is no serious risk to populations at the present CO
2
emission
rates, since concentrations are below the “hazardous” threshold of
5000 ppm of CO
2
(Table 3). However, it is important to consider
that this threshold refers to a selected population (working-age peo-
ple in good health) exposed to the gas for a limited time period (8 h).
The carbon dioxide originating from the active volcanic area of Solfa-
tara adds to the huge amount of CO
2
produced by anthropogenic activ-
ity in the city, primary by the localised burning of fossil fuels. Naples is a
densely-populated metropolitan area that hosts an industrial area and
one of the most highly trafficked seaports (passengers and containers)
in the Mediterranean (data from Naples Port Authority, http://www.
porto.napoli.it/en/statistiche/stat1.php, accessed Jan. 10, 2012). Follow-
ing official inventories submitted by Italy in conformity with the guide-
lines of the Intergovernmental Panel on Climate Change (IPCC, 2007),
the CO
2
emitted by the metropolitan (city plus province) area of Naples
(Table 4) was approximately constant during the 2000–2005 period
(22,062 ton/d equivalent to 8.05 Mton/y in 2000 and 22,105 ton/d
equivalent to 8.07 Mton/y in 2005).
The emission of anthropogenic CO
2
determines a buildup of CO
2
over the urban environment. Several studies have documented this
phenomenon in some large-sized cities throughout the world where,
depending on human activity cycles as well as trace gas mixing
dynamics in the atmospheric boundary layer, CO
2
concentrations are
persistently greater than background levels in rural and remote sites
(Berry and Colls, 1990; Ghauri et al., 1994; Derwent et al., 1995; Reid
and Steyn, 1997; Idso et al., 1998). The phenomenon has been called
an urban CO
2
dome by Idso et al. (1998), by analogy with the more
well-known urban heat island (Goward, 1981; Oke, 1982). Considering
the scattered disposition of the CO
2
sources (primarily domestic
heating and vehicular traffic), the CO
2
dome generally mantles the
whole city and is responsible for a general moderate increase (from
several ppm to a few tens of ppm) in CO
2
. Although a thorough and
well-documentedsurvey of CO
2
concentrations inair has not been com-
pleted in the urban area of Naples, the “dome” phenomenon can be rea-
sonably assumed to exist considering the high degree of urbanisation
and the intense traffic in the city.
This study focussed on the dispersion of volcanic CO
2
plume emis-
sions at Solfatara. Although they do not constitute a human health haz-
ard at the current emission rate, volcanic CO
2
emissions contribute to
build up the load of carbon dioxide in the urban environment, particu-
larly during the summer months, when high concentrations of primary
pollutants (principally NO
x
) and photochemical smog stagnate near the
ground (Barone et al., 2000). At present, volcanic CO
2
represents on
average 4.8% of the entire production of CO
2
in the metropolitan area
of Naples (about 22,000 ton/d in the 2000–2005 period), with a maxi-
mum contribution of 8.1% in July 2000 and a minimum contribution of
2.6% in March 2005. In the SNAP97 classification this natural emission
falls in the “Source 11”, which includes volcanic activity. Source 11 has
a negative value (namely CO
2
consumption) in all Italian provinces ex-
cept Catania (Sicily), where it has been ascribed to the positive contri-
bution of volcanic CO
2
from Etna (ISPRA, 2007). Official inventories
Fig. 11. Maps of CO
2
concentrations in air assuming the maximum CO
2
emission rate measured in the 1998–2008 period (MCE rate ~1800 ton/d). a) Values averaged over a whole
diurnal cycle (24 h) and b) nighttime values (2:00–7:00, LT).
Table 3
Threshold values for CO
2
concentrations in the air (from Costa et al., 2008, modified).
CO
2
thresholds for human health Principal effect
5000 ppm (0.5%) TWA (time weighted average — 8 h/day for 5 days per week)
a
Slight increase in breathing rate
15,000 ppm (1.5%) (10 min max exposure time in working area)
b
Breathing deeper and more frequent
30,000 ppm (3%) STEL (short term exposure limit — 15 min max time exposure
four times a day)
a
Breathing increases to twice normal rate, weak narcotic effect, headache for
long time exposure
100,000 ppm (10%)
c
Respiratory distress with loss of consciousness in 10–15 min
120,000–150,000 ppm (12–15%)
c,d
Lethal concentration, exposure to levels above this is intolerable
a
National Institute of Occupational Safety and Health (NIOSH), 1997.
b
International Volcanic Health Hazard Network (IVHHN), 2005.
c
Le Guern et al. (1982).
d
Baxter et al. (1999).
59 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
submitted by Italy in the years 2000 and 2005 did not take into account
for the CO
2
originating from the active volcanic area of Solfatara.
The exposure to Solfatara CO
2
emissions would not be negligible if
fluxes were to increase. CO
2
concentrations should not consistently ex-
ceed 15,000 ppm (1.5%), a threshold which our simulations suggest
could happen in some locations if emissions increased by at least
ten-fold (up to ~10,000 ton/d). Arecent study, based on a dendrochrono-
logical methodology, showed that the last (1982–1984) bradyseismic
crisis at Campi Flegrei was probably accompanied by a higher-than-
the-present release of deep
14
C-depleted CO
2
into the atmosphere
(Mostacci et al., 2009). Enhanced release lasted for several years. It is
thus likely that dangerous threshold levels have been sporadically
attained in the past around the Solfatara and in the inhabited areas NE
of the crater (western sector of Naples), where gases are preferentially
transported by the dominant marine breezes during spring and
summer.
6. Conclusions
In order to investigate the spatial and temporal evolution of the volca-
nic CO
2
plume emitted by Solfatara, several simulations were performed
using a numerical code. Simulations were performed for the most signif-
icant local wind and atmospheric conditions and were validated by mea-
surements. Even considering the maximum CO
2
emission rate measured
in the last ten years and the more unfavourable atmospheric conditions
(i.e. onshore wind and atmospheric stability), simulated values do not ex-
ceed the recommendedthresholdvalues. Nevertheless, volcanic CO
2
adds
to the amount of CO
2
produced by anthropogenic activity in Naples and
contributes to the deterioration of urban air quality, particularly during
the summer months when the city of Naples is often affected by
photosmog episodes or high concentrations of primary pollutants. The
magnitude of this very local source of CO
2
indicates that it may be impor-
tant inthe regional budget of CO
2
emissions andshouldbe includedinthe
official inventory submitted by the Italian authorities in the framework of
actions to quantify greenhouse gas emissions.
Appendix
Model DISGAS: numerical solution method
Considering a null-divergence windfield, ina terrainfollowing coordi-
nate system(Douglas and Kessler, 1990), the mass conservation equation
for the scaled concentration C may be re-written in a generalised formas
(Toon et al., 1988; Jacobson et al., 1996; Park and Kim, 1999):
∂C
∂t
þ U
∂C
∂x
þ V
∂C
∂y
þ W
∂C
∂z
Ã
¼

∂t
K
h
∂C
∂x
_ _
þ

∂y
K
h
∂C
∂y
_ _
þ

∂z
Ã
K
z
∂C
∂z
Ã
_ _
þ Q
Ã
ð1Þ
where t is time, (U, V, W) are the scaled wind speeds, K
h
and K
z
are the
diagonal scaled diffusion coefficients and Q
*
the source term in the gen-
eralised coordinate. If we consider the simple transformation changing
only the vertical coordinate as: z
*
= z − h(x,y), the Jacobian is equal to
the unit (J ¼
∂z
∂z
Ã
¼ 1). Concerning the turbulent diffusion tensor, we ne-
glect the off-diagonal horizontal and vertical turbulent diffusion compo-
nents (Jacobson et al., 1996). For a more general treatment that include
the off-diagonal diffusion components see Byun and Chin (1999).
The advective terms are discretised according to the second-order
Lax–Wendroff scheme (e.g., Lax and Wendroff, 1960; Ewing and Wang,
2001). For instance, the advective term in the x-direction we have:
−Δt U
∂C
∂x
_ _
n
i;j;k
¼ −
Cr
2
C
n
iþ1;j;k
−C
n
i−1;j;k
_ _
þ
Cr
2
2
C
n
iþ1;j;k
−2C
n
i;j;k
þ C
n
i−1;j;k
_ _
ð2Þ
where Cr ¼ U
Δt
Δx
denotes the Courant number (Δx is the grid spacing
and Δt the computational time step), n is an index for time
discretisation, (i, j, k) for the spatial grid. In order to reduce the numer-
ical over- and under-shooting that commonly affects high-order
schemes near discontinuities one can use slope limiter methods. In
fact, these methods preserve the monotonicity of the solution while
the accuracy remains higher than the first order upwind methods
(Sweeby, 1984; Ewing and Wang, 2001; Wang and Hutter, 2001). For
instance, applying the minmod slope-limiter method and considering
the general case with non-uniform velocity, the Eq. (2) becomes:
−Δt U
∂C
∂x
_ _
n
i;j;k
¼ −
Δt
Δx
U
n
iþ1;j;k
C
n
iþ1;j;k
−U
n
i−1;j;k
C
n
i−1;j;k
_ _

Δx
2
Cr
n
i;j;k
1−Cr
n
i;j;k
_ _
σ
n
i;j;k
−Cr
n
i−1;j;k
1−Cr
n
i−1;j;k
_ _
σ
n
i−1;j;k
_ _
ð3Þ
where Cr
n
i;j;k
¼ U
n
i;j;k
Δt
Δx
, and (Ewing and Wang, 2001):
σ
n
i;j;k
¼ minmod
C
n
iþ1;j;k
−C
n
i;j;k
Δx
;
C
n
i;j;k
−C
n
i−1;j;k
Δx
_ _
ð4Þ
with minmod a; b ð Þ ¼
1
_
2
sgn a ð Þ þ sgn b ð Þ ½ Š min a j j; b j j ð Þ. The introduc-
tion of alternative limiter methods is straightforward.The diffusion terms
are evaluatedusing a central difference scheme for the general case witha
not uniform turbulent diffusivity tensor, e.g. in the x−direction:

∂x
K
h
∂C
∂x
_ _
¼
1
Δx
2
_
K
i;j;k
h
þ K
i−1;j;k
h
_ _
C
i−1;j;k
− K
iþ1;j;k
h
þ2K
i;j;k
h
þ K
i−1;j;k
h
_ _
C
i;j;k
þ K
iþ1;j;k
h
þ K
i;j;k
h
_ _
C
iþ1;j;k
_
: ð5Þ
The stability of the numerical scheme is ensured by using a time
step ∆t lower than the critical. As established by Hindmarsh et al.
(1984), an explicit scheme for the multidimensional advection diffu-
sion equation is numerically stable if the following condition is veri-
fied:
Δt ≤
1
U
Δx
þ
U
Δx
þ
U
Δx
þ2
K
h
Δx
2
þ
K
h
Δy
2
þ
K
z
Δz
Ã
2
: ð6Þ
Table 4
Carbon dioxide emitted by the metropolitan area of Naples (ISPRA, 2007).
Source
a
2000
(ton/y)
2005
(ton/y)
01 Combustion in energy and transformation industries 698,698 881,989
02 Non-industrial combustion plants 1,245,025 1,515,737
03 Combustion in manufacturing industry 617,276 308,836
04 Production processes 24,909 22,707
06 Solvent and other product use 42,739 45,429
07 Road transport 4,393,564 4,400,325
08 Other mobile sources and machinery 1,292,317 1,215,360
09 Waste treatment and disposal 13,133 19,528
11 Other sources and sinks (nature) −275,051 −341,466
Total 8,052,612 8,068,445
a
Source nomenclature according to SNAP97 (Selected Nomenclature for sources of Air
Pollution). SNAP97 categories were developed as part of the CORINAIR (CORe INventory
of AIR emissions) project (EMEP/CORINAIR, 2006) for distinguishing emission source sec-
tors, sub-sectors andactivities. SNAP97 is fully consistent with the IPCC (Intergovernmental
Panel on Climate Change) nomenclature (IPCC, 2007). Emissions are categorised under
eleven sources (or macro-sectors), each source including sub-sectors and activities. Sources
05 (Extraction and distribution of fossil fuels and geothermal energy) and 10 (Agriculture)
do not contribute to the total CO
2
budget in the area: they are therefore not present in the
inventory. Source 11 mainly includes the effects of managed and unmanaged forests, with
positive values for CO
2
emission and negative ones for CO
2
consumption by photosynthesis
in green plants. In this category the specific activity “Volcanoes” would include “emissions
from eruptive and non-eruptive volcanoes”.
60 D. Granieri et al. / Journal of Volcanology and Geothermal Research 260 (2013) 52–61
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