Environmental Pollution 157 (2009) 1506–1512

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Ozone and urban forests in Italy

Elena Paoletti
IPP-CNR, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy

European criteria to protect human health from ozone may not protect urban forests in the Mediterranean area.

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

Article history: Ozone levels along urban-to-rural gradients in three Italian cities (Milan, Florence, Bari) showed that
Received 3 September 2008 average AOT40 values at rural and suburban sites were 2.6 times higher than those determined at urban
Accepted 5 September 2008 sites. However, O3 also exceeded the European criteria to protect forest health at urban sites, even when
the standards for human health protection were met. For protecting street trees in Mediterranean cities,
Keywords: the objectives of measurement at urban sites should extend from the protection of human health to the
Air quality
protection of vegetation as well. A review of forest effects on O3 pollution and of O3 pollution on forest
EU Directive
conditions in Italian cities showed that it was not possible to distinguish the effect of O3 in the complex
UFORE
Urban air pollution mixture of urban pollutants and stressors. A preliminary list of tree species for urban planning in the
Tropospheric ozone Mediterranean area shows the average tree capacity of O3 removal and VOC emission.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction rural stations have to be used to evaluate the protection of vege-

tation. On this basis, it is hard to know the potential of O3 impact on
Ground-level ozone (O3) is the most widespread and harmful urban trees.
pollutant to trees (Paoletti, 2007). Trees in cities are confronted by Although emissions of O3 precursors fell substantially during
a variety of adversities, including O3 pollution. Yet it frequently the period 1990–2004 in Europe resulting in improved air quality
occurs that O3 levels at traffic hot spots are lower compared to over the region (EEA, 2007), ambient O3 concentrations have not
urban background sites, where O3 concentrations are in turn lower shown any improvement since 1997 (EEA, 2007). This might be due
than at rural locations (EEA, 2007). The main reasons for this are to meteorological variability and growing long-distance transport
(Paoletti, 2007): (a) O3 is a secondary pollutant, in that it is not of pollution. As a result, O3 is still the air pollutant of major concern
directly emitted from sources. It is therefore probable that for forests (Paoletti et al., 2007a). Ozone’s toxic potential to urban
a considerable fraction is formed at a certain distance from the forests should be better evaluated, in particular in the Southern
precursor sources; (b) the increased pollution level in urban areas European countries around the Mediterranean, where high rural O3
favours return reactions with nitrogen oxides which lead to O3 concentrations are most pronounced (EEA, 2007). Due to its central
depletion; (c) in green areas, biogenic hydrocarbons (BVOCs) may position in the Mediterranean, Italy may be considered as a hot-
contribute to the formation of O3, since they are more reactive than spot for O3 and representative of O3 impacts on Mediterranean
anthropogenic hydrocarbons. vegetation (Paoletti, 2006). An analysis of 34 O3-exposure metrics
In spite of lower O3 levels at urban than rural sites, from 1996 showed that O3 pollution in Italy regularly exceeds the European
onwards 13–60% of the urban population in Europe has been standards at rural sites (Paoletti et al., 2007b). This paper reports O3
exposed to ambient O3 concentrations exceeding the European levels along urban-to-rural gradients in three Italian cities as a case
target value set for the protection of human health (EEA, 2007). The study, and reviews the state-of-knowledge of O3 pollution effects
potential of these exceedances to damage urban forest health is on urban forest condition in Italy.
unclear, as the recent Directive 2008/50/EC on ambient air quality As O3-exposure affects trees, trees affect O3 in the air. Pollution
and cleaner air for Europe uses different O3 metrics to protect mitigation, in fact, is among the many benefits urban forests can
human and vegetation health (Table 1). In addition, the Directive provide (Brack, 2002). Urban trees affect O3 pollution through three
2008/50/EC states that urban monitoring stations have to be used major processes: 1. cooling of ambient temperature and hence
to evaluate the protection of human health, while suburban and slowing the smog formation process (Akbari, 2002). Trees reduce air
temperature through shading and evapotranspiration (Oke, 1989),
thus they: reduce emissions of O3 precursors from air-conditioning
E-mail address: [email protected] and other cooling equipment; decrease temperature-dependent

0269-7491/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2008.09.019
 E. Paoletti / Environmental Pollution 157 (2009) 1506–1512 1507

Table 1
Summary of European criteria to protect human health and trees from ozone.

Receptor Acronym Indicator Value

Human Number of days exceeding the target value, calculated as maximum daily Target value: 60 ppb not to be exceeded on more than 25 days per calendar
healtha 8-h meane year averaged over three yearsf
Human HHdird Maximum daily 8-h meane Long-term value: 60 ppb in a calendar year
healtha
Human N90d 1-h average Information threshold: 90 ppb
healtha N120d Alarm threshold: 120 ppb
Human SOMO35 SOMO35g Not suggested
healthb
Vegetationa AOT40dir AOT40h May–July (8:00–20:00 CET) Target value: 9 ppm h as 5-yr averagef
Long-term value: 3 ppm h
Forestsc AOT40F AOT40h Growing season (daytime hours >50 W m2) Critical level: 5 ppm h in a year
a
Source: Directive 2008/50/EC.
b
Source: UNECE (2004).
c
Source: LRTAP Convention (2004).
d
Cases of excess.
e
The maximum daily 8-h mean concentration is selected by examining 8-h running averages.
f
If the three or five year averages cannot be determined on the basis of a full and consecutive set of annual data, the minimum requirement for checking compliance with the
target values is one year for human health, and three years for vegetation.
g
Sum of excess of daily maximum 8-h means over the cut-off of 35 ppb.
h
Cumulative exposure above a threshold of 40 ppb O3.

emissions of hydrocarbons from biogenic and anthropogenic leading to increased deposition velocities would lead to greater
sources; change the reaction rates of O3-forming chemical reac- downward flux and total removal) (Nowak et al., 2006). Only two
tions; change the depth of the mixing layer (Nowak et al., 2000). The other studies about O3 mitigation by urban forests have been
role of trees to improve urban climatic conditions differs across carried out in Mediterranean-type climates (Fuenlabrada, Spain,
Europe and is particularly important in southern countries (Tyr- Vilela Lozano, 2004; Santiago, Chile, De la Maza et al., 2005), where
väinen et al., 2005). 2. Dry deposition (including stomatal uptake O3 levels are of most concern. This paper reports two new case
and non-stomatal deposition upon plant surfaces) by which O3 is studies from Italy.
removed from the air (Akbari, 2002). Once inside the leaf, O3 In summary, the aims of this paper are: 1. to summarise O3 levels
diffuses into the intercellular spaces and dissolves in water films to along urban-to-rural gradients in three cities representative of
form toxic reactive oxygen species (Paoletti, 2007). Deposition of Northern (Milan), Central (Florence) and Southern (Bari) Italy; 2. to
gaseous pollutants is greater in woodlands than in shorter vegeta- review the state-of-knowledge of forest effects on O3 pollution and
tion (Fowler et al., 1989) as, in addition to having greater leaf areas of O3 pollution on forest conditions in Italian cities.
than other types of vegetation, trees create more turbulent mixing
of the air passing over land. 3. Emission of biogenic volatile organic 2. Ozone pollution along urban-to-rural gradients in
compounds (BVOCs), which can contribute to O3 formation Italian cities
(Benjamin and Winer, 1998). The amount of BVOCs in major urban
areas is minimal or negligible when compared to anthropogenic The relationship between O3 levels at rural and urban locations
sources (Carter, 1994). BVOCs, however, are estimated to be 2–3 in Italy has never been studied in detail. Quality assured data
times more reactive than a weighted average of hydrocarbons from (annual sampling efficiency  80%) were collected from monitoring
gasoline combustion (Carter, 1994), thus increasing their relative stations run by the local authorities in charge of air pollution
contribution to O3 formation. BVOCs include the isoprenoids monitoring for the cities of Milan, Florence, and Bari, during 2005.
(isoprene and monoterpenes as well as sesquiterpenes and homo- These cities were selected to represent three typical climates of
terpenes) and minor compounds such as alkanes, alkenes, Italy, according to the Köppen climate classification (Peel et al.,
carbonyls, alcohols, esters, ethers, and acids. Isoprenoids protect 2007). Milan has a humid subtropical climate with damp and cold
plant membranes against oxidative stressors, including O3 winters, while summers are hot and very humid. Florence is clas-
(Calfapietra et al., this issue). A taxonomic methodology to classify sified between the Mediterranean and the humid subtropical
tree and shrub species on the base of hourly emission rates of climates. It experiences hot, humid summers with little rainfall and
isoprene and monoterpene, thus identifying low O3-forming cool, damp winters. Bari has a typical Mediterranean climate, with
potential species, has been proposed (Benjamin et al., 1996; mild winters and hot summers. The mean annual temperature and
Benjamin and Winer, 1998). Ozone mitigation by urban trees, precipitation are 12.5, 14.7, and 15.8  C and 944, 912, and 586 mm,
however, is usually greater than O3 formation (Nowak et al., 2000). respectively. Three sites were selected for each city, one rural, one
In the US, urban forests were estimated to remove about suburban and one urban station (Fig. 1). Because of the large size of
711,000 metric ton ($3.8 billion value) of air pollution per year Milan, two urban stations were selected for this city. A rural station
(Nowak et al., 2006). The amount of pollution removed was typi- was not available in Bari. The monitoring station types were
cally greatest for O3, followed by particulate matter, nitrogen defined according to the Directive 2008/50/EC, namely urban
dioxide, sulfur dioxide, and carbon monoxide. Pollution removal stations were located in the main city, suburban stations were
varies among cities depending on the amount of tree cover located in urban green areas, while rural stations were far away
(increased tree cover leading to greater total removal), pollution from the city. The O3-exposure indices in Table 2 show that the
concentration (increased concentration leading to greater down- criteria to protect forest health were exceeded at urban sites in
ward flux and total removal), length of the in-leaf season (increased Milan and Bari, although the criteria to protect human health were
growing season length leading to greater total removal), amount not (Table 1). Exceedances at suburban and rural sites were,
of precipitation (increased precipitation leading to reduced total however, much greater than at urban sites, being on average 1.6–1.7
removal via dry deposition), and other meteorological variables and 4.2–4.7 times higher than the AOT40dir and AOT40F standards,
that affect tree transpiration and deposition velocities (factors respectively. All the indicators of human health showed a similar
1508 E. Paoletti / Environmental Pollution 157 (2009) 1506–1512

Fig. 1. Location and main characteristics of the investigated cities and ozone monitoring stations. Numbers in brackets show distance of the stations from the city centre [in km].
Numbers in parenthesis are the ID code of the stations in the maps.

trend, i.e. were higher at suburban and rural sites than in the city. from urban to suburban and then rural sites. The annual absolute
The only exception was Bari, where urban concentrations of O3 peak showed a similar trend. According to Landry and Cupelin
were higher than concentrations at the suburban site from June to (1981), the ratio of urban O3/rural O3 (M24) was lower than 1 (0.6–
December (Fig. 2). The coastal location of Bari may have affected 0.7), while the ratio of urban O3/suburban O3 was 0.8 in Milan and
this result (Entwistle et al., 1997; Adeeb and Shooter, 2004). The Florence, and 1 in Bari. Higher O3 concentrations were recorded
target value to protect human health (HHdir) at rural sites was on during the weekends than during weekdays at urban and suburban
average twice the 25 days per year set by the Directive 2008/50/EC sites, most likely due to the large reduction in NOx emissions at the
(Table 2). At suburban stations, i.e. in urban green areas, HHdir was weekend in these areas (Blanchard and Fairley, 2001). No
22% larger than at rural sites, on average. Hourly peaks exceeded weekend–weekday effect was observed at rural sites.
120 ppb (N120) just once at a rural site, while 90 ppb (N90) was The average daily profiles of O3 concentrations showed a similar
frequently exceeded at rural and suburban sites, not at urban pattern in all the sites, the only exception being the early morning
stations. Except Bari, the annual averages of hourly O3 concentra- minimum values that were more marked at urban and suburban
tions (M24) and of weekly peaks (M1) increased as expected, i.e. sites (Fig. 2), suggesting higher development of the night inversion

Table 2
Ozone metrics (annual values in 2005) for the protection of human health and forests along urban-to-rural gradients in the cities of Fig. 1. HHdir, number of exceedances of the
daily maximum 8-h running mean over the cut-off of 60 ppb in a year (2008/50/CE Directive); N90, number of hourly concentrations >90 ppb in a year (2008/50/CE Directive);
N120, number of hourly concentrations >120 ppb in a year (2008/50/CE Directive); SOMO35, sum of excess of daily maximum 8-h means over the cut-off of 35 ppb in a year
(Amann et al., 2005); AOT40dir: sum of the excess of hourly concentrations over the cut-off of 40 ppb between 8 am and 8 pm over the 3 months May to July (2008/50/CE
Directive); AOT40F: AOT40 during light hours (around 6 am–8 pm) over the 6 months April to September (ICP, 2004); Max, maximum hourly concentration in a year; M1,
annual mean of the weekly hourly peaks; M24, annual mean of the weekly daily averages; annual mean and maximum value of weekly daily averages in weekends (including
public holidays) and weekdays. Bold numbers show exceedance of the standards.

Milan Florence Bari

Urban1 (1) Urban2 (2) Suburban (3) Rural (4) Urban (5) Suburban (6) Rural (7) Urban (8) Suburban (9)
HHdir [no. days] 18 3 61 54 0 61 46 10 19
N90 [no. hours] 3 0 31 18 0 21 28 0 0
N120 [no. hours] 0 0 0 0 0 0 1 0 0
SOMO35 [ppb h] 1763 869 3467 3581 690 3990 3224 3124 2991
AOT40dir [ppb h] 6982 3714 17,155 16,508 2054 17,510 14,325 10,651 9152
AOT40F [ppb h] 10,388 4391 23,646 23,723 2905 25,587 22,957 16,830 14,666
Max [ppb] 94.50 74.50 106.00 102.50 75.10 118.85 129.50 78.84 77.95
M1 [ppb] 45.12 37.38 53.97 57.86 40.03 58.41 57.38 52.57 51.77
M24 [ppb] 18.01 14.25 20.13 24.41 18.02 25.17 30.07 30.42 30.57
Max weekdays [ppb] 32.02 24.17 38.78 41.77 29.76 44.85 43.46 44.01 42.76
Max weekends [ppb] 33.87 27.35 39.68 40.54 30.30 44.57 37.55 45.41 44.62
Average weekdays [ppb] 17.20 13.01 19.16 24.07 17.69 24.00 30.02 29.03 29.19
Average weekends [ppb] 19.75 16.03 22.18 24.88 18.85 25.98 30.28 33.09 33.11

For SOMO35 and HHdir, the daily maximum 8-h mean for a given calendar day is the highest of all the possible 8-h means computed for that day.
 E. Paoletti / Environmental Pollution 157 (2009) 1506–1512 1509

80
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Milan

Ozone hourly av., ppb

70
60
50
40
30 Urban1
20 Urban2
10 Suburban
Rural
0
0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12
Daytime

80
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Florence
Ozone hourly av., ppb

70
60
50
40
30
20 Urban
10 Suburban
Rural
0
0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12
Daytime

80
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Bari
Ozone hourly av., ppb

70
60
50
40
30
20
10 Urban
Suburban
0
0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12 0 12
Daytime

Fig. 2. Mean daily trend of ozone concentrations in the stations of Fig. 1 over the year 2005. Regular gaps show the time of daily instrumental calibrations.

layer and/or higher NO sources (PORG, 1997; Duenas et al., 2004). sites compared to samples from rural sites (Manes et al., 1988;
Peaks increased from urban (75–95 ppb) to suburban (75–120 ppb) Altieri et al., 1994). These alterations, however, may be induced by
and rural (100–130 ppb) stations. They occurred during the early several stressors, and it was not possible to identify the role of O3
afternoon (14–15 CET), independently of station type and city. pollution. The response to atmospheric pollutants was studied in
Only in November and December did O3 concentrations peak the Mediterranean evergreen broadleaf tree Quercus ilex,
earlier (13–14 CET). The largest amplitudes between minimum and measuring foliar isotopes (radiocarbon activity and isotopic
maximum concentrations were in Milan and Florence. Onshore composition), chemical (Pb concentration) and ecophysiological
breezes in the coastal Bari may lead to little nighttime depletion of (gas exchange and chlorophyll a fluorescence) parameters (Alessio
O3 (Coyle et al., 2002). The profiles were similar to those reported et al., 2002). Measurements were carried out along a transect from
by Klumpp et al. (2006a) for 11 cities in Europe, including Verona in the road bordering an urban park in Rome (Villa Ada) towards the
Italy, where a north–south gradient of increasing O3 pollution interior. All the parameters showed a decreasing pollution gradient
across Europe was recorded. Because of the limited number of towards the inner park. Again, it was not possible to distinguish the
stations, such a gradient is not clear in the present study. effect of O3 in the complex mixture of urban pollutants. Conclusive
proof of O3 impacts on urban forests is lacking in the international
3. Urban forest and ozone interactions literature (Impens, 1999), as it is the nature of this pollutant that it
does not accumulate in plant tissue or cause specific responses
In Italy, urban boundaries are referred to by administrative (Paoletti, 2007). Indirect proof may come by the cross-comparison
municipalities. Inventories of urban green area refer to public of results from ambient and controlled conditions. Leaf gas
spaces only. Public green open space represents on average 5% of exchange in Mediterranean urban ornamental plants (Laurus
municipal surface, and the availability per person is 17.7 m2 (APAT, nobilis, Viburnum tinus, Hedera helix, Hedera canariensis var. azorica,
2006). Nerium oleander, and Arbutus unedo) was significantly reduced by
Only a few studies carried out in Rome, the capital of Italy, exposure to one O3 spike (200 ppb per 5 h in closed chambers)
investigated functional changes of urban trees in response to O3 in (Lorenzini et al., 1999). Q. ilex was more tolerant than the previous
the air. In Pinus pinea, a rise in peroxidase activity and structural species, as gas exchange, chlorophyll fluorescence, and peroxidase
alterations of stomata were observed in needles collected at urban activity were not influenced up to 300 ppb O3 (6 h/d per 2 days in
1510 E. Paoletti / Environmental Pollution 157 (2009) 1506–1512

closed chambers) (Manes et al., 1998). Hourly O3 concentrations thus varying the life-span during which BVOC emissions occur
>100 ppb, however, are unrealistic compared to the real level of O3 (Centritto et al., 2004).
pollution in Italian cities (Table 1). Biomonitoring with herbaceous The physical effects of vegetation on O3, however, are more
and woody plants has been used to obtain information on O3 important than atmospheric chemical interactions with BVOCs
pollution in Italian cities (reviewed in Nali et al., 2006; Klumpp (Nowak et al., 2000). The addition of 11 millions of trees in Los
et al., 2006b) and suggests that urban O3 levels are high enough to Angeles would scavenge 1% of the O3 mass by dry deposition, plus
damage plants. 0.6% by also scavenging NO2, an O3 precursor (Taha et al., 1997),
Much attention is now focusing on the influence of urban forest thus reducing the exceedance over the California standard of
on O3 pollution, rather than on O3 impacts on city trees. Emission 90 ppb by 6% and resulting in an estimated savings of about US$180
of BVOCs can contribute to the production of secondary organic million/year (Rosenfeld et al., 1998). Modeling of the New York City
aerosols and O3 (Chameides et al., 1988). BVOC emission rates are metropolitan area suggested that increasing tree cover by 10%
plant species-specific and vary by as much as four orders of would reduce O3 peaks by about 4 ppb, which was about 37% of the
magnitude (Benjamin et al., 1996). The actual O3-forming potential amount needed for attainment of the standard (Luley and Bond,
(OFP) of individual trees depends on hourly mass emission rates, 2002). Most recent results have been obtained with the Urban
environmental factors, and differences in tree biomass and Forest Effects (UFORE) model, a computer model designed to use
photochemical reactivity. Taha (1996) showed that the net effect of tree allometric, air pollution and meteorological data to statistically
increased urban tree cover in the California South Coast Air Basin estimate urban forest characteristics and various urban forest
would be a decrease in O3 concentrations if the additional trees functions including O3 removal and BVOC emission (Nowak, 2006;
were low VOC emitters. The simulation suggested that species Nowak et al., 2006). Average percent improvement in air quality
emitting roughly more than 2 mg of isoprene or 1 mg of mono- from O3 removal by trees during the daytime of the in-leaf season
terpenes per g leaf dry weight in an hour should not be introduced in 13 US cities was 0.62% (Nowak et al., 2006).
in the basin in large amounts. For the city of Beijing, BVOC emis- UFORE was applied to two case studies in Italian cities: a park in
sion resulted in 9.1 g O3/g isoprene emitted and 3.3 g O3/g Milan (Porta Venezia gardens; Siena and Buffoni, 2007) and
monoterpene emitted (Yang et al., 2005). The current knowledge a tramway under construction in Florence (Line 1 and 3; Paoletti,
about BVOC emission, however, is not adequate with regard to unpublished). Among all pollutants (SO2, NO2, CO, O3 and Particu-
urban environments. In particular, different management (e.g. late Matter <10 mm), the highest annual removal by urban trees
pruning, fertilisation) and the stressful conditions to which urban was for PM10 (196 and 198 g/tree in Milan and Florence, respec-
trees are exposed (including exposure to pollution and acclimation tively) and O3 (68 and 170 g/tree in Milan and Florence, respec-
of ornamental exotic species to environmental constraints) may tively). Higher efficiency in Florence may depend on both different
affect BVOC emission rates (Centritto et al., 2005). Elevated CO2 tree species and climate, and higher O3 pollution. M24 was 22 ppb
concentrations and higher air temperature compared to rural in Florence and 17 ppb in Milan. The most effective individuals in O3
areas are common in cities. These factors can directly affect BVOC removal differed in the two cities (Table 3): Tilia in Milan, and
emissions (Loreto and Sharkey, 1990) and accelerate leaf ontogeny, Cedrus sp. in Florence. Although Acacia dealbata individuals were

Table 3
Ozone removed and total VOC emitted in a year (g/tree) in two UFORE case studies in Italy: Milan (Porta Venezia gardens; Siena and Buffoni, 2007) and a tramway under
construction in Florence (Line 1 and 3; Paoletti, unpublished).

Milan Florence

Species O3 removal VOC emission Species O3 removal VOC emission

Acer platanoides 45 86 Acacia dealbata 603 1103
Aesculus hippocastanum 71 135 Acer campestre 26 354
Ilex aquifolium 26 135 Acer negundo 137 442
Magnolia sp. 60 179 Aesculus hippocastanum 257 372
Taxus baccata 70 143 Ailanthus altissima 174 320
Tilia sp. 84 83 Catalpa bignonioides 43 407
Quercus robur 45 345 Cedrus atlantica 924 213
Cedrus deodara 644 173
Celtis australis 230 348
Cercis siliquastrum 0 62
Chamaecyparis lawsoniana 52 42
Crataegus sp. 44 279
Cupressus sempervirens 260 313
Fraxinus sp. 280 224
Laurus nobilis 296 249
Ligustrum lucidum 54 435
Liquidambar styraciflua 13 688
Magnolia sp. 85 318
Olea europaea 35 200
Paulownia tomentosa 125 853
Pinus pinea 179 385
Platanus acerifolia 140 276
Populus alba 193 467
Populus nigra 353 327
Prunus armeniaca 14 698
Prunus cerasifera 52 311
Quercus ilex 112 341
Quercus rubra 65 312
Robinia pseudacacia 30 320
Tilia cordata 193 332
Ulmus sp. 216 307
 E. Paoletti / Environmental Pollution 157 (2009) 1506–1512 1511

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