Revista Brasileira de Meteorologia, v.21, n.

2, 190-200, 2006

ESTIMATED IMPACT OF BIOGENIC HYDROCARBON EMISSIONS ON

PHOTOCHEMICAL OXIDANT FORMATION IN SÃO PAULO DURING TWO
PERIODS OF THE WINTERS OF 1999-2000.

LEILA DROPRINCHINSKI MARTINS1, PÉROLA DE CASTRO VASCONCELLOS2, LILIAN R.

FRANCO DE CARVALHO2 & MARIA DE FÁTIMA ANDRADE1

1
Departament of Atmospheric Sciences, Institute of Astronomy, Geophysics and Atmospheric Sciences.
University of São Paulo. Rua do Matão 1226, São Paulo, Brazil. CEP: 05508-090. Fax 55-11-3091-4714.
E-mails: leiladro@model.iag.usp.br, mftandra@model.iag.usp.br
2
Institute of Chemistry. University of São Paulo, São Paulo, Brazil. CEP: 05315-970.
E-mails: perola@iq.usp.br, lrfdcarv@iq.usp.br

Recebido Março 2005 - Aceito Abril 2006

ABSTRACT
In this study, the impact of emissions of biogenic volatile organic compounds (BVOCs) was studied.
The primary focus was on formation of ozone (O3) in the Metropolitan Area of São Paulo (MASP),
analysed using the California Institute of Technology (CIT) photochemical model. A biogenic emissions
inventory was compiled from data in the existing literature. In order to estimate the concentration of the
most important compounds emitted by vegetation, environmental BVOCs were measured. Simulations
of atmospheric O3 formation were carried out from August 9 to August 12, 1999 in order to calibrate
the model and from August 22 to August 24, 2000 to verify the quality of the simulations. Simulations
either included or excluded biogenic emissions. Comparing the results of simulations including biogenic
emissions with those from simulations excluding such emissions revealed that biogenic emissions
contributed to the formation of, on average, 15.3% higher O3 concentrations, 20.4% higher peroxyacetyl
nitrate (PAN) concentrations, 1.7% higher nitrogen dioxide (NO2) concentrations and 2.4% lower
nitric oxide (NO) concentrations for first period. In second period of simulation similar behaviour was
observed, but with smaller contribution than in the first period.
Keywords: CIT model; biogenic volatile organic compounds; tropospheric ozone; urban atmosphere;
emissions

RESUMO: ESTIMATIVA DO IMPACTO DAS EMISSÕES DE HIDROCARBONETOS

BIOGÊNICOS NA FORMAÇÃO DE OXIDANTES FOTOQUÍMICOS EM SÃO PAULO
DURANTE DOIS PERÍODOS DOS INVERNOS DE 1999-2000.
Neste trabalho, o impacto das emissões de compostos orgânicos voláteis biogênicos (COVBs) foi
estudado, com ênfase na formação do ozônio (O3) na Região Metropolitana de São Paulo (RMSP).
A análise foi realizada usando o modelo fotoquímico California Institute of Technology (CIT). O
inventário de emissões biogênicas foi compilado de dados existentes na literatura. Medidas ambientais
dos COVBs foram realizadas para estimar a concentração dos principais compostos emitidos pela
vegetação. Simulações Atmosféricas da formação de O3 foram conduzidas de 9 de agosto a 12 de
agosto de 1999 para calibração do modelo e de 22 de agosto a 24 de agosto de 2000, para verificação
da qualidade das simulações. Simulações essas incluindo ou excluindo as emissões biogênicas. A
comparação dos resultados das simulações incluindo as emissões biogênicas com as excluindo essas
emissões, revelaram que as emissões biogênicas contribuíram para o aumento da concentração de O3
em 15,3%, de peroxiacetil nitrato (PAN) em 20,4%, de dióxido de nitrogênio (NO2) em 1,7% e para
a redução da concentração de óxido de nitrogênio (NO) em 2,4% para o primeiro período de estudo.
O Segundo período apresentou similar comportamento, porém com menor contribuição.
Palavras-chave: modelo CIT; compostos orgânicos voláteis biogênicos; ozônio troposférico;
atmosfera urbana; emissões.
Agosto 2006 Revista Brasileira de Meteorologia
1. INTRODUCTION
Emissions of volatile organic compounds (VOCs),
whether biogenic or anthropogenic, lead to a series of complex
chemical and physical transformations, resulting in various
environmental effects, such as photochemical pollution,
acid deposition, alterations in ozone (O3) concentrations and
modification of the global climate (Fehsenfeld et al., 1992).
The VOCs are not only O 3 precursors, but their
degradation can generate other products, such as organic acids,
aldehydes, ketones and peroxyacetyl nitrates (PANs). The
mechanisms by which plants produce and emit biogenic volatile
organic compounds (BVOCs) have not been, as yet, completely
described. The exceptions are isoprene and terpenes (Fall, 1999;
Monson et al., 1995), which have been studied extensively due
to their ubiquity in plant emissions (Fall, 1999).
Urban vegetation, trees in particular, can directly or
indirectly affect the quality of urban air. Tree canopies and
plant transpiration affect meteorological variables such as air
temperature, radiation absorption (heat storage), wind speed,
relative humidity, turbulence, surface albedo and surface
roughness (consequently affecting the evolution of boundary-
layer height). In addition, urban vegetation affects dry deposition
of gases to the surface and emission of VOCs, which can,
in turn, contribute to formation of O3 and carbon monoxide
(CO). These effects of vegetation, which lead to changes in
atmospheric chemistry and physics, all interact to affect ozone
concentrations (Nowak et al., 2000).
Few studies integrating the cumulative effects of
urban vegetation on air quality, particularly the effect it
has on O3 formation, have been performed. Cardelino and
Chameides (1990) simulated the effects of vegetation on O3
concentrations in the Atlanta region. The work demonstrated
that an urbanisation-driven 20% decrease in forested area could
result in a 14% increase in O3 concentration (Nowak et al.,
2000).
Vogel and collaborators (1995) studied the influence
of BVOCs on O3 concentrations during episodes of high air-
temperature in the state of Baden-Wurttemberg in Germany.
They concluded that BVOCs could play an important role
at high temperatures (± 35°C), and that biogenic emissions
contributed between 10 to 20% to the total O3 concentration.
Other important study was developed by Thunis and Cuvelier
(2000). They estimated the impact of BVOCs performing
simulations with and without biogenic emissions and found that
the maximum impact of biogenic emissions on ozone formation
represents at the most 10 ppbv. However at different locations
the maximum impact is reached at different times and this
impact does not coincide in time with the maximum simulated
ozone concentration.
191
The present work is a first attempt at evaluating the
contribution of BVOC emissions on formation of O3, PAN,
NO and NO2 in the urban sectors of the Metropolitan Area of
São Paulo (MASP). The eulerian air-quality photochemical
model employed was the CIT model developed at the California
Institute of Technology (Caltech) and Carnegie Mellon
University.
2. MATERIALS AND METHODS
2.1. Model description
To evaluate the impact of biogenic emissions on O3
formation, the CIT photochemical model was used. The CIT
model was developed for the study of formation and transport
of photochemical pollutants in the atmospheric boundary layer.
More details about the model can be found in McRae et al.
(1982), Russel et al. (1988) and Cardoso (1997).
The basis of the model is the atmospheric diffusion
equation:
∂ Ci
∂t
( ) (
= −∇ ⋅ u Ci + ∇ ⋅ ( K∇ Ci ) + R i Ci ,...., Cp + Qi )
i = 1, 2, ..., p. (1)
where: Ci is the species i concentration; Qt is the rate of species
i emission; Ri is the species i generation
_ rate by chemical
reactions, K is the eddy diffusivity, u is the mean horizontal
( )
wind speed, ∇ ⋅ u Ci is the transport term caused by wind
and ∇ ⋅ ( K∇ Ci ) is the transport term caused by turbulence.
The CIT model has three modules: meteorology, emissions
and chemistry.
The input data for the model used to solve the
atmospheric diffusion equation are the meteorological variables
(temperature, absolute humidity, solar and ultraviolet radiation,
mixing-layer height and three-dimensional wind fields),
topographical characteristics (including surface roughness), the
rate of emission of the chemical species, and air-quality data
for initial and boundary conditions. The chemical mechanism
used in the CIT model was the 1999 version of the Statewide Air
Pollution Research Center (SAPRC-99) mechanism developed
by Carter (2000).
2.2. Study area
The Metropolitan Area of São Paulo is the largest
industrialised region in Latin America. It has an area of 8,051
km2 with a population of 18 million inhabitants. Currently
there are approximately 7.2 million passenger and commercial
vehicles: 93.5% light-duty and 6.5% heavy-duty diesel vehicles.
Of the light-duty vehicles, approximately 76.3% burn a mixture
192 L. Droprinchinski-Martins et al.
of 78-80% (v/v) gasoline and 22% ethanol (referred to as
gasohol), and 17.2% use hydrated ethanol (95% ethanol + 5%
water). These data are for 2002 and were obtained from the State
Department of Traffic. The addition of ethanol to motor vehicle
fuels reduces CO but increases aldehyde emissions (especially
acetaldehyde), inducing a unique photochemical smog problem
in urban areas. Over the past several years, ambient ozone
concentrations in the MASP have reached levels of more than
five times that considered protective of public health by the
World Health Organization. In the springtime, ozone levels
routinely exceed the 80 ppbv (approximately) hourly Brazilian
National Ambient Air-Quality Standard. Ozone is not emitted
directly but is formed as a result of photochemical interactions
involving VOCs and nitrogen oxides (NOx = NO + NO2).
Approximately 90% of the ozone precursors in the MASP
atmosphere are emitted by the vehicle fleet.
The CIT airshed model was applied to the domain
depicted in Figure 1 (22.9°S, 24.2°S, 48°W and 45°W). The
domain is composed of a grid system of 1800 (60 x 30) 5x5-
km cells. In the vertical direction, the area was divided into 5
layers, delineated in such a way that the resolution was greater
near the surface. The model top was at an altitude of 1700 m
and the top layer was divided into sub-layers of 59.5; 178.5;
238; 561 and 663 meters.
Figure 1 – Illustration of the topography from modelled area (in meters)
and the localization of air-quality stations from CETESB.
2.3. Period of study
The model was applied to two different periods: The first
period of study was from August 9 to August 12, 1999. This
period was characterised as a typical winter weather situation
of in São Paulo, with clear sky, absence of precipitation and
occurrence of pollution events (Montero et al., 2001). The
pollution episode observed on 10 August was driven mainly
by meteorological parameters. On 10 August a system of high-
pressure developed about MASP and this system persisted for
Volume 21(2)
about 3 days. During this period light winds and high-pressure
system, combined with increased temperatures and solar
radiation, provided ideal conditions for O3 production in MASP.
The evolution of this pollution episode resulted in high levels of
ozone concentration observed also in others areas near MASP.
Figure 2 shows surface measurements of ozone performed by
the automatic monitoring air quality stations of CETESB. These
measurements showed the evolution of a pollution episode
beginning on August 10 and resulting in a peak on August 12.
Figure 2 – Hourly observed O3 concentrations from August 10 to
13, 1999.
The second period was from August 22 to August 24,
2000. This period presented absence of precipitation, with
moderate wind, partial cloud covering, lower concentrations of
O3 and others species and with more conditions of dispersion
of pollutants than the first period.
2.4. Data acquisition
The meteorological data used in this study were obtained
by the São Paulo Environmental Protection Agency (CETESB)
and by winter campaigns carried out on August 1999 and 2000
in São Paulo downtown area.
The meteorological fields were defined through
interpolation and posterior objective analysis of the data
collected at the stations, according to the procedures described
by Goodin et al. (1979). Topographical characteristics and
surface types were determined using Regional Atmospheric
Modeling System (RAMS, version 4.3) preliminary data
derived from satellite images. Surface roughness values were
obtained from land use data generated by the RAMS model
and interpreted according to references given by McRae et al.
(1992).
Initial and boundary condition inputs, as well as O3, CO,
NOx, and SO2 concentrations were obtained from CETESB air-
quality measurements taken at twenty-nine automatic stations.
The hourly data were spatially interpolated and used as initial
Agosto 2006 Revista Brasileira de Meteorologia
condition for O3, CO, NOx, and SO2. Boundary conditions were
based on measurements and literature information, being the
model very sensitive to them (Ulke; Andrade, 2001).
2.4.1. Anthropogenic emissions inventory
The anthropogenic emissions inventory used in the
source module of the CIT model was created according to the
annual estimate of mobile and fixed emission sources in the
MASP for the year of 1999, supplied by CETESB. According to
the official state inventory of HC emissions from mobile sources,
22% are from gasohol-powered vehicles, 15% from diesel-
powered vehicles, 6% from ethanol-powered vehicles, and 5%
from motorcycles. In addition, a significant contribution to HC
emissions comes from evaporative emissions, which constitute
48% of total HC emissions to the atmosphere. Hydrocarbons
contribute to the formation of the photochemical smog, and
are generally attributed to mobile sources. In the specific case
of NOx, 78% comes from diesel-powered vehicles, 13% from
gasohol-powered vehicles, and 4% from ethanol-powered
vehicles (CETESB, 2000).
Speciation of hydrocarbons emitted by combustion of
fossil fuels was performed for each fuel – alcohol, gasoline
and diesel. Three processes were considered: 1) emission by
evaporation that occurs in the combustion chamber, together
with other evaporative gas emissions from liquid fuel;
2) emission resulting from vehicle replenishment or from fuel
transfer from tanker to pump at petrol stations; and 3) exhaust
emissions.
Speciation of liquid fuel, in order to calculate the
emission by evaporation, was achieved by chromatographic
analysis of fuel samples collected from the major distributors
in MASP. After analysis that permitted identify and quantify the
compounds in gasohol and alcohol, they were lumped according
to the groups of SAPRC99.
The species used to represent the organic emissions were:
methane (CH4), ethane (C2H6), propane (C3H8), ethene (ETHE),
butadiene (BUTD), isoprene (ISOP), benzene (C6H6), acetylene
(C2H2), ethanol (ETOH), group of alkanes 1 (ALK1), group
of alkanes 2 (ALK2), group of alkanes 3 (ALK3), olephines 1
(OLE1), olephines 2 (OLE2), aromatics 1 (ARO1), aromatics
2 (ARO2) and not identified (UNID). The species in SAPRC99
are lumped in accordance with the reactivity of compounds.
Hydrocarbon species emitted by evaporation, due to fuel
transfer process, were also determined from the composition
of the liquid fuels and based on the partial pressure of the
hydrocarbon compounds, according to the work of Harley et al.
(2000).
Speciation of hydrocarbons emitted by vehicular exhaust
was based on the works of Kirchstetter et al. (1996), Murgel
193
(1990) and Chuí et al. (1975). For gasoline, approximately 60%
of liquid fuel was determined to consist of compounds which
fall into one of the following groups: ALK1, ALK2, OLE2,
ISOP, ARO1, ARO2 and ETOH. For alcohol and diesel fuels,
percentages were estimated based on the works of Murgel (1990)
and Chuí et al. (1975).
Finally the daily emission from gasohol, alcohol and
diesel were distributed in fifty grid points (similar area of
MASP). The distribution was based on information on traffic
density during the day in MASP provided by the São Paulo’s
Traffic Control Agency (CET), with two peaks of emission (at
9 o’clock a.m. and 7 o’clock p.m.).
The inventory used utility emission data from mainly
stationary industrial sources in the city of Cubatão, as well as
from mobile emissions in the MASP, in São José dos Campos,
and in the Baixada Santista.
2.4.2. VOC sampling
On August 31, 2001, air samples were collected in a
secondary forest located in an urban area of São Paulo and
featuring Atlantic forest type vegetation (Struffaldi-De, 1985).
The canopy height was approximately 18 m.
Samples were collected hourly from 8:00 to 18:00
at two levels of a 20-m high tower within the forested area.
From the base of the tower, the two levels were approximately
8 m and 20 m high. One litre of air was passed through a
stainless steel cartridge (9 cm x 0.06 cm) containing 100 mg
of Tenax TA (Supelco) adsorbent (60/80 mesh) and 50 mg of
Carbotrap (Supelco) adsorbent (20/40 mesh). The flow rate was
approximately 200 mL min-1, over 5 min using a 1-L syringe.
After collection, the cartridges were stored in glass tubes
and refrigerated until analysis.
2.4.3. VOC analysis
Cartridges were analysed using a gas chromatograph
equipped with a mass selective detector. The species were pre-
concentrated by a purge and trap system (AERO Trap Desorber,
Tekmar 6000) and analysed in the chromatograph using a DB-1
fused silica capillary column (0.32-mm ID x 30-m length, 1-µm
film thickness, J&W Scientific Company, Folson, CA).
The analysis was made based upon a two-stage cryogenic
sample trapping technique (Greenberg et al., 1999). First, for
water removal, helium was introduced upstream of the cartridge
for 4 min. The thermal desorber was pre-heated at 250°C for
10 minutes and the VOCs were transferred to the first stage, a
-165°C, glass bead-filled sample trap. This stage was heated
rapidly (from -165°C to 240°C in 10 sec), the VOCs were
transferred to the GC analytical column and the analyses were
194 L. Droprinchinski-Martins et al. Volume 21(2)

made in selected ion mode. The instrument was calibrated Table 1 – Ambient isoprene and terpenes concentrations obtained from
daily against a 10 ppbv White Martins standard of isoprene, samples collected on August 31, 2001 at the Estadual das Fontes do
Ipiranga Park in the city of São Paulo.
toluene, m-xylene, 1,3,5-trimethylbenzene, p-xylene, 1,3,5-
trimethylbenzene and n-alkanes (C4-C12). Method detection Concentration of Concentration of
limits for the repeatedly analysed results were three times the Local time isoprene (ppbv) terpenes (ppbv)
standard deviation (TO-17, USEPA, 1997). Level 1 Level 2 Level 1 Level 2
8:00 0.43 0.53 2.77 1.88
2.4.4. Flux estimation 9:00 0.49 0.44 2.79 0.41
10:00 0.53 1.07 0.97 1.95
Fluxes of isoprene and terpenes were estimated through 11:00 0.68 0.71 2.10 1.50
use of the Gradient Flux method, (Guenther et al., 1996) and the 12:00 0.63 0.87 0.53 0.40
gas coefficient of diffusivity was determined according to the 13:00 0.49 0.94 1.52 1.35
theory of Turbulent Kinetic Energy (TKE), expressed for: 14:00 0.62 0.68 0.37 0.26
15:00 0.56 0.31 2.83 0.50
K m = C1lE1 / 2 (2) 16:00 0.24 0.24 0.12 0.15
where: C1 is a constant considered as 0.4, l is the mixture length 17:00 0.13 0.13 n.d. n.d.
and E is the turbulent kinetic energy given by: 18:00 0.21 0.21 0.41 n.d.
n.d. = not detected.
σu 2 + σv 2 + σw 2
E= (3)
2
where: σu2, σv2 e σw2 are the standard deviations of u, ν and
w obtained by Sonic Detection And Ranging (SODAR) equi-
pment (Freitas et al., 2000; Nair et al., 2000) installed in the
sampling site. The length of mixture l was obtained through
the relationship:
l = kz (4)
where: k and z are Von Karman’s constant (0.4) and the height
(20 m) respectively (Holt; Raman, 1988).
Figure 3 – Profile of normalised eddy diffusivity for momentum
(Km* = Km/ku0*Zi), at 0:00 and 14:00.
3. RESULTS AND DISCUSSION
3.1. Biogenic emissions inventory Fluxes were measured between 11:00 and 15:00 and were
found to be between -2.5 and +0.7 mg m-2 h-1 for isoprene and
The results of isoprene and terpenes analysis are +0.9 and +13 mg m-2 h-1 for terpenes. The negative fluxes values
illustrated in Table 1 and the K m * normalised profile for isoprene can be attributed to the fact that most isoprene
(Km* = Km/ku0*Zi, where u0* is the surface friction velocity sources are in the canopy and the measurements were taken at
and Zi is the inversion height) obtained at 0:00 and 14:00 only 2 levels (8 and 20 m), both below the canopy. The values
are illustrated in Figure 3. The profile obtained here was of terpene fluxes were positive, possibly indicating that most
similar to others currently found in the literature (Ulke, terpene sources are located at lower levels.
2000). However, the values were higher than those previously Since below-canopy isoprene values were negative and
reported (Degrazia et al., 1997; Ulke, 2000; Velho et al., 2001). don’t represent any emission of isoprene, these data were not
Experimental data are subject to uncertainty and error that in included in the CIT model biogenic emissions inventory used
many situations cannot be controlled or predicted, especially to estimate the impact of those emissions on O3 formation.
when the site is complex, as it is the case of the site where the Further studies involving measurements taken on different days,
samplings were performed. and at various levels, are necessary in order to obtain a more
Ambient concentrations of isoprene and terpenes were consistent estimate of the fluxes. However, levels and ambient
found to be between 0.13 and 1.07 ppbv for isoprene and 0.12 concentrations of the most important compounds emitted by
and 2.83 ppbv for terpenes. The contribution of urban sources vegetation were estimated in this study. This represents a first
of isoprene can be accounted for by the proximity of the site to attempt to estimate BVOC concentrations and fluxes in the
urbanised areas (Reimann et al., 2000). Atlantic forest.
Agosto 2006 Revista Brasileira de Meteorologia 195

Determination of fluxes and Km is problematic, since
it requires that measurements be taken at various levels, with
great accuracy and over short periods of time (Grünhage et al.,
2000; Ulke, 2000).
The biogenic emissions inventory was prepared
using isoprene and terpene emission values obtained by
Zimmerman et al. (1988) and presented in the Table 2. Only
those emissions recorded between 8:00 and 18:00 were included,
since this was judged to be the period during which the majority
of isoprene and terpene emissions occurred. The isoprene and
terpene emission profile time variation structure in the model
was built based on the temperature profile recorded on August
11, 1999 (simulation day), when maximum emission should
have been in phase with maximum temperature. The emissions
showed in Table 2 were converted for adequate unit
(ppm.m.min -1 ) and represented by group ISOP and TERP (all
terpenes were considered in this group).
and 6 for the two different periods analysed. A first evaluation
of behaviour of concentrations simulated in relation to observed
was carried through.
There was an increase in O3 concentration on August 11
and August 12. Compared with the observed concentrations,
the model overestimated O3 concentrations on August 12. This
difference can be attributed to meteorological conditions (mainly
mixing-layer height and wind field) that did not represent the
actual conditions present on that day. In the model, the wind
field plays an important role in calculating the distribution of
concentrations. Ynoue (1999) demonstrated the impact of the
wind field, as well as that of other meteorological parameters,
on O3 concentrations.

Table 2 – Isoprene and terpene emission values obtained by

Zimmerman et al. (1988) for the Amazon Forest and used in the inven-
tory for this study.
Compounds Emission rate (mg m-2 h-1)
Isoprene 4.00
Terpenes 0.26

The grid points considered for analysis of biogenic

emissions were the areas occupied by forest, as documented by
the RAMS model (version 4.3) (Tripoli; Cotton, 1982; Walko; Figure 4 – Illustration of grid points considered with biogenic
Tremback, 2000). Data relating to types of vegetation and (number 5) and anthropogenic emissions (number 1) inside of chemical
area (smaller region). Each number means one grid point.
land occupation were obtained from International Geosphere
Biosphere Programme (IGBP) and are available on the home
page of the U.S. Geological Survey (USGS) (Freitas, 2003).
Figure 4 shows the grid points considered with biogenic
emissions (number 5) and anthropogenic emissions (number
1) in modelled area. The Park of Ibirapuera (localized in
26(x), 14(y)) and the Park das Fontes do Ipiranga (localized
in 27(x), 13(y)) were also considered for analysis of biogenic
emissions. Figure 5 – Hourly observed and model-simulated O3 concentrations
for the Ibirapuera Park air-quality station for the two periods: August
3.2. CIT model simulations 10 to 12, 1999 (right) and August 23 and 24, 2000 (left).

CIT model simulations were carried out with and without

the inclusion of the biogenic emissions inventory. In the first
simulation, biogenic emissions were not considered and only
anthropogenic emissions were used. In the second simulation,
biogenic emissions other than the anthropogenic ones (mobile
and stationary sources) were included.
The results of these simulations for O3 formation, as Figure 6 – Hourly observed and model-simulated O3 concentrations for
well as experimental data from the Ibirapuera Park and São the São Caetano do Sul air-quality station for the two periods: August
Caetano do Sul air-quality stations, are illustrated in Figures 5 10 to 12, 1999 (right) and August 23 and 24, 2000 (left).
196 L. Droprinchinski-Martins et al.
In Figure 7, space distributions of O3 are illustrated for
simulations and maximum O3 concentration reaching a value of
210 ppbv at 16:00 in the southern portion of the MASP. In the
second period studied the maximum concentrations of O3 were of
180 ppbv and a similar behaviour of the plume was observed.
Figure 7 – Model-simulated spatial variation in O3 concentrations:
a) excluding biogenic emissions and b) including biogenic emissions.
Data are for August 11, 1999 at 16:00 and are expressed in ppbv.
In Figure 8, vertical O3 profiles for the five levels of the
model obtained from simulations for August 11, 1999 at the
Ibirapuera Park station. The results of the simulation, which
included biogenic emissions, show a small increase in O3
concentration at the surface, as well as at high altitudes (over
1000 m), at 13:00.
Figure 8 – Hourly simulated variation in the vertical profile of O3:
a) excluding biogenic emission and b) including biogenic emission.
Data are for August 11, 1999 for Ibirapuera Park air-quality station and
are expressed in ppbv. Level heights: level 1 = 59.5 m; level 2 = 238 m;
level 3 = 476 m; level 4 = 1037 m; level 5 = 1700 m.
In the vertical profile of O3 during the daylight hours,
one can see that the concentration gradients by altitude were
small. This was due to the heating of the surface and the resultant
mixing of air masses. Maximum concentrations at the upper
levels, stratification of the layers and a significant decrease in
O3 concentration near the surface were observed during the
night. This profile can be attributed to O3 produced during the
day and transported to higher levels. The O3 is then trapped in
the stable boundary layer and due to lack of proximity to NOx
sources, O3 consumption is reduced. The absence of O3 during
the nocturnal simulations can be attributed to an overestimation
of NO simulated values.
The results for the first period simulations and the
observed results for NO in the São Caetano do Sul station are
illustrated in Figure 9, as an example.
Volume 21(2)
Figure 9 – Hourly observed and model-simulated NO concentrations
from August 10 to August 12, 1999 for the São Caetano do Sul air-
quality station.
The simulation data show that the inclusion of biogenic
emissions resulted in a decrease in NO concentrations caused
by NO consumption in the reaction with free radicals. The
simulated NO concentration values were overestimated in
comparison with the observed values.
In these simulations, the behaviour of the model indicates
that three types of complications may have occurred in the
chemistry design of the model. It is possible that the values of
NO concentration inputs used were overestimated, that VOC
emissions were underestimated; that the chemical species
vertical transport was inappropriately described, or that there
was a combination of these factors.
In simulations including biogenic emissions, the
impact of biogenic emissions varied among the stations due to
factors such as proximity of emission sources. The effect (in
percentages) of those impact values on concentrations of O3,
PAN, NO and NO2 was calculated as follows:
 x =n 
 ∑ X pBIO ⋅100 
impact =  x =1 x = n  − 100 (5)
 


∑
x =1
Xp 

where: XpBIO is the value from simulations including biogenic
emissions and XP is the value from simulations excluding
biogenic emissions. The sum refers to all simulated hours.
The impact values were calculated for eight CETESB
stations for both periods and are illustrated in Table 3. The first
numbers in column indicated the results for August 10 to 12,
1999 and the second for August 23 and 24, 2000.
Simulations including biogenic emissions produced
different results than did those from which biogenic emissions
were excluded (illustrated in figures: observed and simulated
concentrations without biogenic emission). Those differences
are evidenced by variations in the concentrations of O3, NO,
NO2 and PAN. Analysing the mean concentration data from
simulations which included biogenic emissions, a 15.3%
increase in O3, a 1.7% increase in NO2, a 20.4% increase in
PAN, and a 2.4% decrease in NO was observed for first period.
Agosto 2006 Revista Brasileira de Meteorologia 197

Table 3 – Impact (%) of biogenic emissions on concentrations of O3, NO, NO2 and PAN for the eight CETESB air-quality stations. The first number
in each column it corresponds to the results for first period of simulate and the second number to another period of simulate.

Impact on O3 Impact on PAN Impact on NO Impact on NO2

Station
(%) (%) (%) (%)
Ibirapuera Park (+) 15.4 – (+) 5.9 (+) 21.2 – (+) 7.8 (-) 1.7 – (-) 1.2 (+) 1.5 – (+) 0.5
SCSU (+) 19.0 – (+) 6.6 (+) 23.2 – 0 (-) 2.5 – (-) 1.5 (+) 1.9 – (+) 0.5
Santana (+) 18.5 – (+) 10.2 (+) 31.5 – (+) 18.4 (-) 2.5 – (-) 2.4 (+) 3.3 – (+) 0.6
St. Amaro (+) 9.5 – (+) 2.4 (+) 14.7 – (+) 6.3 (-) 1.2 – (-) 0.09 (+) 0.9 – (+) 0.7
PQDP (+) 18.5 – (+) 10.2 (+) 31.5 – (+) 18.4 (-) 2.5 – (-) 2.4 (+) 3.3 – (+) 0.6
Diadema (+) 17.3 – (+) 4.2 (+) 20.2 – (+) 10.8 (-) 1.6 – (-) 3.8 (+) 0.7 – (-) 0.9
Cubatão (+) 11.2 – (+) 7.2 (+) 9.3 – (+) 4.0 (-) 6.5 – (+) 0.8 (+) 1.6 – (+) 2.0
IAG-Água Funda (+) 13.1 – (+) 4.0 (+) 11.3 – (+)8.8 (-) 0.6 – 1.3 (+) 0.5 – (-) 0.3
Average (+) 15.3 – (+) 6.3 (+) 20.4 – (+) 9.3 (-) 2.4 – (+) 1.5 (+) 1.7 – (-) 0.7
SCSU = São Caetano do Sul; PQDP = Parque D. Pedro II; IAG = Instituto de Astronomia, Geofísica e Ciências Atmosféricas.

In the Second period the values were lower and the impact over
concentrations result in an increase of 6.3%, 9.3% and 1.5%
for O3, PAN and NO2 respectively, although for NO a decrease
of 0.7 % was observed.
An increase in organic compound emissions promotes
an increase in the concentration of free radicals, leading to
increased O3 production and consumption of NO, which is
converted to NO2.
The values of isoprene and terpenes concentrations
simulated were all lower than 1 ppbv for both periods studied
as well as the observed values. Although the direct comparison
is not suitable, because the meteorological conditions of
periods are different, these results show that the model provide
consistent data.
Two simulations were performed for each period of
study. In the first one, values were set 30% higher than the
values reported in the literature (Table 2), and in the second one,
those same values were set 30% lower. In Table 4, the average
values for eight stations from these simulations are presented.
The results represent the impact (%) of these emission values
on concentrations of O3, NO, NO2 and PAN.
Table 4 – Estimation of the average impact of biogenic emissions on
concentrations of O3, NO, NO2 and PAN.
Species 30% Decrease 30% Increase
O3 (-) 4.3 (+) 3.8
NO (+) 1.0 (-) 0.5
NO2 (-) 0.2 (+) 0.6
PAN (-) 4.8 (+) 3.9
The positive (+) and negative (-) symbols indicate increases
or decreases in estimated species concentration values.
The results presented in Table 4 show that large variations
in biogenic emissions did not result in significant variations in
concentrations of O3, NO, NO2 or PAN. These results describe a
chemical reaction that shows that the processes of O3 formation
and degradation are non-linear and that control of O3 formation
is a non-linear function of decreases in the concentrations of
each O3 precursor.
4. CONCLUSIONS
The impact of biogenic emissions on the formation of
photochemical oxidants (primarily O3) was examined in this
study through the use of simulations for two different periods
employing a photochemical model.
The CIT model simulations that included biogenic
(isoprene and terpene) emissions showed the formation of O3
and other compounds. This effect was observed for all stations
studied. The impact of biogenic emissions on O3 formation was
significant mainly for the first period, resulting in an average
increase of 15.3%. Concentrations of PAN, NO and NO2 were
also affected, evidenced by 20.4% and 1.7% increases in mean
concentrations of PAN and NO2, respectively, and a 2.4%
decrease in mean NO concentration. For the second period
also were observed an impact of biogenic emissions over
concentrations of compounds, but of lower importance.
This study revealed potential interference by environmental
conditions (meteorology and chemical composition of the
atmosphere) in the processes of VOC reaction and O3 formation.
The results obtained for the MASP show that, due to their impact
on the chemistry of the O3 layer, biogenic emissions are important
and should be taken into consideration, even in urban areas,
because it have high potential of ozone formation.
198 L. Droprinchinski-Martins et al.
Further studies, of greater precision and complexity, are
warranted in order to ensure more accurate identification of
anthropogenic and biogenic emission sources. Measurements
of biogenic emissions from leaves and branches using
enclosure and surface-layer methods are important to be
accomplishment as well as other important parameters as PAR,
leaf temperature and foliar density. These data are required by
models in the module of biogenic inventory. The measurement
of these parameters are probably the most adequate to estimate
biogenic emissions, but consist in a difficult task, due to many
uncertainties related to the parameters required by models (for
example BEIS2). However a big effort should be done in this
way, because BVOCs participate of important chemical and
physical processes in atmosphere.
5. ACKNOWLEDGEMENTS
We would like to thank C. S. Pool, Institute of
Chemistry, University of São Paulo for the analysis of VOCs.
We are also grateful to our colleagues in the Department of
Atmospheric Sciences of the University of São Paulo for the
helpful suggestions. Air-quality data was kindly provided by the
technicians at CETESB (São Paulo Environmental Protection
Agency). This work was supported by grants from FAPESP
(Fundação de Amparo à Pesquisa de São Paulo; project nº
00/01400-2).
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