ENVIRONMENTAL ENGINEERING SCIENCE

Volume 31, Number 8, 2014

ª Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2014.0100

Photooxidation of Gaseous Benzene by 185 nm VUV Irradiation

Haibao Huang,* Huiling Huang, Lu Zhang, Peng Hu, Ying Xu, Xinguo Ye,
Xiaoshan Liang, Jiandong Chen, and Muyang Ji

School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou, China.

Received: February 23, 2014 Accepted in revised form: May 13, 2014

Abstract
Benzene is a toxic, volatile organic pollutant and does great harm to both human beings and atmospheric en-
vironment. Vacuum ultraviolet (VUV) photooxidation, an emerging efficient process for the oxidation of pol-
lutants, was used to destroy gaseous benzene. The effect of key operating parameters such as relative humidity,
residence time, initial benzene concentration, and reaction temperature was investigated to study the perfor-
mance and mechanism of benzene VUV photooxidation. Results indicated that vapor can greatly improve
benzene removal efficiency and inhibit ozone formation since it can be used by energetic VUV photons to

produce hydroxyl radicals ( OH), highly reactive for benzene oxidation. The increase of residence time and
decrease of initial benzene concentration can greatly improve both the removal efficiency and mineralization

rate of benzene. OH is mainly responsible for benzene oxidation in the VUV photooxidation process.

Key words: benzene; hydroxyl radical; photooxidation; vacuum ultraviolet; vapor

Introduction Driessen et al., 1998; Jeong et al., 2005). It is very inter-

esting to develop other VOC destruction processes without
W ith the rapid development of economic and in-
creasing demand of organic chemical materials, the
emission of volatile organic compounds (VOCs) was dra-
catalysts.
Vacuum ultraviolet (VUV) photooxidation, as an
emerging, efficient, and simple process for pollutant oxi-
matically increased correspondingly (Atkinson, 2000).
dation, has been paid much attention recently. VUV lamps
VOCs not only contribute to the high incidence of asthma,
can emit partial 185 nm UV light and energetic photons.
allergies, and building-related symptoms but also cause
Under VUV irradiation, oxygen and water are dissociated
serious compound atmospheric pollution such as photo-
into highly reactive oxidants such as hydroxyl radicals
chemical smog pollution and haze (Korologos et al., 2012). 
( OH) (Alapi and Dombi, 2007). VUV photooxidation has
Therefore, it is vital to remove them to improve air quality.
been intensively studied for the treatment of wastewater.
Benzene, a typical important VOC pollutant, does great
Some efforts have also been made to destruct gaseous pol-
harm to both human being and atmospheric environment
lutants such as naphthalene (Zhao et al., 2013), a-pinene
(Korologos et al., 2011). It is highly toxic and carcinogenic.
(Chen et al., 2010), and chlorinated methanes (Alapi and
Some methods such as adsorption, catalytic oxidation, bi-
Dombi). The removal efficiency of benzene photocata-
ological degradation, plasma and photocatalysis have been
lytic oxidation under the irradiation of 254 nm is less than
applied to remove it (Ollis, 1985; McGregor et al., 1988;
10% of that of VUV photooxidation under similar condi-
Sundstrom et al., 1989; Kang et al., 2002; Daifullah and
tions (such as operating parameters, the power of UV lamp)
Girgis, 2003; Wang et al., 2005; Farhadian et al., 2008;
to this study (not shown here). Therefore, VUV photooxi-
Darracq et al., 2012). As for the adsorption system, the
dation provides an economic and efficient method for
absorbents easily get saturated and need frequent regener-
VOC removal. However, few attempts were made to the
ation, which leads to tedious operation and extra energy
study on benzene removal and its mechanism. Especially,
consumption. Catalytic oxidation is one of the most efficient
the way that water vapor is involved in the reaction and
processes for VOC abatement. However, it is greatly limited
the contribution of different active species in this process
by disadvantages such as high cost and deactivation of
is still unclear.
catalysts (Kosusko et al., 1988; Agarwal and Spivey, 1993;
In this experiment, a VUV low-pressure Hg-lamp was used
to destruct benzene. The VUV lamp has a peak spectral
*Corresponding author: School of Environmental Science and
Engineering, Sun Yat-Sen University, Guangzhou 510275, China. emissive power at 254 nm and a smaller (about 8%) emission
Phone: (8620)3933-6475; Fax: (8620)3933-6475; E-mail: seabao8@ at 185 nm. The removal efficiency of benzene, mineralization
gmail.com rate, and ozone concentration were studied under different

481
482
key operating parameters such as relative humidity (RH),
residence time, initial benzene concentration, and reaction
temperature. The mechanism of benzene VUV photooxida-
tion was also proposed. This study provided an insight into
VUV photooxidation in benzene abatement.
Experimental
Experiments were performed in a home-made flow reactor
under different ranges of RH (0–95%), flow rate (0.5–2 L/
min), initial benzene concentration (25–200 ppm), and tem-
perature (21C, 36C, 48C). The experimental setup is
shown in Fig. 1. The setup constituted three parts: gas dis-
tribution, VUV photooxidation, and gas analysis system. The
gas from zero air generator is dry and free of CO, CO2, and
hydrocarbon. It was used to bubble water and benzene liquid
to generate water and benzene vapor, respectively. The
benzene concentration, humidity, and gas flow can be regu-
lated by the mass flow controllers (S49; Horibametron). Two
VUV lamps (4 W; Sungreen) were vertically placed inside a
glass reactor with a diameter of 7 cm and an effective volume
of 0.5 L. The effluent concentrations of benzene, CO, and
CO2 formed from benzene oxidation were monitored by gas
chromatography (GC) (GC9790II; Fuli) equipped with an
FID and methanizer online. The ozone concentration at the
outlet was measured by an ozone analyzer (202; 2B Tech-
nology). Residual ozone was decomposed by an ozone de-
composition catalyst before emission to the air.
Results and Discussion
Effect of water vapor
To study the effect of water vapor, the initial benzene
concentration and the flow rate were fixed at 50 ppm and 1 L/
FIG. 1. Schematic diagram
of experimental setup.
HUANG ET AL.
min, respectively, and RH was in the range 0–95%. Figure 2
shows the effect of RH on benzene removal efficiency. Results
indicated that benzene photooxidation is significantly affected
by water vapor. Benzene removal efficiency was only 12.5% at
0% RH, while it was greatly increased to 27.1% at 25% RH.
Benzene removal efficiency reached 37.9% at 50% RH, which
is about 3 times of that at 0% RH. With further increased RH,
benzene removal efficiency did not significantly change when
RH was higher than 50%. Therefore, water vapor can greatly
promote benzene oxidation.
The possible pathways for benzene destruction under VUV
irradiation include (1) direct photolysis by energetic photons
emitted from 185 nm VUV light, (2) oxidation by active
oxygen generated from oxygen dissociation by 185 nm pho-

tons, and (3) oxidation by hydroxyl radicals ( OH) (Bergonzo
and Boyd, 1993; Hashem et al., 1997; Zhang et al., 2004).
The pathways to form active species are as follows:
H2 O þ hm (185 nm)/ H þ  OH (1)
O2 þ hm (185 nm)/2 O 
(2)

O þ H2 O/2 OH (3)

O þ O2 /O3 (4)
where O represents the first excited state as in O(1D), which

is highly active and can react with H2O to form hydroxyl
radicals.
It is necessary to clarify the contribution of various
pathways and active species to benzene oxidation. To study
the contribution of photolysis, the experiment was con-
ducted in dry N2 gas flow, in which there is no H2O and
 
oxygen. O and OH is not involved and photolysis is the
only pathway to benzene oxidation. The removal efficiency
PHOTOOXIDATION OF GASEOUS BENZENE BY 185 NM
FIG. 2. Effect of relative humidity (RH) on the removal
efficiency of benzene under vacuum ultraviolet (VUV)
photooxidation (initial benzene concentration: 50 ppm, flow
rate: 1 L/min).

of benzene is only 5.5%. To identify the contribution of O,
the experiment was conducted in dry air flow, in which

there is no H2O and OH is not involved in benzene oxi-
dation. The removal efficiency of benzene is 12.5%, as
shown in Fig. 2. It can be deduced that only about 7%
 
benzene was oxidized by O after excluding the contribu-
tion of photolysis. In case of 50% RH, the removal effi-
ciency of benzene reached 37.9%. It can be deduced that

25.4% benzene was oxidized by OH after excluding the
 
contribution of photolysis and O. The contribution of dif-
ferent pathways on benzene removal is shown in Fig. 3. It is

clear that OH is mainly responsible for the removal of
benzene.
VUV light with 185 nm wavelength corresponds to pho-
ton energy of 6.7 eV, which is larger than the bond disso-
ciation energy (BDE) of the CeC bond of benzene
(6.04 eV). One hundred eighty-five nanometer energetic
photons can directly destruct the benzene ring. However,
the BDE of benzene is larger compared with the OeH bond
of water molecule (5.11 eV) (McKoy, 2003) and OeO bond
of oxygen molecule (5.12 eV). Therefore, water and oxygen
molecules are easier to be broken down by energetic pho-
tons than benzene. In addition, the concentrations of water
and oxygen are much higher compared with benzene. As a
result, the contribution of direct photolysis to benzene re-
moval is not crucial, as confirmed in Fig. 3. Compared with
the reaction of O3 generation ( O + O2/O3), the reaction of


OH generation ( O + H2O/2 OH) can proceed quickly
 
since its reaction rate constant is 2.2 · 10 - 10 cm3/(mol$s),
while that of O3 generation is only 5.6 · 10 - 34 cm3/(mol$s)

(Atkinson et al., 2004). The rate constant of OH with
benzene (1.23 · 10 - 12 cm3/[mol$s]) (Taatjes et al., 2010) is
much larger compared with O (1.16 · 10 - 14 cm3/[mol$s])

 Effect of residence time
(Atkinson, 1994). OH is much more active for benzene
 
oxidation than O. As a result, OH dominated benzene
oxidation in the VUV photooxidation process, as confirmed
in Fig. 3. Since the molar absorption coefficient of oxygen
VUV IRRADIATION 483
FIG. 3. Contribution of different pathways on benzene
removal under VUV photooxidation (initial benzene con-
centration: 50 ppm, flow rate: 1 L/min).
(eH2O = 36 mol/dm3) at 185 nm wavelength is larger com-
pared with water (eH2O = 19 mol/dm3) (Alapi and Dombi,
2007), the oxygen concentration (about 21 vol.%) is also
much larger than the water concentration (*0.5 vol.%).
Energetic photons from 185 nm irradiation have more

chance to be absorbed by oxygen to form O than by water.

OH should be mainly formed from the reaction of H2O
with O instead of direct water photolysis, which well
agreed with Alapi and Dombi (2007). Therefore, it is un-
derstandable that water vapor played a vital role in the VUV
photooxidation process since water vapor is essential to
OH formation. It is also found from Fig. 2 that benzene
removal efficiency was slightly increased with the fur-
ther increase of RH higher than 50%. It is possibly subject
to the limited amount of energetic photons and concentra-

tion of OH.
Ozone formed from 185 nm UV irradiation is also
greatly influenced by water vapor. The effect of RH on the
ozone concentration is shown in Fig. 4. It is quite different
from its effect on benzene removal. The ozone concen-
trations were decreased with the increase of RH in the
range of 0–50%, and then showed little changes with the
further increase of RH over 50%. The ozone concentra-
tion is 266 ppm at 0% RH, while it dropped to about
120 ppm at 50% RH and to nearly 100 ppm at 95% RH.
VUV light can be absorbed by the increased moisture,
leading to less irradiation by O2 and O3 formation. In ad-
dition, the increase of water vapor can promote the reaction
of OH generation ( O + H2O/2 OH), which inhibits the
  
reaction of O3 generation ( O + O2/O3), as discussed

 
above. Furthermore, benzene oxidation by O and OH can
promote the decomposition of O3, resulting in the de-
creased O3 concentration.
To study the residence time on benzene removal effi-
ciency, the initial benzene concentration and RH were kept at
50 ppm and 50%, respectively. The flow rates varied from 0.5
484
FIG. 4. Effect of RH on the ozone concentration under
VUV photooxidation (initial benzene concentration: 50 ppm,
flow rate: 1 L/min).
to 2 L/min, and the corresponding residence times spanned
from 60 to 15 s. As shown in Fig. 5, benzene removal effi-
ciency decreased from 65.5% to 20% with the increase of
flow rates. A similar behavior was observed in photocatalytic
oxidation of toluene by Sleiman et al. (2009). In the VUV
process, the amount of photons absorbed by per unit volume
air was decreased with the increase of flow rate. Oxygen,
water, and benzene molecules have less chance to be acti-

vated by energetic photons at a higher flow rate. The O and

OH amount is limited by the amount of energetic photons
emitted from 185 nm irradiation. The decrease of residence
time led to the drop of benzene removal efficiency. However,
the actual amount of removed benzene, which took account
of both the gas flow rate and benzene removal efficiency, was
only slightly increased with the increase of gas flow rate, as
shown in Fig. 5.
FIG. 5. Effect of flow rate and residence time on benzene
removal efficiency and amount under VUV photooxidation
(initial benzene concentration: 50 ppm, RH: 50%).
HUANG ET AL.
FIG. 6. Effect of flow rate on the mineralization rate of
benzene under VUV photooxidation (initial benzene con-
centration: 50 ppm, RH: 50%).
The benzene mineralization rate represents the degree of
complete oxidation of removed benzene. It is defined as
follows:
[CO2]out þ [CO]out
mineralization rate ¼  100%
6([Benzene]in  [Benzene]out )
where [CO2]out and [CO]out represents the concentration of
CO2 and CO generated from benzene oxidation, and [Ben-
zene]out and [Benzene]in is the benzene concentration at the
outlet and inlet of the reactor, respectively.
Although benzene cannot be efficiently mineralized by the

direct irradiation of VUV, OH from the irradiation of VUV
in the presence of moisture is highly active and can com-
pletely oxidize benzene into CO2. Figure 6 shows the varia-
tion of the benzene mineralization rate as a function of flow
rates. As it can be seen, the mineralization rates of benzene at
stable stage are decreased with the increasing gas flow rate.
The mineralization rates of benzene reached 90% at a flow
rate of 0.5 L/min, while it dropped to about 60% at a flow rate
of 2 L/min. It is proposed that there was not enough residence
time to completely oxidize benzene due to the increasing flow
rates and benzene molecules. The results also imply that
some intermediates are formed from benzene destruction.
Further work will be focused on the identification and elim-
ination of the intermediates.
Effect of initial benzene concentration
The concentrations of benzene emitted from industrial
processes generally vary from dozens of ppm to hundreds of
ppm. To study the effect of benzene concentration, the RH
and flow rate were fixed at 50%, respectively. The benzene
concentration varied from 25 to 200 ppm. The effect of initial
concentration on benzene removal efficiency is shown in Fig.
7. It was decreased significantly from 48% to 14% when the
initial concentration was increased from 25 to 200 ppm. Since
the benzene photooxidation strongly depends on the amount
PHOTOOXIDATION OF GASEOUS BENZENE BY 185 NM
FIG. 7. Effect of initial benzene concentration on removal
efficiency of benzene under VUV photooxidation (flow rate:
1 L/min; RH: 50%).
of oxidants, benzene molecule under conditions of low con-
centration has more chance to be oxidized.
The effect of initial concentration on the actual amount of
removed benzene was also investigated, as shown in Fig. 8. It
is noted that the amount of removed benzene was obviously
increased when the initial benzene concentration was in-
creased from 25 to 100 ppm. At low-concentration levels,
 
partial energetic photons and active oxidants ( O and OH)
were attenuated and not involved in benzene oxidation. As
the initial benzene concentration was increased, more ener-
getic photons and active oxidants were absorbed and utilized.
However, the actual amount of removed benzene negligibly
changed as the initial benzene concentration was further in-
creased from 100 to 200 ppm due to the limited energetic
photons and active oxidants generated from VUV lamps.
This might be because of the competitive adsorption of
photons between benzene and oxygen molecules since they
have similar absorbance at 185 nm. Less oxygen molecules
FIG. 8. Effect of initial benzene concentration on the
amount of removed benzene under VUV photooxidation
(flow rate: 1 L/min; RH: 50%).
VUV IRRADIATION 485
FIG. 9. Effect of initial benzene concentration on ozone
concentration under VUV photooxidation process (flow rate:
1 L/min; RH: 50%).
would be decomposed to active oxygen atoms because of an
increasing benzene concentration. This will accordingly re-

duce the concentration of OH and, ultimately, lead to the
decreased amount of removed benzene.
Figure 9 shows the variation of ozone concentration as a
function of initial concentration. Obviously, the ozone
concentration was decreased with an increase of initial

concentration because most active oxygen atoms ( O) had
reacted with benzene, leading to generate less O3 ( O + 
O2/O3). In addition, the adsorption competition of VUV
light between oxygen molecules and benzene molecules, as
discussed above, would also lead to the decrease of ozone
concentration.
Effect of temperature
To evaluate the effect of temperature on benzene removal
efficiency and outlet ozone concentration, the experiments
were conducted at temperatures of 21C, 36C, and 48C,
respectively. Table 1 shows the results at three different
temperatures. With increasing temperatures, the benzene
removal efficiency and ozone concentration were increased
from 25.9% to 37.7% and from 102.7 to 128 ppm, respec-
tively. Increased temperature could not only promote the
formation of hydroxyl radicals ( O + H2O/2 OH) but also
 

accelerate reaction between OH and benzene molecules.
Similarly, the increase of reaction temperature can also ac-
celerate the reaction ( O + O2/O3), leading to the increase of

ozone concentration at a higher temperature.
Table 1. Benzene Removal Efficiency and Ozone
Concentration in Different Temperatures
Temperature (C)
21 36 48
Benzene removal efficiency (%) 25.9 29.6 37.7
Ozone concentration (ppm) 102.7 117.1 128
486
Conclusions
The effect of key operating parameters such as RH, resi-
dence time, initial benzene concentration, and reaction tem-
perature was investigated to study the performance and
mechanism of benzene VUV photooxidation. Results indi-
cated that vapor can greatly improve benzene removal effi-
ciency and reduce the ozone concentration since it can be

used by energetic VUV photons to produce OH, which is
highly reactive for benzene oxidation. The increased resi-
dence time and the decreased initial benzene concentration
can greatly improve both the benzene removal efficiency and
mineralization rate since benzene has more chance to be

oxidized by active species. OH dominates benzene oxidation
in the VUV photooxidation process.
Acknowledgments
The authors gratefully acknowledge the financial support
from the Research Fund for the Doctoral Program of Higher
Education of China (No. 20120172120039), the National
Nature Science Foundation of China (No. 51208207), the
Research Fund Program of Guangdong Provincial Key La-
boratory of Environmental Pollution Control and Remedia-
tion Technology (No. 2013K0001), and the Fundamental
Research Funds for the Central Universities (No. 13lgzd03).
Author Disclosure Statement
No competing financial interests exist.
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