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Atmospheric Environment 39 (2005) 5219–5225 Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences V. Altuzar a , S.A. Toma´s a, , O. Zelaya-Angel a, , F. Sa´nchez-Sinencio a , J.L. Arriaga b a Departamento de Fı´sica, Centro de Investigacio´n y de Estudios Avanzados del IPN, AP 14-740, Me´xico 07360 DF, Me´xico b Laboratoriode Quı´mica de la Atmo´sfera,Instituto Mexicano del Petro´leo,Eje CentralLa´zaro Ca´rdenas 152, Me´xico 07730 DF, Me´xico Received 25 March 2004; received in revised form 21 August 2004; accepted 28 September 2004 Abstract Monitoring of atmospheric ethene was carried out in Mexico City with a 12 C 16 O 2 -laser-based photoacoustic spectrometer. We assessed the variation of the ethene content in atmospheric samples simultaneously collected in stainless-steel containers at three stations of the local government’s air quality monitoring network in November 1999 and March 2000. The ethene levels in November were higher than those detected in March, reaching up to 36.9 ppbV. In addition, continuous measurements of ethene were carried out in February 2001 for 1 week, with a time resolution of 1 min. It allowed recording of real-time ethene levels of up to 68 ppbV. A comparison between ethene profiles recorded on weekends and working days clearly shows a pronounced difference in concentration, which is almost three-fold higher on working days. r 2004 Elsevier Ltd. All rights reserved. Keywords: Ethene; CO 2 -laser; Photoacoustic spectroscopy; Vehicle exhaust-emission 1. Introduction Ethene is a gas of extreme importance in the fields of plant physiology and the environmental sciences. In plant physiology, this gaseous phytohormone plays a crucial role in many physiological processes. For instance, it is emitted by fruits and plants in response to saline, thermal, mechanical, or chemical stresses, and regulates processes such as ripening, growth, germina- tion, and senescence (Abeles et al., 1992). The environ- mental interest in this molecule is related to its anthropogenic origin, namely, its production in combus- tion processes that include fires, industry and mainly vehicle exhausts. As a consequence, ethene has been considered to be a potential human carcinogen, since this alkene is partly metabolized by mammals via ethene oxide, a direct-acting alkylating agent that induces cytogenetic alterations, mutations, and cancer. As claimed by To¨rnqvist (1994), exposure to 10 ppbV of ethene per hour during a week is expected to lead to a lifetime risk of cancer death amounting to approxi- mately 70 per 100,000. Since ethene is mostly detected at ppbV levels in urban atmospheres, the development of sensitive and selective detection systems that allow for its detection has been strongly encouraged during the last few years (Sigrist, 1994). During the last decades, air pollution in Mexico City has become the greatest concern. Mexico City, a metropolis with nearly 20 million inhabitants, is located on a high valley surrounded by mountains, at ARTICLE IN PRESS www.elsevier.com/locate/atmosenv 1352-2310/$ - see front matter r 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2004.10.002 Corresponding authors. Fax: +52 55 5061 3386. E-mail addresses: stomas@fis.cinvestav.mx (S.A. Toma´s), ozelaya@fis.cinvestav.mx (O. Zelaya-Angel).

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Page 1: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESS

1352-2310/$ - se

doi:10.1016/j.at

�Correspond

E-mail addr

[email protected]

Atmospheric Environment 39 (2005) 5219–5225

www.elsevier.com/locate/atmosenv

Atmospheric ethene concentrations in Mexico City:Indications of strong diurnal and seasonal dependences

V. Altuzara, S.A. Tomasa,�, O. Zelaya-Angela,�,F. Sanchez-Sinencioa, J.L. Arriagab

aDepartamento de Fısica, Centro de Investigacion y de Estudios Avanzados del IPN, AP 14-740, Mexico 07360 DF, MexicobLaboratorio de Quımica de la Atmosfera, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, Mexico 07730 DF, Mexico

Received 25 March 2004; received in revised form 21 August 2004; accepted 28 September 2004

Abstract

Monitoring of atmospheric ethene was carried out in Mexico City with a 12C16O2-laser-based photoacoustic

spectrometer. We assessed the variation of the ethene content in atmospheric samples simultaneously collected in

stainless-steel containers at three stations of the local government’s air quality monitoring network in November 1999

and March 2000. The ethene levels in November were higher than those detected in March, reaching up to 36.9 ppbV.

In addition, continuous measurements of ethene were carried out in February 2001 for 1 week, with a time resolution of

1min. It allowed recording of real-time ethene levels of up to 68 ppbV. A comparison between ethene profiles recorded

on weekends and working days clearly shows a pronounced difference in concentration, which is almost three-fold

higher on working days.

r 2004 Elsevier Ltd. All rights reserved.

Keywords: Ethene; CO2-laser; Photoacoustic spectroscopy; Vehicle exhaust-emission

1. Introduction

Ethene is a gas of extreme importance in the fields of

plant physiology and the environmental sciences. In

plant physiology, this gaseous phytohormone plays a

crucial role in many physiological processes. For

instance, it is emitted by fruits and plants in response

to saline, thermal, mechanical, or chemical stresses, and

regulates processes such as ripening, growth, germina-

tion, and senescence (Abeles et al., 1992). The environ-

mental interest in this molecule is related to its

anthropogenic origin, namely, its production in combus-

tion processes that include fires, industry and mainly

e front matter r 2004 Elsevier Ltd. All rights reserve

mosenv.2004.10.002

ing authors. Fax: +5255 5061 3386.

esses: [email protected] (S.A. Tomas),

vestav.mx (O. Zelaya-Angel).

vehicle exhausts. As a consequence, ethene has been

considered to be a potential human carcinogen, since

this alkene is partly metabolized by mammals via ethene

oxide, a direct-acting alkylating agent that induces

cytogenetic alterations, mutations, and cancer. As

claimed by Tornqvist (1994), exposure to 10 ppbV of

ethene per hour during a week is expected to lead to a

lifetime risk of cancer death amounting to approxi-

mately 70 per 100,000. Since ethene is mostly detected at

ppbV levels in urban atmospheres, the development of

sensitive and selective detection systems that allow for its

detection has been strongly encouraged during the last

few years (Sigrist, 1994).

During the last decades, air pollution in Mexico

City has become the greatest concern. Mexico City,

a metropolis with nearly 20 million inhabitants, is

located on a high valley surrounded by mountains, at

d.

Page 2: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESSV. Altuzar et al. / Atmospheric Environment 39 (2005) 5219–52255220

approximately 2270m over the sea level. Such moun-

tains work as natural wind barriers, obstructing the

dispersion of air pollutants released by industry and

emitted by over 4 million cars. As a result, frequent

thermal inversion phenomena and severe smog events

were reported from the 1980s to the mid 1990s (Blake

and Rowland, 1995).

Previously, we have used an infrared photoacoustic

spectroscopy to detect atmospheric ethene in Mexico

City. Air samples were simultaneously collected in

electropolished stainless-steel containers at three differ-

ent sites, and they were later analyzed in our laboratory

with a CO2-laser-based photoacoustic spectrometer

(Altuzar et al., 2001). We have also reported the

continuous (on-line) monitoring of ethene; such mea-

surement was recorded in a single sampling site in two

different seasons (Altuzar et al., 2003). Here, we

conducted measurement campaigns in order to analyze

the variation of the ethene content in atmospheric

samples collected at three sites in two different seasons.

In addition, we analyze in detail the ethene time profile

over a 1-week period, including a comparison between

profiles recorded in weekends and working days. The

analysis of the ethene time profile is complemented with

ozone and nitrogen oxides data.

2. Methodology

2.1. Experimental set-up

The photoacoustic (PA) effect is based upon the

conversion of electromagnetic energy into acoustic

energy (Sigrist, 1994; Harren and Reuss, 1997). A

system that is excited by the absorption of light and

that undergoes subsequent non-radiative de-excitation

processes transfers its electronic, vibrational, or rota-

tional energy into translational energy, producing a

temperature increase. When the absorption is modu-

lated, the temperature changes periodically, leading to

pressure (acoustic) oscillations that can be detected by a

sensitive microphone. The photoacoustic spectrometer

used in this work (Altuzar et al., 2003) consists of a

continuous wave 12C16O2 laser and a PA trace gas

detection system. The laser wavelength can be tuned at

around 80 lines in the 9–11 mm infrared region. The

intracavity laser power typically reaches 40 W at the

lines selected for measurement. The PA cell is placed

inside the cavity of the laser and is designed as a

cylindrical acoustic resonator, extended by two buffer

volumes, to amplify the generated sound wave due to

absorption. The volume of the acoustic resonator is

4.24 cm3, which implies that the resonator has an

exchange rate of 3.8 s when using a flow rate of 4 l h�1.

The laser beam is intensity-modulated by means of a

mechanical chopper locked at the resonance frequency

of the PA cell (1160Hz). The PA system was calibrated

using a certified gas mixture of ethene buffered in air

(1.2 ppmV ethene). The PA signal is recorded by means

of an electret microphone connected to a lock-in

amplifier.

The most general situation in PA gas detection

involves the measurement of multicomponent samples.

PA signals, normalized with the laser power to account

for power fluctuations, have thus to be measured on

several laser lines coinciding with absorption bands of

the compounds under study. A subsequent least-squares

analysis (Bernegger and Sigrist, 1990) provides the

concentration of the different gases constituting the

mixture. In the present work, we have restricted

ourselves to the detection of ethene. The 10P14

(l=949.48 cm�1) and 10P12 (l=951.19 cm�1) laser lines

were selected to determine the ethene concentration. At

these lines, the optical absorption coefficients for ethene

are 30.4 cm�1 atm�1 and 4.31 cm�1 atm�1, respectively.

The recording of the PA phase was not important

because CO2 and water vapor were eliminated from the

airflow by inserting KOH and CaCl2 scrubbers in

combination with a cold trap (Moeckli et al., 1998).

To avoid additional problems, Teflon tubing was used.

The time resolution is mainly imposed by the time

needed to position the grating on the selected laser lines.

It resulted in nearly 1min. The detection limit for ethene

was 100 pptV, as determined from a signal-to-noise ratio

equal to one when the PA cell is operated in a

continuous-flow mode. Estimating an average uncer-

tainty of 3% for the cell constant, 2% for the certified

gas concentration, 1% for the 4 l h�1 flux of molecules

transported through PA cell, and 1% of random error of

the measurement, one finds an overall uncertainty for

PAS data of about 7%.

2.2. Air sampling

Electropolished stainless-steel canisters were used to

collect air samples. Field campaigns were conducted in

collaboration with the Instituto Mexicano del Petroleo

(IMP). The campaigns took place from 22 to 26

November 1999 and from 20 to 24 March 2000. Uptake

of ambient air was achieved by the use of an automated

portable air pumping system, type VOCS, provided with

a mass flow controller. The equipment was placed at 3m

above the ground. Sampling was simultaneously per-

formed from 06:00 to 09:00 h at three different sites,

at a filling rate of 33ml min�1. The selection of the

sampling sites was made according to meteorological

conditions, especially wind speed and wind direction, as

well as to urban characteristics, such as industrial acti-

vity and traffic density. The sites selected were Xalostoc,

La Merced and Pedregal (Fig. 1). Xalostoc, located

in a northeastern suburb of Mexico City, presents

intense industrial activity, as well as a high density of

Page 3: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESS

440000

460000

480000

500000

520000

540000

2080000

2100000

2120000

2140000

2160000

2180000

2200000

2220000

Xalostoc

Merced

Pedregal

Cinvestav

N

S

W

UTMX, M

UT

MY

, M

E

Fig. 1. Map of the metropolitan area of Mexico City showing

the location of the sampling sites: (a) Xalostoc, (b) La Merced,

(c) Pedregal, and (d) CINVESTAV. UTMX and UTMY stand

for the longitude and latitude, respectively, of the Universal

Transverse Mercator grid.

20 21 22 23 240

10

20

30

40

50

60

March 2000

22 23 24 25 260

10

20

30

40

50

60

La Merced Pedregal

ethe

ne c

once

ntra

tion

[ppb

V]

November 1999

Xalostoc

Fig. 2. Ethene concentration measured in air samples collected

simultaneously in Xalostoc, La Merced, and Pedregal. Air

sampling was carried out in November 1999 and March 2000.

V. Altuzar et al. / Atmospheric Environment 39 (2005) 5219–5225 5221

heavy-duty automotive vehicles. La Merced, situated in

central Mexico City, near downtown, is characterized by

a strong commercial and administrative activity, with

intense flux of cars and small-to-medium-size trucks.

Pedregal is a southwestern wealthy residential area with

low traffic density.

Real-time monitoring of ethene was carried out at the

Department of Physics, Centro de Investigacion y de

Estudios Avanzados del Instituto Politecnico Nacional

(CINVESTAV-IPN), located in northern Mexico City

(see Fig. 1). This sampling site is situated in a green area

of about 4� 104 m2, about 100m away from an avenue

with heavy traffic density. Ambient (outdoor) air was

continuously pumped to the photoacoustic spectrometer

from 05:00 to 23:00 h, from 17 to 23 February 2001.

3. Results and discussion

3.1. Samples collected in canisters

The ethene concentrations determined in integrated

samples collected in November 1999 and March 2000

are shown in Fig. 2. Except for 1 day, the highest ethene

concentrations in March were detected in the industrial

site, Xalostoc, with a mean value of 36.9 ppbV. It

supports previous works reporting this place as one of

the most polluted suburbs of Mexico City (Edgerton

et al., 1999). In spite of a strong industrial activity,

which permanently contributes to air pollution, noctur-

nal background levels of around 5 ppbV imply that

ethene comes mostly from vehicle emissions. This result

is in agreement with studies concluding that urban

ethene is primarily produced by motor vehicles (Doskey

et al., 1992). The place with the second highest presence

of ethene was La Merced (near downtown), with a mean

value of 34.1 ppbV, whereas Pedregal showed a mean

concentration of 11.6 ppbV. Regarding the field cam-

paign carried out in November, a similar order was

observed, namely, the highest ethene content was found

in Xalostoc followed by La Merced and Pedregal; the

measured concentrations were 40.3, 37.0, and 18.7 ppbV,

respectively. The fact that the ethene levels detected in

November are higher than those registered in March is

most probably due to a lower initial height of the

atmospheric boundary layer (ABL), associated with a

lower ambient temperature. Particularly, the average

temperature measured in La Merced was 4.570.4 1C

Page 4: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESSV. Altuzar et al. / Atmospheric Environment 39 (2005) 5219–52255222

lower in November than in March, with a minimum

8.3 1C registered at 07:00 h and a maximum 19.5 1C

reached at 16:00 h.

Measurements of ambient ethene in Mexico City have

been previously performed by other authors (Blake and

Rowland, 1995). These researchers determined by gas

chromatography ethene levels of 15.5 and 27.8 ppbV in

samples collected in canisters at 06:00 and 12:00 h,

respectively. Their sampling site was Zocalo, which is

located near La Merced. As will be shown below, levels

at 06:00 h are low mainly due to low vehicular activity.

Therefore, for comparison with our results, we have

considered the second datum. In our case, except for the

unusually high value obtained on 22 March (see Fig. 2),

the mean value in La Merced was 28.8 ppbV, in

agreement with the levels reported by Blake and

Rowland (1995).

Mugica et al. (1998) have also reported the ambient

ethene concentration in samples collected in tunnels and

crossroads in Mexico City. They found concentration

values in the interval from 0.49 to 4.06 ppbC%,

measured with a gas chromatograph. It should be

mentioned that in such articles, the abundance of each

hydrocarbon in the source profile is the ratio of each

concentration in ppbC to total non-methane organic

compounds in ppbC, the latter varying from 7.27 to

30.79 ppmC. The ethene concentration therefore ranges

from 17.81 to 625 ppbV. Using the CO2-laser PA

technique, Sigrist et al. have reported ethene levels of

the order of 20 ppbV in open-traffic urban areas (Meyer

4 6 8 10 12

0

10

20

30

40

50

60

70

ethe

ne c

once

ntra

tion

[ppb

V]

dayt

Fig. 3. Time profile of ethene recorded with a CO2-laser-based photo

(Tuesday 20 February, 2001).

and Sigrist, 1990) and of 250 ppbV inside tunnels

(Moeckli et al., 1996) in Switzerland. All these data

are in correspondence with the data obtained in our

work and confirm the reliability of our system.

3.2. Real time (on-line) measurements

Fig. 3 shows the real-time concentration profile of

ambient ethene measured at the facilities of CINVES-

TAV-IPN on a typical weekday (Tuesday 20 February

2001). In general, two broad peaks were observed in the

ethene concentration versus daytime plot. The first peak

increased steeply from a background level of approxi-

mately 5 ppbV after 05:00 h and reached a maximum

value of 68 ppbV at 08:20 h. Thereafter, the ethene

concentration decreased down to 3 ppbV, oscillating

around this level from 12:20 to 18:20 h. A second peak

with a lower intensity took place at 20:30 h. This profile

is in agreement with the measurements performed in

Mexico City with an open-path Fourier transformed

infrared spectroscopy (Grutter et al., 2003). The intense

vehicle emissions, the expansion of the ABL, as well as

the presence of compounds that react with ethene play

an important role on these patterns (Horie and

Moortgat, 1998). Moreover, the high emission factor

for ethene due to cold-start conditions of vehicles

strongly influences the high concentrations observed in

the morning rush-hours; this is accentuated by the

presence of an old and technologically heterogeneous

vehicular fleet (Schifter et al., 2000).

14 16 18 20 22 24ime [h]

acoustic spectrometer during a typical weekday in Mexico City

Page 5: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESSV. Altuzar et al. / Atmospheric Environment 39 (2005) 5219–5225 5223

The ABL is greatly influenced by the topography of

the city and the thermal forcing. Raga et al. (1999) and

Doran et al. (1998) studied the time evolution of the

ABL and found that it is stable until 200m above the

ground at 06:00 h and that it experiences an expansion

up to approximately 1 km at 11:00 h; then, the ABL

height increases rapidly, reaching between 2500 and

3000 m in the late afternoon. It is also known that the

ethene released into the troposphere can be removed by

reaction with hydroxyl radical. The production of this

alkene is enhanced by the topographic setting of Mexico

City and a relatively high insolation related to its

tropical latitude (191190N). Particularly, ozone exceeded

the maximum permissible exposure regulations on most

days in the mid 1990s (MARI, 1994). Atkinson (2000)

has estimated that the atmospheric ethene lifetime is 1.4

days, due to a 12-h daytime average OH radical

concentration of 2� 106 molecules cm�3. Other factor

contributing to ethene removal is associated with the

presence of high ozone levels. Thus, the reaction of NOx,

ozone, atomic oxygen, and hydroxyl radicals with

ethene contribute to the destruction of the latter

compound (Fenske et al., 2000).

By monitoring ethene on days with expected differ-

ences in the time profile of this pollutant, e.g. on

weekends and working days, the excellent sensitivity of

our instrument was tested. Ethene was measured during

the week from Saturday 17 to Friday 23 in February

2001, and in Fig. 4 the profile of two consecutive days

(Sunday 18 and Monday 19) was plotted. The highest

4 6 8 10 12

0

10

20

30

40

50

60

ethe

ne c

once

ntra

tion

[ppb

V]

dayt

Fig. 4. Comparison of the time profile of ethene recorded during two

value detected on Sunday reached 18 ppbV at around

12:30 h. On Monday morning, the maximum ethene

concentration was nearly three times higher, reaching

53 ppbV at 08:20 h. The difference in concentration is a

clear indication of the contrasting traffic density

observed during weekends and working days. Moreover,

the time lag between such maxima reflects a delay in the

start of activities of most people on Sunday. As seen

from the time lag of the second maximum, the activities

remain delayed for the whole day, although with a

smaller difference in the evening.

Fig. 5 presents the ethene profile registered at

CINVESTAV during the three consecutive days 17–19

(Saturday–Monday) of February 2001 For clarity, the

profiles recorded from February 20 to 23 are not

shown. The maximum concentrations were detected in

the range from 14 to 68 ppbV. As expected, the highest

ethene concentrations were invariably measured on

working days, with the global maximum taking place

on Tuesday. The mean dose of human exposure to

ethene was obtained by integrating the area under the

curve from 05:00 to 22:00 h, resulting in 13.7 and

7.8 ppbV on working days and weekends, respectively.

For comparison, the time profile of nitrogen oxides

(NOx) and ozone (O3) are also illustrated in Fig. 5.

These pollutants were monitored in La Merced by an

air-pollution-monitoring government network, the so-

called RAMA (Automatic Network for Atmospheric

Monitoring). No information about them is available

at the CINVESTAV-site. In spite of this, a good

14 16 18 20 22 24

ime [h]

Monday

Sunday

consecutive days in February 2001 (Sunday 18 and Monday 19).

Page 6: Atmospheric ethene concentrations in Mexico City: Indications of strong diurnal and seasonal dependences

ARTICLE IN PRESS

0 12 24 36 48 60 720

50

100

150

200

MondaySundaySaturday

ethe

ne, o

zone

and

NO

x [p

pbV

]

time [h]

C2H4

O3

NOx

Fig. 5. Time profile of ethene, nitrogen oxides, and ozone recorded in the winter of 2001, from 17 to 19 February. For clarity, the

profiles recorded from 20 to 23 February are not shown. Ethene was monitored at CINVESTAV, whereas the nitrogen oxides and

ozone data were recorded at La Merced by the Automatic Network for Atmospheric Monitoring.

V. Altuzar et al. / Atmospheric Environment 39 (2005) 5219–52255224

correlation between these profiles was found. Specifi-

cally, both ethene and NOx peaked at around the same

time. This result is expected because ethene and NOx are

strongly associated with vehicular emissions. On the

other hand, the maximum ozone concentrations were

measured between 13:00 and 15:00 h, showing the

photochemical nature of this compound.

4. Conclusions

In summary, infrared photoacoustic spectroscopy has

been successfully applied to the detection of atmospheric

ethene in Mexico City. The on-line monitoring of ethene

has revealed that levels of about 68 ppbV are frequently

reached in the morning. A mean dose of human

exposure to ethene of over 10 ppbV on working days

represents a potential risk for adverse human health

conditions, indicating an urgent need for additional

emissions control.

Acknowledgments

The authors thank the Instituto Mexicano del

Petroleo that partially financed the project IMP-FIES-

97-07-VI and to the RAMA authorities for allowing the

use of the meteorology database. This work was also

supported by CONACyT via the Project 33126-E.

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