Atmospheric Environment Vol. 28, No. 1, pp. 141-148, 1994. 1352-2310/94 $6.00+0.

00
Printed in Great Britain. Pergamon Pr~'~ Ltd

COMPARISON OF OZONE EXPOSURE CHARACTERISTICS

IN FORESTED REGIONS NEAR MEXICO CITY AND
LOS ANGELES
PAUL R. MILLER
Pacific Southwest Research Station, Forest Service, U. S. Department of Agriculture, 4955 Canyon Crest
Drive, Riverside,CA 92507, U.S.A.

MARIA DE LOURDES DE BAUER a n d ABEL QUEVEDO NOLASCO

Programa de Agrometeorologla, Coleglo de Postgraduados, 56230 Montecillo-Chapingo, Edo. M6xico

TOMAS HERNANDEZTEJEDA
Instituto Nacional de InvestigacionesFores/ales Y Agropecuarias,Ave. Progreso # 5, Col. Coyacan, 04110,
M6xico, D. F.

(First received 8 December 1992 and in final form 12 February 1993)

Abstract--This comparison of forest exposure to ozone in the vicinity of M6xico City and Los Angeles
provides preliminary evidence of the seasonal differencesin ozone concentrations. Summer concentrations
near M6xico City are not as high as those near Los Angelesbecausemost of the precipitation and associated
cloudiness occurs near M6xico City during the months of June through September. Winter concentrations
remain nearly as high as summer concentrations at M6xico City, because in winter skies are clearer and
incident sunlight remains high. Latitudinal influenceson solar zenith angle and the higher altitude of the
M6xico City region both contribute to a higher actinic flux than in the Los Angeles region. The primary
difference in forest exposure is that there is very little respite from adverse ozone concentrations during the
entire year in the M6xico City region. Also, the rainy summer season would likelydiminish water stress and
result in greater ozone uptake at the Desierto de los Leones compared to dry summer conditions in
California. The closer proximity of the Desierto de los Leones monitoring site to the urban area also
contributes to high winter exposures. There is some respite from exposure during the winter in the San
Bernardino mountain region; however, summer concentrations are higher than near M6xico City. The
greater transport distance from the Los Angelessource region also contributes to lower winter exposures.

Key word index: Ozone, M6xico, California, conifers, injury.

INTRODUCTION M6xico City is located in a broad valley at the

The Los Angeles and M6xico City regions are reputed
to have very severe photochemical oxidant air pollu-
tion problems. The purpose of this paper is to provide
a preliminary exploration of similarities as well as
differences in seasonal changes in ozone concentra-
tions at mountain locations downwind from these
metropolitan areas.
In the mid-1980s symptoms resembling ozone in-
jury were reported on Pinus hartweoii Lindl. (de Bauer
et al., 1985) and P. montezumae Lamb. var. lindleyi
(Hernandez and de Bauer, 1984) in the mountains to
the south and southwest of M6xico City. By this time
considerable morbidity and mortality of Abies re-
ligiosa Schl. were reported in the same general region
(Vasquez, 1987). No ozone monitoring data were
available for the rural areas in question; however,
much circumstantial evidence was presented to im-
plicate ozone as the cause (de Bauer and Krupa, 1990).
For example, exposure of indicator plants in M6xico
City suggested the presence of damaging concentra-
tions of ozone in the early 1970s (de Bauer, 1972).
141
southern end of the Central M6xican plateau at an
elevation of 2240 m (7349 ft). To the south rises the
Ajusco range with mountains as high as 3930 m, and
to the east are the prominent volcanoes Popocatepetl
(5465 m) and Iztaccihuatl (5230 m). These mountains
restrict horizontal advection and thus are a major
cause of the confinement of air pollution.
A major controlling feature of M6xico City's wet
and dry tropical climate is the Intertropical Conver-
gence Zone (ITCZ) (Metcalfe, 1987). In summer the
ITCZ moves north, accompanied by the semi-perma-
nent Bermuda-Azores and the East Pacific highs.
During this period, a deep northeasterly flow brings
major rains to the M6xico City area. This flow may be
temporarily disrupted in August. The resulting drier
period, called the canicula, is very important because
its length determines the sufficiency of summer rain.
The prevailing surface winds are from the north and
northeast during the summer months (J~iueregui,
1958). In winter the ITCZ moves south and the region
is under the influence of the subtropical high pressure
belt with westerly winds aloft. Weather is very dry and
142 P.R. MILLER et al.
stable during this period and air pollution levels in the
Valley of M6xico are at their worst (de Bauer and
Krupa, 1990).
The effects of transported ozone on forests of the
San Bernardino Mountains east of Los Angeles, Cali-
fornia were first reported in the early 1960s (Miller et
al., 1963; Richards et al., 1968). The summer-dry
Mediterranean climate of Southern California is one
of the major factors allowing accumulation and trans-
port of pollutants. The Pacific high pressure system
results in a persistent marine temperature inversion
layer--the principal feature of the summer climate
that prevents upward dispersion of pollutants. The
onshore flow of marine air in the afternoon delivers
the polluted air mass to inland valley and mountain
areas (Edinger et al., 1972). One result is a gradient of
decreasing ozone concentrations along the west to
east axis of the San Bernardino Mountains (Miller et
al., 1986). Summer heat in the deserts east of the San
Bernardino Mountains plays an important role in
ozone transport because the rising hot air over the
deserts is replaced by the cooler marine air. In winter,
lower temperatures and the frequent occurrence of low
pressure systems often followed by offshore, Santa
Ana winds, prevent both the accumulation and trans-
port of pollutants. Therefore, elevated ozone concen-
trations are observed mainly during the months of
April through October.
In 1990, an ozone monitoring station was estab-
lished in the forested area about 10 km west of the
urban boundary of M6xico City. The project was
initiated in response to deliberations of the tri-
national (Canada, M6xico and the U.S.A.) study group
on Atmospheric Deposition and Climate Change, a
part of the F A O North American Forestry Com-
mission. In this paper, we compare the monthly and
seasonal ozone concentrations from May 1990 to
October 1991 at this site with an ozone monitoring
station at Crestline, California, U.S.A. The results are
discussed in terms of differences in the relative dis-
tances of forested areas from the urban source area,
climate, and solar conditions attributable to the lat-
itudes of the two locations. The consequences of the
seasonal pattern of ozone exposure conditions typical
of each location are considered in relation to forest
damage.
METHODOLOGY
Locations of monitoring sites
The station near M6xico City (Fig. 1) is located at the
Parque Cultural y Recreative Desierto de los Leones (DL) at
latitude 19°, 21' N, and longitude 99 °, 15' W at an elevation of
2970 m (9742 ft). The center of densely urbanized M6xico
City, at a mean elevation of 2240 m (7349 ft), is located within
25 km to the northeast (Fig. 1). The surrounding landscape is
forested with a mixture of fir (Abies religiosa), pines (Pinus
patula Sehiede & Deppe), (P. hartwegii) and oaks (Quercus
spp.) (Vasquez, 1987).
The station at Crestline, California (CR) is located within
the boundaries of the San Bernardino National Forest at
latitude 34° 14' N, and longitude 117°, 16' W. The center of
the major air pollution source area, the metropolitan Los
Angeles area, is located about 100 km to the west (Fig. 1).
The elevation is 1525 m (5000ft). The surrounding forest
cover is principally the California mixed conifer type. The
most abundant tree species in the mixture are ponderosa pine
(Pinus ponderosa Dougl. ex Laws.), white fir [Abies concolor
(Gord. & Glend.) Lindl. ex. Hilderbr.], and California black
oak (Quercus kelloggi Newb.) (McBride and Miller, 1987).
This is the region of the San Bernardino National Forest with
the highest ozone exposure and highest levels of chronic
ozone damage (Miller et al., 1986).
Instruments and calibration
At DL, a DASIBI Model 1003, UV ozone photometer is
located at an "ancient" (1601 ad) monastery in a room
within 5 m of the rooftop. A TeflonTM sample line extends
outside to a position approximately 0.5 m above the rooftop.
The intake orifice is protected from insects by a fine metal
screen and moisture is prevented from entering the line by
looping it downward. A filter holder with a Teflon filter disc
was placed in the sample line immediately preceding the
instrument intake. This filter was changed monthly. Several
times weekly the sample and control frequencies were re-
corded and corrective actions were taken to keep the instru-
ment within specified ranges. The monitor was calibrated in
Riverside, California and at time of installation the span was
changed to correct for the elevation difference between
Riverside and DL. Subsequent calibrations used a DASIBI
Model 1003PC fitted with an internal ozone generator. This
instrument was calibrated against a secondary standard
immediately prior to shipment to DL and the span was
changed on arrival to correspond to the higher altitude.
Calibrations were repeated in October 1990 and March 1991.
Data were recorded by a Leeds and Northrup, Speedomax
H, strip chart recorder. Time marks were placed on the strip
chart several times weekly. Chart speed was approximately
5 cm h- 1. The average ozone concentration for each hour
was transferred from the strip chart and key-ponched by the
same individual.
The DASIBI Model 1008, UV ozone spectrometer at CR is
operated and maintained by the South Coast Air Quality
Management District as part of the monitoring network in
the California Southcoast Air Basin. Validated data were
available from the headquarters at Diamond Bar, CA.
Because of the elevational difference between DL and CR
(1445 m) there is a need when comparing data from these
stations to acknowledge recent papers expressing concern
about which units of measurement are most appropriate
(Lefohn et al. 1990; Larson and Vong, 1990). Comparisons of
ozone concentrations at stations differing in elevation have
been reported as mixing ratios (parts per billion) (Angle and
Sandhu, 1986), and mixing ratios or mass concentrations
(#g m-3) corrected to standard temperature and pressure
(STP) (Lefohn et al., 1990). We recognize some concern about
using mixing ratios uncorrected for temperature and pres-
sure; however, we do not presently have the additional data
needed to calculate a temperature and pressure corrected
mass concentration.
RESULTS
Ozone concentrations in summer and winter
The diurnal pattern of ozone concentrations at both
D L and CR in summer shows peaks occuring at
midday at D L and 1700 hr at C R local time (Fig. 2a).
The earlier peak time at D L is primarily because it is
only 25 km from the center of the urban source while
CR is nearly 4-times that distance from the center of its
 Comparison of 03 exposure characteristics 143

....-''" ""

,~'," " / \ ~i ~ ~ ~ " .

~°~.... { ~'7
.,~,~'_~ y..: ~ i
!
~ ... . . .'w<,
- ~,

o 2 4 6 8 1o "~ "¢.~.
I I I I r I ~

Fig. 1. MapofM~xicoCityandLosAngelesregionsshowinglocationsoftheDesiertode
los Leones and Crestline monitoring sites.
144 P.R. MILLERet al.

Ozone (ppb)
120

80

40

20 l- . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

0 L L I l
0 5 10 15 20 25
Hours

Deslerto --~ Creltllne

a

Ozone (ppb)
1001

40208~080
. . . . . . . . . . . . . . . . . . . . i . . . . . . . . . . . . . . . . . ~
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. .. . . . . . . . . .

O-- ~ [ _ _ i _ _ _ i

0 5 10 15 20 25
Hours

Deeierto --~ Creetline

Fig. 2. Hourly averages of ozone over the 24-hr period (a) May-October 1990,and (b)
November 1990-April 1991.

source region (Fig. 1). Summer peak concentrations concentration at CR was in the range above 310 ppb
are considerably higher at CR than at DL. Diurnal in June compared to a maximum in the range above
patterns in winter show less evidence of a transported 290 ppb and DL in December.
peak at CR and concentrations are lower than at DL A complete distribution of concentrations in the
(Fig. 2b). 0-340 ppb range during two summers is shown in
The 0600-2000 h (maximum day length) average Table 2. In both 1990 and 1991, the highest percentage
ozone concentrations for May 1990-April 1991 of hourly concentrations fell in the 0-20 ppb range at
(Fig. 3) show that CR averages are distinctly higher DL. At CR the highest percentage was in the 21-40
than DL in June, July, August and September. On the (1991 ) and 41-60 (1990) ranges. This difference is likely
other hand, DL averages are slightly higher than CR due to the distances of these stations from their
during November-March (with the exception of respective source areas. DL is much closer to its source
December). Table 1 shows the number of occurrences so it is expected that more ozone quenching would
in 20 ppb increments of hourly concentrations from 70 occur because of higher levels of nitric oxide near the
to 310 ppb for May 1990-April 1991. The maximum source, particularly in the evening and early morning
 Comparison of 0 3 exposure characteristics 145

14 Hour O=one Mean (ppb)

....................................................................
120

100

80~~~l~[~[l~~[
80

,o
~.......~.....................................
.............................. ~

20 ............ ~ . . . . . . . . . . . . . . . . . . .

o ~"
May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr
Months

1 Deslerto ~ Cmltllne

Fig. 3. 0600-2000 ozone average from May 1990 to April 1991.

Table 1. Monthly distribution of ozone concentrations equal to or greater than 70 ppb during May 1990-April 1991

Concentration Month
range May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr
(ppb) Number of occurrences

70 DL 121 132 133 122 103 114 156 145 39 105 96 72

CR 237 323 442 361 338 190 36 0 1 17 11 135
90 DL 71 79 84 95 76 77 117 103 19 78 82 51
CR 96 239 29 242 186 84 2 0 0 0 2 41
110 DL 43 51 51 61 45 59 81 65 8 51 58 39
CR 24 174 198 156 104 28 0 0 0 0 0 11
130 DL 26 34 37 38 29 37 63 48 3 39 43 25
CR 4 122 124 89 69 13 0 0 0 0 0 1
150 DL 14 17 25 22 18 20 36 29 1 27 27 16
CR 0 78 76 54 45 7 0 0 0 0 0 0
170 DL 7 10 9 12 4 11 16 19 1 17 11 I0
CR 0 45 35 23 22 4 0 0 0 0 0 0
190 DL 3 5 3 1 2 6 6 14 0 11 6 8
CR 0 18 88 12 9 0 0 0 0 0 0 0
210 DL 1 2 0 1 1 4 3 6 0 8 6 4
CR 0 12 3 4 5 0 0 0 0 0 0 0
230 DL 0 0 0 0 1 0 1 3 0 6 3 1
CR 0 5 0 1 1 0 0 0 0 0 0 0
250 DL 0 0 0 0 0 0 1 2 0 3 0 1
CR 0 3 0 1 1 0 0 0 0 0 0 0
270 DL 0 0 0 0 0 0 0 1 0 2 0 0
CR 0 3 0 0 1 0 0 0 0 0 0 0
290 DL 0 0 0 0 0 0 0 1 0 0 0 0
CR 0 1 0 0 1 0 0 0 0 0 0 0
310 DL 0 0 0 0 0 0 0 0 0 0 0 0
CR 0 1 0 0 0 0 0 0 0 0 0 0

hours. CR is m o r e distant from the m a j o r source area
and largely decoupled from fresh infusions of nitric
oxide.
Effect of climate on seasonal ozone differences
A partial explanation for the lower J u n e - S e p t e m b e r
averages at D L is found by c o m p a r i n g the annual
distribution o f precipitation at these locations
(Fig. 4a) Donley et al., 1979; U. S. D e p a r t m e n t of
State, 1988). The highest precipitation a m o u n t s come
in J u n e - S e p t e m b e r to the M6xico City area. The Los
Angeles region has virtually no precipitation during
these months. In addition, summer temperatures are
much higher in Los Angeles than in M6xico City
146 P.R. MILLER et al.

Table 2. Number of average hourly ozone occurrences in 20 ppb intervals from 0 to 340 ppb during two growing seasons,
May~October 1990 and 1991 at the Desierto de los Leones and Crestline, CA

Concentration DL CRES
(ppb) 1990 1991 1990 1991

No. h % No. h % No. h % No. h %

0-20 1609 38.4 2017 61.3 444 10.5 528 12.6

21-40 1388 33.1 434 13.2 863 20.5 959 22.8
41---60 466 11.1 280 8.5 1014 24.1 972 23.1
61-80 243 5.8 148 4.5 754 17.9 676 16.1
81-100 172 4.1 106 3.2 453 10.8 441 10.5
101-120 109 2.6 tO 1 3. I 263 6.2 264 6.3
121-140 85 2.0 65 2.0 161 3.8 179 4.3
141-160 63 1.5 54 1.6 131 3A 87 2.1
161-180 33 0.8 40 1.2 82 1.9 52 1.2
181-200 11 0.3 19 0.6 23 0.5 24 0.6
201-220 8 0.2 16 0.5 17 0.4 12 0.3
221-240 I .02 10 O.3 2 0.04 4 0. l
241-260 0 0.0 1 0.03 1 0.02 2 0.05
261-280 0 0.0 1 0.03 2 0.04 1 0.02
281-300 0 0.0 0 0.0 1 0.02 0 0.0
301-320 0 0.0 0 0.0 0 0.0 0 0.0
321-340 0 0.0 0 0.0 1 0.02 0 0.0
0 -340 4188 100.0 3292 100.0 4212 100.0 4201 100.0

Precipitation {ram)
200 r

150

100

0
Jsn Feb Msr ADr May dun Jul Aug Sep Oct Nov Dec
Months

Mexico ~ Loa Angeles

Average Temperature C

" 1
2O

15

10

0
Jan Feb Mar Apr Msy Jun Jul Aug 8ep Oot Nov Deo
Months
b
m Mexico ~ Los Angelea

Fig. 4(a) and (b).

 Comparison of Oa exposure characteristics
Hours Daylongth Dlfferenoe at Mid Month
1.6
O.6
-0.8
-1
I I I I
- 1.6
Jsn Feb Mar Apt
Los Angeles (upper), Mexico City
Fig. 4. Environmental differences between the M6xico City and Los Angeles
regions: (a) precipitation, (b) temperature, and (c) daylength.
(Fig. 4b) (Donley et al., 1979; U. S. Department of
State, 1988). The cloudiness and lower temperatures
associated with the rainy period undoubtedly limit the
number of days when photochemical oxidants can be
produced, accumulate to significant levels, and be
transported to the mountains. Conversely, the rela-
tively dry winter in the M6xico City region with its
bright sunlight appears to be conducive to buildup of
ozone.
DISCUSSION
The major reason for comparing seasonal ozone
concentrations between the M6xico City and Los
Angeles regions was to help understand the conditions
under which forest vegetation near each site is ex-
posed. A secondary goal was to interpret the ways in
which climate differences and geographic position
may influence ozone formation. An important factor
influencing ozone formation is the latitudinal differ-
once between the two regions. Winter day lengths are
slightly longer in M6xico City than Los Angeles, while
summer day lengths are longer in Los Angeles
(Fig. 4c) (List, 1976). Solar zenith angle is consistently
smaller in all months at M6xico City (List, 1976). Since
the sun is higher there is a shorter path through the
atmosphere to the lower troposphere and therefore
the actinic flux (photons c m - 2 s - 1 ) , in wavelengths
that increase photochemical reactivity, is expected to
be higher (Finlaysen-Pitts and Pitts, 1986). Further-
more, the higher altitude at M6xico City (2240 m) also
results in a higher actinic flux.
One of the most important climatic differences is the
annual distribution of rainfall. It may be possible that
forest vegetation at D L is near its maximum sensitivity
147
I I I I I I I I
Mgy Jun Jul Aug l o p Oot Nov Doo
Month
LA minus Mexico
(lower)
in summer because rainy weather and adequate soil
moisture would maximize gas exchange rates leading
to more ozone uptake (Showman, 1991). Trees may
be sensitive even to the lower levels of ozone typical
of the summer. Furthermore, there is evidence
that ozone concentrations remain higher at DL in
September-March; therefore, there is really no respite
from exposure as in the winter at CR. At CR the
maximum sensitivity of vegetation would be expected
in May, June and July when stored soil moisture is still
available; however, sensitivity would be expected to
decline in August and September when soil moisture is
depleted. The highest ozone levels are present during
June, July August and September.
Concentrations may he consistently higher
throughout the year at DL because it is much closer to
the source area and depends mainly on the daily
upslope flow of air for effective transport of polluted
air (Fig. 1). This terrain-dominated feature of air flow
is shared by CR; however, the inland transport of
polluted air must take place over a 100 km distance
from metropolitan Los Angeles before upslope flow
can be involved (Edinger et al., 1972).
Acknowledgements--Special l~cognition is extended to Ing.
Carlos E. Gonzalez Vicente, Secretario T~nico, Instituto
Nacional de Investigaciones Forestales y Agropecuarias for
his leadership role in establishing the project. Recognition is
deserved by Ing. Manuel Alberto Mendoza Gutierrez and
other staff at the Desierto de los Leones who performed
regular maintenance on the monitoring equipment. This
study would not be possible without the Crestiline ozone
data provided through the courtesy of Albert Ehm and
Margaret Hogan of the California South Coast, Air Quality
Management District. We recognize the important data
analysis work of Minn Poe and review of the manuscript by
Patrick Temple, both from the statewide Air Pollution
Research Center, University of California, Riverside. We also
148 P.R. MILLER et al.
express appreciation to Susan Schilling, Anthony Gomez and
Bernard Meisner, all from the Forest Service, Pacific South-
west Station, for help with graphics preparation and manu-
script review.
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