GEOPHYSICAL RESEARCH LETTERS, VOL. 26, NO.

9, PAGES 1283-1286, MAY 1, 1999

Toluene Emissions from Plants

A. C. Heiden,1 K. Kobel,1 M. Komenda,

2 R. Koppmann,
2 M. Shaol'a
and J. Wildt I

Abstract. The emission of toluene from different plants (e.g. sunflower)or in soil. For emissionstudieswe usedsun-
was observed in continuously stirred tank reactors and in flower(HelianthusannuusL. cv. Gigantheus)as a model
field measurements.For plants growingwithout stress,emis- plant becausethey are a fast growingplant speciesshowing
sion rates were low and ranged from the detection limit up high emissionsof severalmonoterpenes.In addition, experi-
to 2.10-6 mol.cm-2-s
- Under conditionsof stress,the mentswith pine (Pinus sylvestrisL.) wereconducted.The 3
emission ratesexceeded10-4 mol.cm-2.s
-. Exposureof to 4 years old pines were dug out from the Harthelmet Wald
sunflower
(Helianthus
annuus
L. cv. Gigantheus)
to aCO2 (SouthernGermany). Only shootsand leavesof the plants
resultedin aC-labelingof the emitted tolueneon a time were placed into the chamber by shielding the nutrient so-
scale of hours. Although no biochemical pathway for the lution or the soil with a PTFE plate tightly closingaround
production of toluene is known, these results indicate that the plants' stems. The plants were illuminated with Osram
toluene is synthesized by the plants. The emission rates HQI 400 W/D lamps at a photosyntheticactive radiation
of toluene from sunflowerare dependent on nutrient supply (PAR) of about450 ttE-m-2-s-atmid canopyheight.
and wounding. Since c-pineneemissionrates are also influ- Ambient air was purified by an adsorptivedrying device
enced by these factors, toluene and c-pineneemissionsshow (Zander, KEA 70, Ecosorb)and subsequentlypassedover
a high correlation. During pathogen attack on Scots pines a heated Pd/A12Oa-catalystat 450 C to reducethe VOC
(Pinus sylvestrisL.) significanttolueneemissionswere ob- concentrations at chamber inlet below the detection limit.
served. In this case emissionsof toluene and c-pinenealso HundredL-min-x wereflushedthroughthe chambers.
Only
show a good correlation. Toluene emissionswere also found during13CO2
exposure
experiments
(> 95 atom%13C)the
in field experiments with pines using branch enclosures. air flow wasreducedto 20 L.min- . Then, the chambers
wereflushedwith syntheticair and 13CO2wasadded.
Introduction VOC emissionswere determined by measuring concen-
trations of individual compounds at chamber inlet and out-
Toluene often is the most abundant aromatic compound let. Preconcentration was performed on solid adsorbents
observed in urban atmosphereswith mixing ratios up to (TenaxTA/Carbotrap). A thermaldesorption system(Ger-
several10 ppb [Atlas et al., 1994 and referencestherein]. stel Online-TDS G) connectedto a cooledinjection system
Despite its reactivity, toluene is also observedin the marine (GetstelCIS 3) wasused. Subsequently,
the substances
were
troposphereat mixing ratios of some 10 ppt in the Northern thermally desorbedinto a GC-MS-system(HP5890 SeriesII
Hemisphere and below 10 ppt in the Southern Hemisphere - HP5972A). A detailed descriptionof the GC/MS device
[Penkerr,1982;Nutmagualet al., 1985].As all aromaticcom- can be foundin Heiden et al. [1999].
pounds, toluene in the continental troposphere is produced Possiblewall losseswere investigatedby adding the stan-
primarily from anthropogenicsources. Biomass burning is dard gas atmosphere from a permeation sourceto the air at
anothersourcefor tolueneespeciallyin the southernhemi- the inlet of the empty chambers. No significantlosseswere
sphere[Koppmannet al., 1997]. found and thus, wall losseswere neglected. Emission rates
Plants produce a large number of VOC, such as isoprene, were calculated according to:
mono- and sesquiterpenesas well as oxygenated compounds Fair.
[e.g. Fehsenfeldet al., 1992]. Tolueneemissions
from plants (I)VOC : ([vOC]ou, -
AL
have not been reported. Here we present results which show
that toluene is emitted from sunflowerand pine. Fair is the air flow through the chamber, AL is the leaf
area of the plants,[VOC]outand [VOC]inare the concentra-
tions of individual VOCs measured at chamber outlet and
Experimental inlet, respectively.
VOC emissions were studied in a continuously stirred Field experiments were performed at Hartheimer Wald
tank reactor (1000 L volume). The chambercontained1 with 40 yearsold Pinus sylvestrisL. usinga branchenclosure
to 4 plants which were either grown in a nutrient solution with a volume of 35 L. Air temperature, relative humidity
and PAR were measured inside the bag using an HTR-1
llnstitut fiir Chemieder BelastetenAtmosph/ire(ICG-2), probe (PP Systems). The air flow through the enclosure
Forschungszentrum Jtilich, D-52425 Jiilich, Germany. was10L-min- Theinletairwaspurified
bya Pd/A12Oa-
2Institut fiir Atmosph/irische
Chemie(ICG-3), Forschungs-catalyst at 450 oC and subsequentlydried. Part of the outlet
zentrum Jiilich, D-52425 Jiilich, Germany.
3Visitingscientistfrom Institute for EnvironmentalSciences, air flow was suckedthrough a glasstube containing Tenax
University of Beijing, PR China. TA and Carbotrap,with a flow rate of 100 mL.min- for
60 min. A detailed description of the enclosuresystem used
Copyright1999by the AmericanGeophysical
Union. for the field experimentscan be foundin Parusel[1996],the
analyticalsystemis describedby Wedelet al. [1998].
Papernumber1999GL900220. Identification was based on mass spectra and retention
0094-8276/99/1999GL900220505.00 times of pure chemicals(Fluka/Aldrich, purity > 93%).
1283
1284 HEIDEN ET AL.: TOLUENE EMISSION FROM PLANTS

area). This woundingagain led to an increaseof the emis-

t=Oh
1,0 sion rates, including toluene emission. Two days after this
t=8h
t=17h experiment, nitrate was replenishedto the nutrient solution
([NO-] = 750/M). Thereafter,tolueneemissionratesre-
mained at a constant level.
Figure 2 also showsa significant diurnal variation of the
toluene
emissions.
Duringdaytime
(PAR- 450/E.m- .s-x ,
T = 23 C) the emissionrates are about a factor of 2
larger than during darkness(T - 19.5 C). Caused by
the nitrogen deficiency,the toluene emissionrates increased
from1.10 -x5 to 2.10-x5 mol.cm-2-s
-x (10-x moltoluene
, . ', : ', ', :
cm-2.s
-x - 89 ng.g(dw)-X.h -x for sunflower).Wounding
92 93 94 95 96 97 98 led to an increaseto 1.3-10-x4 mol.cm-.s -x The emission
mass fraction [m/z] rates of c-pineneshoweda similar behavior and a significant
correlation between the emissionsof toluene and c-pinene
Figure 1. Relativeabundanceof m/z - 92 to 99 in toluene wasfound(r - 0.91,n - 554).
emitted from sunflowerbefore(t=0 h), during (t=8 h under Figure 3 showsthe labeling of toluene for a time period
illumination)andin darkness
after xaCO2exposure
(t=17 of about 80 h during this experiment. Labeling occurs on
h). a time scaleof 12 h (fit to 1-exp(-t/rincr.... )), decreases
during the night, increasesagain the next day and there-
after decreasesagain on a time scale of 25 + 3 h (fit to
Data analysis was performed by integration of target ion exp(-t/-decay)).
Toluene Emissions from Pine To find out if
peaks in the extracted ion mode or using an FID. The GC
systemswerecalibratedusingdifferentpermeation/diffusion toluene is also emitted from coniferous plant species, the
sourcescontainingpure chemicalsin individual vials. A de- emissions frompine (4 plantstogether)werestudied. Toluene
tailed description of the permeation and diffusion sources emissions are low as long as the pines do not suffer from
canbe foundin $chuhet al. [1997]and Gautroisand Kopp- stress. During this experiment, about 1% of the needles
mann[1999],respectively. became yellow within a time period of five days. This ef-
fect was probably caused by a pathogen attack, implied by
Results the emissionsof compoundsproduced during lipoxygenase
activity [e.g. Heiden et al., 1999]. However,the pathogen
Laboratory Experiments attacking the plants was not identified. Obviously caused
For both investigated plant speciestypical emissionsof by the pathogen attack, the emissionrates of all compounds
monoterpenesand sesquiterpeneswere observed. The re- increasedabout one order of magnitude. During this time a
sults of these measurements will be described elsewhere. significant correlation between the emissionrates of toluene
Also emissions of toluene were found. and c-pinenewas found again, but the ratio between these
To confirm that toluene is not formed as an artifact in our emissionrates (toluene/c-pinene
= 0.5) was differentfrom
chamber, the air of the empty chamber was measured. For- that foundfor sunflower(0.07).
mation of toluene from compoundsemitted from the plants In addition to toluene other aromatic compounds were
was excluded by measuringthese compoundsin the air from emitted from pines as a reaction to pathogen attack. Among
the calibration system. In neither case toluene was found. those was methyl salicylate, which is produced in the shiki-
The field measurements were conducted using a different mate pathway [e.g. Yalpaniet al., 1993]. The correlation
between the emissionrates of toluene and methyl salicylate
analytical system. These results confirmed that toluene was
not produced artificially. wasmuchlesssignificant(r= < 0.3) than the correlation
Toluene Emission from Sunflower During ex- between the emission rates of toluene and c-pinene.
posureof a sunflower
with x3CO.(8 h underillumination),
the emitted toluene was found to be labeled with x3C atoms.
1,4x10
"4 - 480
Figure i showsthe relativeabundanceof the m/z fractions:
92to 99fortolueneasfoundbefore,during,andafterx3CO-
exposure. The occurrenceof peaks with massesq- i to q- 7 -r(1,2x10
-14 360 ,
?

abovem/z = 92 (molar massof toluene= 92 ainu) shows oE1,0x10

"4 E
clearly that all 7 C-atoms are labeled. At the end of the illu- 240 LU
E
mination period the exposurewas stopped and air including
CO. with natural abundanceof x3C was used. 2,0x10
'15 120 O_
To test the factors that control the toluene emissions o

from sunflower, the nitrogen supply of the sunflower was

changed
andthe plantwaswounded.Fourdaysafterx3CO- 0 i ' i
100 ' { ,
2 0 i
300 ' i
400 ' i
500 ' i
600
exposure,the nitrate containingnutrientsolution([NO-] - ,

time [hi
750/M) wasreplacedby a solutionof the samecomposition
exceptof nitrate ([NO] - 0/M). The nitrogendeficiency Figure 2. Time sequenceof toluene emissionsfrom sun-
led to an increaseof the emissionrates of many VOC includ- flower.XaCO2
exposure:
t=0-8 h, removal
of nitrate:t=100
ing toluene (seefigure 2). Eleven days later the sunflower h, wounding: t=364 h, replenishment of nitrate: t=420 h.
was woundedby cutting off a leaf (< 5% of the total leaf Bars show PAR, right scale.
 HEIDEN ET AL.: TOLUENE EMISSION FROM PLANTS
500
4OO
IO0
time [h]
Figure 3. Time sequence of aC-labeling
in toluene.La-
for the sumof 3C-atomsin the emitted labeling experiments show that toluene is synthesizedand
belingis calculated
toluene.PAR is indicatedby the line,3CO2exposure time emitted in parallel to biosynthesis.On the other hand, the
is indicated by the black bar.
Thepineswerealsoexposed
to aCO2(8 h underillumi-
nation). Again, labeling of toluenewas observed,but the
amountof labeling(< 3%) was much lowerthan that ob-
served for the sunflower. Under pathogen attack, the emis-
sionrates of all compoundsdid not showthe significantdiur-
nal variation as observedbefore. It seemedthat pools were
openedand the compoundswerejust evaporatingfrom these
storage pools.
After finishingthe measurementswith the living plants,
some green and yellow needleswere taken and introduced
into flasksflushedwith synthetic air. A head spaceanalysis
showed that the abundance of toluene relative to that
a-pinene was 0.5 for yellow and 0.05 for greenneedles.
Field Experiments
In addition to the laboratory studies, 4 measurement
campaignswere conductedbetweenApril and Octoberwith
pine at Hartheimer Wald. In all experiments,toluene emis-
sions were observed. The emission rates ranged from the
detectionlimit up to 2.10-6 mol.cm-'.s
- (10-5 mol
toluene.cm-'-s
- = 13 ng.g(dw)-.h
- for pine), much
lower than found for the plants in the laboratory under
stress. A diurnal variation was observed(Figure 4). In
April, when pines came into leaf, emissionsof all VOC in-
cluding those of toluene were higher than those found in
the other experiments.During the other campaignstoluene
emissionswere low and data were highly scattered. This
might explain that a significantcorrelation between the
emissionrates of toluene and a-pinene was found only dur-
ing the campaignin April (r2 - 0.74, n= 36; r2 = 0.10,
n - 53; r2 = 0.14, n- 48, andr2 - 0.07, n = 53 for the
measurements
in April, July, September,and October).
Discussion
The resultsof our experiments,especiallythe labeling of
toluenewith aCafterexposure
to CO2 showthat toluene
is synthesizedby the plants. However, the biosynthetic
pathwayof tolueneproductionis far from beingunderstood.
It is known that aromatic compoundsare producedby plants
within the shikimatepathway. Our experimentsgiveno hint
to a couplingbetweenthe emissionrates of suchcompounds
and toluene. Hence, it seemsunlikely that toluene is pro-
duced within the shikimate pathway. It is also known that
1285
aromatic compounds can be produced from monoterpenes
within the plants [e.g. Hess,1988]. The significantcorrela-
tion between toluene and a-pinene emissionssuggeststhat
toluene may be produced within the mevalonate pathway.
However, we have no proof for this hypothesisyet.
The time dependenceof labeling implies that toluene is
producedfrom a substratewith a turnover time of about 12
h. The decay occurson a time scaletwice as long. Further-
more, the amount of labeling during night is significantly
smaller than during daytime.
$chuh et al. [1997]argue that monoterpeneemissions
from plants occur from two processes:Emissionsin paral-
lel to biosynthesis
(only daytime) and emissions
from pools
(day- and nighttime). On the one hand, the resultsof the
large increase of toluene emissionscaused by wounding of
sunflowerimplies that pools may have been opened. The
results of the experiments with green and yellow needles
also imply that there are pools for toluene in plants. Thus,
in analogy, we conclude that toluene emissionsalso occur
from pools as well as in parallel to biosynthesis.
On time scalesof several days there is a good correlation
between the emission rates of toluene and a-pinene. Ratios
of toluene emissionrates relative to those of a-pinene are dif-
ferent for pines under pathogen attack and sunflowerunder
nitrogen deficiencyand wounding. With respect to the emis-
sionsfrompinetherelationship
changed
(0.005,r2 = 0.8, n
- 224 before,0.15,r2 = 0.86, n = 10 at the beginning,and
0.5, r2 - 0.9, n = 48 duringpathogen
attack).Hence,the
of ratio of these emissionsalso changeswith the physiological
state of the plant. Therefore, the ratios measuredbetween
the emissionsof toluene and a-pinene cannot be used to es-
timate concentrations of toluene from this natural source in
remote areas.
For plants without stressthe emissionsare relatively low.
But, for plants sufferingfrom stressas pathogen attack, ni-
trogen deficiency or wounding, the emissionrates may be
high. In such casesthere may be non negligible intrusion
of natural emitted toluene. Toluene, benzene or the ratio
of the concentrationsof these compounds are often used as
tracersfor polluted air masses[e.g. Gelencseret al., 1997].
2,0xl0'15-
''1,5xl
0'15 295
'E
1,0x10.16
285
E
::J5,0X10
'17
, 280
275
0,0,
12:00 00;00 ' 12;00 ' 00;00 12;00
270
00:00
daytime
Figure 4. Diurnal variationof tolueneemissions measured
usingthe branchenclosure(left scale,circles). Right scale,
squares: Temperature, the bars represent the variation of
temperature during sampling time.
1286 HEIDEN ET AL.: TOLUENE EMISSION FROM PLANTS

If toluene is emitted from biogenic sources,misleading re- and their impact on the formation of tropospheric ozone, J.
sults may be obtained. Geophys. Res. 102, 18879-18888, 1997.
Nutmagual, YV., and D. R. Cronn, Determination of selected aro-
matic hydrocarbons at remote continental and oceanic loca-
Acknowledgments. This work wasfinanciallysupported
tions using photoionization/flame-ionizationdetection, J. At-
by the German Ministry for Education, Science, Research and
mos. Chem. 2, 415-433, 1985.
Technologywithin the TroposphericResearchProgram (grant
Parusel, E., Zur Bedeutung der Pfianzen als Quelle leichter
No. 07TFS23/O7TFS24). J. YV. thanks Fonds der Chemischen Nicht-Methan-Kohlenwasserstotte fiir die Atmosphiire, Land-
Industrie for financial assistance.
bauforschung VSlkerode, Sonderheft 167, Bundesforschungsan-
stalt fiir Landwirtschaft, Braunschweig-V61kerode, ISSN 0376-
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