Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ o, , 3 ects), emis- ff Discussions ´ arzea and Igap Biogeosciences , W. R. Costa 2 1 ´ ujo, 2936 Manaus, Brazil ect atmospheric chemistry (ox- ff ´ e Ara , M. Staudt 1,2 15280 15279 ine by collection on adsorbent tubes and sub- ˆ onia, Av. Andr , and J. Kesselmeier ffl 3 -pinene). Mediterranean plants showed additional , S. Welter 1 > β sabinene > , N. M. Knothe , M. T. F. Piedade 1,2 4 limonene > erent environments of the Amazon basin, i.e. Terra firme, V ff -pinene This discussion paper is/has been under review for the journal Biogeosciences (BG). Please refer to the corresponding final paper in BG if available. Max Planck Institute for Chemistry, Hahn-Meitner-WegCentre 1, d’Ecologie 55128 Fonctionnelle Mainz, et Germany Evolutive, UMRInstituto 5175, Nacional 54293 de Montpellier, Pesquisas France da Amaz Universidade do Estado do Amazonas, Av. Djalma Batista, Chapada, 69050-010 Manaus, α under ambient conditions. species were monoterpene emitters( exhibiting a quiteemissions conservative of emission sesquiterpenes, pattern whereasno in sesquiterpenes the were detected case probably ofsystems. due On to plants the a from other lack hand the of methanolin sensitivity Amazon emissions, in most an region the indicator of measuring of the growth,tems were tropical showed common and acetone Mediterranean emissions.reactive species. The VOC A species observed few which heterogeneous speciesson are emissions from to not perform both including easily more ecosys- detected screening by at flux leaf measurements, level and, give whenever rea- possible, within the forests Analysis of the volatilemass spectrometer organics (PTR-MS) was and performedsequent o online gas by chromatographic anant analysis. compound proton-transfer-reaction Isoprene emitted followed was by monoterpenes,Mediterranean quantitatively methanol species and the acetone. emitted Most most a of variety domi- the of monoterpenes, whereas only five tropical poorly described tropical vegetationand to highly be heterogeneous comparedcommon emissions with plant from the species Mediterranean quite offrom well vegetation. both the investigated For Mediterranean ecosystems area, were thisplant which investigated. task, species, is Sixteen were known chosen. plant for Ining species its emissions contrast, special of little VOCs diversity information from in isfrom tropical VOC currently tree di emitting species available at regard- thewere leaf level. screened Twelve plant for species emission of VOCs at leaf level with a branch enclosure system. As volatile organic compoundsidative (VOCs) capacity) significantly and a physics (secondarysion organic inventories aerosol defining formation regional and and e portant. global biogenic The VOC aim emission strengths of are this im- work was to achieve a description of VOC emissions from Abstract M. A. R. Liberato 1 2 3 4 AM, Brazil Received: 17 August 2012 – Accepted: 11Correspondence October to: 2012 J. – Kesselmeier Published: ([email protected]) 1 November 2012 Published by Copernicus Publications on behalf of the European Geosciences Union. Biogeosciences Discuss., 9, 15279–15328, 2012 www.biogeosciences-discuss.net/9/15279/2012/ doi:10.5194/bgd-9-15279-2012 © Author(s) 2012. CC Attribution 3.0 License. Leaf level emissions of volatilecompounds organic (VOC) from some Amazonian and Mediterranean plants A. Bracho-Nunez 5 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | culties, ffi ect cloud ff culties, methodological di ffi 15282 15281 ine gas-chromatograph coupled to a mass spec- ¨ oschl et al., 2010; Sjostedt et al., 2011; Wang et al., ffl nity higher than water; an online gas-chromatograph with ffi erent methods for characterization and quantification of VOCs ff ) to the atmosphere Singh et al., 2001. Other compounds of high in- 1 − ect chemical and physical properties of the atmosphere (Atkinson and Arey, ff ine GC-FID along with an o ffl The present study aims to contribute towards a more complete assessment of VOCs In general, most of these studies concentrated on the emission of isoprene and Emission inventories and model calculations have been produced to define regional Screening for VOC emissions wasmon carried out for with terra a total firme of twelve and plant species floodplain com- areas in the Amazonas region (Table 1). Three trometer (GC-MS) for the determination of higher VOCs including sesquiterpenes. 2 Material and methods 2.1 Plant material and environmental conditions 2.1.1 Tropical vegetation VOC species, several di were used: a proton-transfer-reactionof mass all spectrometer VOCs (PTR-MS) with fora the proton flame detection a ionization detector (GC-FID)an for o the determination of isoprene emissions; and et al., 2004) as2007). evidenced by indirect approaches (Di Carlo etreleased al., at 2004; leaf Kuhn level etspecies. contrasting al., We flux studies chose which thegion may Amazonian and miss vegetation compared the because it more with itexhibits reactive the a is VOC much very a better described heterogeneous poorlyVOC Mediterranean emission investigated emissions ecosystem composition. re- between which tropical To enable and a Mediterranean vegetation comparison over of a the broad range of genated compounds were identified(150–500 TgCyr only recently asterest being are a sesquiterpenes large (Jardine etto source al., of their 2011), carbon high but they reactivitytive are compounds (Fuentes not may et constitute easily a measured al., considerable due 2000). amount of Sesquiterpenes the missing and VOCs other (Goldstein highly reac- ethanol and formic and acetic acids (Seco et al., 2007). Emissions of these oxy- compounds (oxVOCs) such as formaldehyde, acetaldehyde, acetone, methanol, 2002; 2006b; Harley et al.,Yet, VOC 2004; emissions Kesselmeier from et tropical forests al.,tion are 2002; to of Kuhn the special et interest global al.,to because VOC 2002b, their their budget 2004). terrestrial contribu- (estimated area to fractionMediterranean of be plant 7 30 % species %) (Guenther are is et knownhave disproportional al., to 1995). already as emit In compared been a contrast great to intensively2002; the variety Owen studied tropics, of et VOC, (Kesselmeier al., many 1997, and of 2001, which Staudt, 2002; Simon 1999; et Llusiamonoterpenes. al., Less et 2006). information is al., available on the emission of short-chain oxygenated on studies of onlyand one VOC Keller, 1997; species (Ferreira Lerdau et2010; and al., Oku Throop, 2010; et 2000; Harley al., Lerdau 2008; etgions, and Pegoraro al., species Throop, et diversity, 2004; inaccessibility, 1999; al., Lerdau logistical 2006). Misztal di etc., Because et of the al., the number heterogeneity of of ecore- investigations made in tropical regions are limited (Geron et al., formation and growth ofdevelopment secondary and precipitation organic (Andreae aerosols and Crutzen, (SOA)et 1997; which al., Claeys et 2002; in al., Lelieveld turn et 2004; Collins al., a 1998). 2002; P and global biogenic VOCVOC emission emissions from strength, vegetation however(Guenther from they et temperate rely al., areas 1995; mostly of Guenther on North et studies al., America of 2006; and Kinnee Europe et al., 1997; Simpson, 1999), or Vegetation is the maindirectly a producer of Volatile2003). Organic Biogenic Compounds VOCs (VOCs)an regulate which indirect the can impact oxidative on capacity the of lifetime the of atmosphere greenhouse and gases have and are also involved in the 1 Introduction 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | . and and from were were erent C and ff ◦ 1.6 ± ort between ff ˜ C oes River. The uent of the Rio ◦ Pseudobombax ¨ ffl afer et al., 1992; , Hevea spruceana, 7 % were recorded Hevea brasiliensis ´ o) were studied. For , ± C. Vatairea guianensis ◦ Hevea spruceana Hevea spruceana , W) an a and Vatairea guianensis 0 concentrations were in the and 2 01 ◦ Scleronema micranthum and 9 % and 91 were collected at the bank of the ´ arzea species ± and S, 60 0 Zygia jurana 08 , ◦ Hevea spruceana Garcinia macrophylla, Hevea spruceana Scleronema micranthum ´ arzea) and three from the floodplain region in- 15284 15283 Zygia juruana W) an island located in the Solim 0 Vatairea guianensis Hevea spruceana , 58 and ˜ a Mirim (03 ◦ Hura crepitans, Pouteria glomerata ´ ´ o such as o, S, 59 ´ ´ arzea) were measured. arzea, and 0 erent floodplain environments was investigated using plants ff 15 ◦ from terra firme were measured in 2006 and 2007. The terra from v from igap ´ o versus v ´ arzea and igap Garcinia macrophylla Hevea brasiliensis, Hevea guianensis C and relative humidity values of 77 % ◦ 1.3 erent enclosure systems were used for the measurement of tropical and ± ff ˆ onia (INPA, Manaus), which took place at the INPA Campus forest in Manaus, C ◦ Hevea guianensis ´ o species The plants which were about 2–3 yr old were collected in March 2008 from the A total of three replicates for each species were measured with some exceptions The tropical vegetation screening experiment was a cooperative e complete plant above ground. Ambient airfilters was (Zefluor scrubbed Teflon of filters, small 2 particles µm using pore Teflon size, Gelman Science, USA) and of ozone with Two di Mediterranean vegetation. For thetem measurement developed at of the tropical MaxThis Planck plants Institute enclosure an for system enclosure Chemistry in has sys- Kesselmeier Mainz, been et Germany described was al., used. in 1996;fully detail Kuhn elsewhere et light (Sch al., permeable 2002a).mance FEP Two Plastics, identical Teflon Germany), branch foil were flushed cuvettes (Norton,used with made as ozone 50 of µm free the ambient reference thickness, air. “empty” One Saint-Gobain cuvette cuvette and Perfor- was a second cuvette enclosed a branch or the surroundings of Montpellier, France, andof were the potted institute and at maintained an in approximate a day/night greenhouse temperature of2.2 25/15 Enclosure techniques and gas exchange measurements tem. Trace gas exchanges were measured during the next2.1.2 day. Mediterranean vegetation A total of sixteenshrubs, potted grasses plant and palm species trees includingdistribution typical ranges deciduous for were the and studied Mediterranean non-deciduous area atmonths and trees, the of having CEFE-CNRS April di in to Montpellier July (France) 2008 during (Table the 2). For each species there were three replicates. during the dry andrange wet of season, 335–408 respectively. ppm. Ambient CO (see Table 1). Dynamicevening before flow-through-enclosures measurements were were made installed to allow at for 08:00 adaptation p.m. to the on enclosure the sys- 27.8 nets, and were irrigated daily. Daily mean temperature conditions of 29 bax munguba, Vatairea guianensis Ilha da Marchantaria (03 igap collected at the bankNegro. of The the influence of Tarum di that occur in v After collection plants were pottedand in allowed earth to adapt obtained to fromsurements. the the Plants new sites conditions were of for the kept at plant’s least under origin one sunlight month before conditions, making were mea- protected by mosquito firme species collected at the ReservaReserva’s area Ducke, which is is coveredzon terra by situated firme primary 40 (Gomes km and vegetationHura Mello-Silva, from crepitans, characteristic 2006). Manaus. Ocotea The of cymbarum, v 90 % Pachira the insignis, of Central Pouteria glomerata, the Ama- Pseudobom- the Max PlanckAmaz Institute for ChemistryBrazil. and One the or Instituto twoVatairea Nacional year guianensis old de saplings Pesquisasmunguba, of da Ocotea cymbarum, PachiraVatairea insignis guianensis and floodplain region which iswhite-water regularly during the inundated flooding with periodundated nutrient (v with rich black and water rich sedimentinterregional in loaded comparison humic the matter, or species clear-waterboth (igap regions (igap representative trees from the upland forest (terra firme) ecosystem, eight from the 5 5 20 25 15 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | er- ff (PAR) 1 − s 2 set of spec- − ff . The air was (Ansyco, Ger- 1 in synthetic air, Pseudobombax − 2 2 for the small cuvette , and 1 − O infrared gas analyzer 2 2 ppm CO /H 2 ± placed up line of the analyzer in- (512 2 1 , Bronkhorst Hi-Tec, Germany). Two Hura crepitans − 1 − O zero point calibration of the infrared ´ 2 o), 5.0, Messer Griesheim, Germany) was ects and with regard to the o 2 ff (igap and H 15286 15285 2 erent heights before and after the measurements ff O was monitored by direct sampling from the sam- 2 C, which was always higher than the cuvette or ambient ◦ , and H 2 for the larger cuvette. 1 − O infrared gas analyzer (LI-COR inc. 7000, Lincoln, Nebraska, USA) 2 O exchange were measured by using a CO /H 2 2 ambient light conditions were followed. In the case of the other plant species and H 2 erent cuvette sizes were used depending on the size of the plant to be measured. Gas exchange of Mediterranean vegetation was measured using a dynamic tem- Measurements of tropical vegetation were performed under semi-controlled condi- A Teflon fan installed in the cuvette allowed a homogenous mixing of the air in the CO ff mately 105 ml was constantly flushed with air at a flow of 650 mlmin course of all otherto gas the exchange chamber measurements system. thesured Light same with intensities thermocouples sensor and of was type thea installed E cuvette datalogger next (Chrom-Constantan, and CR23X OMEGA) leaf were (Campbell recorded temperaturesrological Scientific with and mea- Ltd. physiological Shepsherd, parameters were UK). monitored(V25). All and other recorded with micrometeo- a control unit perature and lightet controlled al., chamber 2004). system This custom (Bracho-Nunez made et gas al., exchange 2011; chamber Staudt with a volume of approxi- closed with reflectingin film the in cuvette. order TheLicor, to USA) irradiation inside obtain was the a checked cuvetteand with homogenous at found a di to distribution quantum be oftion homogeneous sensor the value for (Model determined light the SB in area 190, the of center the of whole enclosed the plant. cuvette The was irradia- taken as the incident PAR. In tions following ambient relative humidity andGarcinia temperature. macrophylla, During the Hevea measurements spruceana of munguba additional photosynthetic active radiation (PAR) wastem constantly consisting provided of by four a double LED chainsand of sys- a designed mixture of by red, the bluemany. and electronics This white LED department light system constructed of supported theand a MPI maximum was for light placed regime Chemistry of perpendicular in 500 µmolm Mainz, to Ger- the cuvette. Gaps between the LED groups were sensitivity and zero drifts asinstrument a function was of corrected time. for Furthermore, temperatureified the e and signal response measured of reference the concentrations.conductance Assimilation, were calculated transpiration according and to stomatal Pearcy, Schulze and Zimmermann (1989). the calibration of the analyzer was checked and the signal response was corrected for ter vapor (Li 610; LI-COR, Lincoln, Nebraska, USA). At the end of each experiment a second CO as reference. Pressurizedused nitrogen as gas the (N referencegas gas analyzers. for The the gas CO unit flow to (membrane the pump, 12 instrument(Omega, Volt; was KNF-NEUBERGER) supplied USA) and by that passed a adjustedlet. through custom the Calibration made a flow pump rotameter of to thea 0.5 lmin analyzer calibration gas was standard accomplished forLI-COR, prior the Lincoln, calibration to Nebraska, of the USA) CO and experiments a by dew use point of generator for the calibration of wa- a constant temperature of 45 temperature in order to avoid condensation in the lines. (LI-COR inc. 7000, Lincoln,ential Nebraska, mode USA). receiving This equipment an was analog operated signal in of di the absolute concentration measured by For the small plantsflow a was 9 l controlled cuvette byand was a to built needle 20–40 and valve lmin and for the adjusted to big 10 plants lmin acuvette. 100 Cuvette l temperature cuvette. and The a relative humidity temperature/relative was humidity measured sensorExchange in of (Model bypassed VOCs, air Rotronics CO by ple YA-100F, Walz, and Germany). reference cuvette. All sample tubing was made of Teflon and maintained at many) placed in aA Teflon combination tube of three to Teflonpump prevent membrane the pumps oxidant filtered (Vacuubrand, interferences Germany) ambient inside wasitored air used the by to to an enclosure. both in-line cuvettes.di flowmeter The (EL-Flow, air 50 flow lmin to each cuvette was mon- an ozone scrubber composed by ten copper nets coated with MnO 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ) C s E ◦ E ) at 1 1 ¨ uller- − ± 30 130 Td; = = erent methods, ff Vmolecule E/N 2 cm ine GC-FID equipped 17 ffl and the aromatic shrub − 10 = O infrared gas analyzer (LI-COR Inc. 2 ects. In order to ensure adaptation of ff /H 2 Pinus halepensis 15288 15287 ). Relative humidity was also maintained constant at 1 − (PAR) (Niinemets et al., 2011). Therefore, as based on s 1 2 − er gas number density, 1 Td − s ff 2 − bu possess glands and ducts which store VOCs. It has been shown N C. Chamber and plants were illuminated with white light (OSRAM 36 µmolm ◦ ± cinalis ffi ine gas chromatographic (GC) method equipped with a flame ionization 1055 ffl = 1) were measured by the PTR-MS with a dwell time of 1 s: m21, m29, m31, + C and 1000 µmolm ◦ 13 %. All data were stored on a 21X datalogger (Campbell Scientific Ltd., Shep- C for at least 48 h before weighing. Errors were estimated at 0.2 % and 2 % for dry ◦ ± For real-time VOC monitoring, the PTR-MS (Ionicon Analytik, Austria) was operated Projected leaf areas were determined either with an optical area meter (Delta-T For the measurements, one or several terminal leaves of an individual plant were m87, m93, m95, m107,complete m121, cycle took m137, 27 m139, s. The m151, main m205. compounds detected The from measurement tropical of vegetation were one tion of GC-FID peaksis and reported PTR-MS by signals. Bracho-Nunez A et detailed al. description (2011). of thein GC systems selected ion-monitoringelectric mode field at strength, standarda operational drift tube settings voltage ( ofWeight 600 V. A total ofm32, 27 mass m33, signals m39, (protonated m42, masses; m45, Molecular m47, m55, m59, m61, m69, m71, m73, m75, m81, m83, Mediterranean vegetation four instrumentsscription were below), used: an AirmoVOC adetection C2-C6 of PTR-MS isoprene online (see and GC-FID detailed lightwith (Chromatotec, a VOCs, de- Chrompack a France) TCT4002 Chrompack thermo-desorber for (all CP9003VOCs the Varian o Inc.) such for as the detection monoterpenes ofGC-MS and higher equipped sesquiterpenes, with and a a Perkin-Elmer Varian Turbomatrix CP3800/Saturn2000 thermo-desorber to back identifica- 2.3 VOC measurements VOC emissions from tropical(i) vegetation were by measured collection using onwith two cartridges an di using o andetector automatic (FID; sampler Kesselmeier et andin al., subsequent Mainz, 2002; analysis Germany, Kuhn and et (ii) al., by 2002b) online in PTR-MS the as MPIC described laboratory below. In the case of Devices Ltd., Cambridge, UK)a sheet or, that was by subsequently copying scannedSoftware) using the (Kesselmeier the software et shape Size al., (Version of 1.10R,60 1996). M the To obtain measured leaf leavesweight dry on and weights, leaf leaves area were determination, dried respectively. at least 12 h before making measurements. the plants toleast the 1 chamber h before environment, thehad all measurements, become species or constant. Leaves until were ofRosmarinus the placed the o VOC conifer in signals measured thethat with chamber mechanical PTR-MS at stress canlarge cause overestimations large of bursts VOC of emissionat 30 VOCs rates from normalized these asour plants standard experiences leading emissions during to ( previous work the leaves of these species were enclosed at placed perpendicular to the light tosurface ensure of homogenous the light leaves. distribution For onto most the enable of adaxial the proper plants, placement itany in was measurements the necessary to to chamber; minimize remove this some disturbance was leaves e done at least one week before chamber air temperatures wereConstantan, monitored with OMEGA). two For thermocouples allture of type measurements and E light of (Chrom- was Mediterraneanand kept PAR vegetation constant tempera- at48 standard conditions (leaf temperature sherd, UK). Photosynthesis andportion transpiration of were the inlet measured and by outlet7000, air directing Lincoln, through Nebraska, a a USA). constant CO then re-humidified by passing abler. variable All portion of tubing the was airtemperature made stream of through of 45 a Teflon water and1000 bub- W) sample filtered lines by were(Licor, a maintained PAR-SB 190, at 5 Lincoln, cm a NE, water USA) constant located bath. next PAR to was the measured chamber system. with Leaf a and quantum sensor purified and dried by a clean air generator (AIRMOPURE, Chromatotec, France) and 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | 1 − − (1) erent ff erent iso- 10 %. For ff ± 1 sample chamber − c . 1 = − for sesquiterpenes, , the leaf dry weight c 1 1 ∆ − − in lh for acetone, 493 pmolmol Q 1 erence ( − ff . C. VOC determination occurred with ten 1 ◦ − 15290 15289 in gmol cult due to their tendency to fragment into di ) of each compound was calculated according 1 ffi M , the chamber flush rate − 1 h − 1 for monoterpenes and sesquiterpenes always refers to − for monoterpenes, and 94 pmolmol for methanol, 579 pmolmol s 1 1 E − − (µgg 3 C (Zero Air Generator, Parker Co., USA). The background signal s ) in nmoll ◦ − E 10 · . For the quantification of sesquiterpenes a calculation of simple 1 − M ·  Q dw  c = ∆ The PTR-MS instrument was calibrated using a VOC standard mixture in nitro- In the case of Mediterranean vegetation PTR-MS measurements were performed As mentioned above, for measurements of tropical vegetation a reference and a sam- -pinene, methanol and acetone) at concentrations of 300 nmolmol s empty or reference chamber E depends on stomatal conductanceduring and night. Thus, accumulation in occurs the in morning a the methanol stomatal peak cavities was detected on some occasions, and the detection limits of the GCs ranged between2.4 0.1 and 0.4 ngl Data treatments The emission rate to Eq. (1)c based on the(dw) measured in g concentration and di the molecular mass For VOC emissions measured(the under conditions non for standard mostlogical light of algorithm and the described temperature measurementsactual by conditions on VOC Guenther tropical emission species), et ratesemission to the al. rate. standard phenomeno- (1993) emission This was rates, algorithmVOC often used describes originating referred to the from to standardize as lightmonoterpenes DMAPP the the and (Dimethylallyl and basal temperature pyrophosphate), distinguishes dependencies suchnewly between for synthesized as emissions VOCs. isoprene Since fromperature and dependency acetone VOC during and this storage study, methanolbe emission pools described rates also of and with showed these the compounds light Guenther could algorithm and also (Guenther tem- et al., 1993). Methanol emission these data were always2011). complemented The detection by limit GC-FID ofdard or the deviation PTR-MS of GC-MS was the (Bracho-Nunez estimated emptywas chamber as et concentrations typically being al., (at 1.6 1.96 nmolmol the times 95 the %for stan- confidence isoprene, level) 201 and pmolmol compounds depending on the VOC species (Demarcke et al., 2009; Tani et al., 2003), with the PTR-MS is usually very di were followed by three cycleswas of repeated instrument 3 to background 10 measurements. times. This process gen (Deuste Steiningerα GmbH, Germany) containingcalibration, some the target gas VOCs0.5–10 was nmolmol (isoprene, further dilutedion-molecule reaction with kinetics synthetic was usedWisthaler air as et to described al., elsewhere 2001). final (Hansel Since concentrations et the al., of quantification 1995; of monoterpenes and sesquiterpenes culations the reference chamber signalsfrom (with background the subtracted) sample were chamber subtracted signals (with background subtracted). similarly as described above butof with enclosure a slightly measurements changed switching sampling between protocol. sample Ten cycles and empty reference cuvette ple chamber were used. Thechamber PTR-MS with was PFA connected tubing to (1/8”) thecycles heated reference of and to the the 45 sample referencesignals and were sample determined chamber with separately.lyst air maintained The at samples instrument 350 after background passingwas over subtracted a from heated the platinumrepeated reference from cata- and 08:00 p.m. sample to chamber 06:00 p.m. signals. of This the procedure following day. was For VOC emission rate cal- m81). On the othercompound hand, classes and Mediterranean additional vegetationmers emissions showed of of emissions sesquiterpenes monoterpenes of (m205).therefore or the Di PTR-MS same sesquiterpenes based cannotthe be sum of distinguished all with monoterpenes and a sesquiterpenes, PTR-MS, respectively. methanol (m33), acetone (m59), isoprene (m69), monoterpenes (m137, fragment on 5 5 25 10 15 20 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | - ´ o γ ) and ´ 1 arzea, Hevea for iso- − -Pinene 0.08) of Vatairea species: Garcinia h s α ´ 1 arzea and E . , out of the − s p < ). Low emis- from v ). and the other E erent ecosys- 1 1 ff − Hevea erences among varied from 0.3 originating from − Scleronema mi- h Garcinia macro- ff h ´ 1 arzea and igap s 1 − E ect in ANOVA was for − ff 1 erences ( − ff h . Only four tree species did not show detectable Zygia jurana) from v 1 , were moderate-emitters 10 µgg − a moderate emitter (emis- > and erence e ff (Fig. 1). Five species ( Hevea spruceana -pinene (90.2 %) and camphene , 1 α − Hevea spruceana -pinene (2.8 %) (Fig. 3). h β Zygia jurana . The latter one was a very weak 1 -pinene (57 %) followed by limonene − Pseudobombax munguba α ). 1 and − saplings was similar for both provenances ´ o. Similarly, the relative composition of the and ) and the other ones were high emitters h Ocotea cymbarum Hevea guianensis 1 1 from two floodplain ecosystems (v − − Garcinia macrophylla, Hevea brasiliensis, He- h 15292 15291 Hevea guianensis emitted 1 and and -pinene (1.8 %). In the case of − ), β 1 Hevea brasiliensis − ). h 1 erences were found in the VOC emissions of 1 − ff − h ) were found to emit monoterpenes. No monoterpene 1 ´ arzea and igap Hura crepitans − ( were mainly composed of 1 Hevea spruceana 1 µgg − Scleronema micranthum h Hevea spruceana < 1 − ´ o followed by of 1.5 µgg Hevea brasiliensis and (Fig. 1). The strongest monoterpene emitting tree was s Pouteria glomerata < ´ arzea). The statistically significant di E 1 − ). Interestingly, the geographic origin of the saplings may be of sig- 1 h 10 µgg -pinene (15.9 %) and sabinene (9.1 %). In contrast, monoterpene emis- − 1 Scleronema micranthum h β − > originating from v from igap 1 ´ ) exhibited methanol emissions in the range of 1–10 µgg o vs. v -Pinene (63 %) was the most abundant monoterpene followed by limonene − , monoterpene species composition was similar to that of the α Hevea guianensis Scleronema micranthum ´ o) (Fig. 1). No significant di 10 µgg The oxygenated VOCs, methanol and acetone, were emitted from several of the All isoprene emitting tree species were high emitters ( One-way anova tests were carried out in order to detect possible di -pinene (35 %) was again the main monoterpene followed by limonene (26.6 %) and > Hevea brasiliensis, Hevea guianensis, Hevea spruceana sions of acetone couldboth be ecosystems detected ( in the case of sions of (9.8 %). investigated plant species. Methanolemission emissions rates were varying detected betweenmacrophylla, 1.5 in to Hevea seven 20.2 brasiliensis, species µgg with Pachiraguianensis insignis, Scleronema micranthum,two Vatairea emitted (17 %), sabinene (7.4 %)terpinene and (6.3 %) p-cymene exceeded (5.9cranthum %), that of but inα this case the emissionin this of case the monoterpene igap guianensis monoterpenes emitted by (Fig. 3). (14 %), sabinene (7.5 %),was p-cymene also (5.4 %) the and species main (35–90 %). monoterpene emitted by the rest of monoterpene emitting tree Hevea guianensis monoterpene emitter ( sion ranged between( 1 and 10nificance µgg as indicated by marginally significant quantitative di spruceana emission was detected into the 67.1 other µgg eight species. Monoterpene ters, eight species were classifiedtwo as species, high emitters (emission above(emission 10 ranged µgg between 1 and 10 µgg prene were estimated tophylla, range Pachira between insignis, 12.1 Vatairea and guianensis ( 63.2 µgg and vea guianensis, Hevea spruceana,munguba, Hura Scleronema micranthum, crepitans, Vatairea Pachira guianensis twelve insignis, plant Pseudobombax species screened,two plant we species, were ableemissons to (Fig. identify 1). Considering VOC emissions. the The total other amount of VOC emissions of the ten emit- tems (igap proven by the Tukey’s test. 3 Results 3.1 Screening tropical vegetation In the case of ten tropical plant species ( morning peak observed for methanol was excluded for the calculationtwo of or more independent groups. Meanor VOCs emissions monoterpenes (methanol, acetone, separately) isoprene emitted from from Mediterranean tropical plant plant species and species the same were species from tested di against those due to the burst of the nocturnally accumulated methanol after stomatal opening. This 5 5 25 15 20 10 20 25 15 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , - - 1 α α − h erent erent 1 Spar- ff ff − Brachy- showed and Buxus sem- were classi- (10 and 19 %, Cistus albidus, Quercus suber Prunus persica . The monoter- myrcene and and and -pinene as the ma- cinalis and and Garcina macrophylla 1 α ffi − Brachipodium retusum, h Olea europaea 1 − and released 1 µgg Ceratonia siliqua Pinus halepensis < s Rosmarinus o and E as non isoprene emitters. . The species -ocimene (14 %), myrcene (11 %) and Buxus semprevirens β - E , and and cinalis, Quercus coccifera cinalis cinalis ffi ffi ffi 15294 15293 with emissions between 11.0 and 69.1 µgg emissions also showed a high contribution of Olea europaea -humulene (m137) have been reported to potentially Cistus monspeliensis α , limonene represented the major contribution (40 %), . Brachypodium retusum, Buxus sempervirens, Ceratonia 1 − -pinene (25 %), h erent and variable monoterpene emission patterns. In the Brachypodium retusum, Buxus sempervirens, Chamaerops Rosmarinus o Rosmarinus o β Rosmarinus o 1 ff − Ceratonia siliqua, Coronilla valentina, Olea europaea, Pinus cinalis Quercus coccifera ffi and and Pinus halepensis, Ceratonia siliqua -pinene (24 %), but were dominated by sabinene (37 %). Myrcene, . PTR-MS measurements indicated low monoterpene emissions β 1 Quercus suber − h Emission rates of these plant species ranged between 18.9 and (Fig. 2). Spartium junceum) 1 ); however this could not be confirmed by GC analysis. This discrep- 1 − 1 − − h h and 1 was not comparable with the emission pattern of other plant species. These 1 − − Rosmarinus o Chamaerops humilis, Cistus albidus, Coronilla valentina -caryophyllene (m81) and β 1 µgg The monoterpene composition of the emissions from Mediterranean vegetation was Fourteen out of the sixteen investigated Mediterranean plants emitted monoter- Emissions from five species were found to be dominated by isoprene, i.e. A noticeable release of mass 73 was detected in the case of -ocimene (10 %) in the case of ≤ emission with 49 % andshowed 95 a %, large respectively. number It of is monoterpene noteworthy species, that with up Mediterranean to plants a maximum of 14 di Z respectively) and bypene myrcene emission (5 %) pattern in by pervirens the case of three species had verycase di of whereas in the casephellandrene of were the species with the highest contribution to the total monoterpene camphene (4 %). pinene (33 %) and limonene, camphene and otherssions contributed of less this than species. 3 %emissions to dominated the by monoterpene E-ocimene emis- with 95, 80, and 90 %, respectively, followed by monoterpene species at ratesthe below masses the detection classified limit asrelated for monoterpene to GC other (m81 analysis. VOC Alternatively, and species.like m137) For example, with interferences the ofcontribute PTR-MS sesquiterpene 7.5 and fragments might 6 be % for each mass (Demarcke ethighly al., 2009). species specific (Fig.jor emitted 4). monoterpene speciesemission with rate, a followed contribution by of 46 % to the total monoterpene and 35.6 µgg also for ( ancy might have been causedan by artifact decomposition of of cartridge more sampling labile for monoterpene GC species, analysis, or by the emission of many di afares, Quercus coccifera,fied Quercus as suber moderate to high monoterpene emitters with emissions ranging between 1.03 could be classified as lowCistus isoprene monspeliensis emitters with penes in significant amounts: siliqua, Chamaerops humilis,tine, Cistus Olea albidus, europaea, Pinus Cistus halepensis,cifera, Prunus monspeliensis, Quercus persica, suber Coronilla Quercus afares, valen- QuercusCeratonia coc- siliqua, Cistus monspeliensis, Olea europaea, Pinus halepensis, Quercus range of 2.6 and 9.3 µgg podium retusum, Buxus sempervirens,tium Chamaerops junceum. humilis, Ficus60.7 µgg carica halepensis, Prunus persica, Quercus afares, Quercus coccifera 3.2 Screening mediterranean vegetation All sixteen Mediterranean plant specieswhich investigated being were high found emitters to ( emithumilis, VOCs, Coronilla nine of valentine, Ficuscus carica, suber Quercus afares,whereas the Quercus rest coccifera, of Quer- the plants were moderate emitters, showing VOC emissions in the during daytime conditions (light). Mass(MEK), 73 a could be known the oxidation protonateddance product methyl with of ethyl ketone the isoprene. high Thisrepresented emissions interpretation by of would this isoprene be mass, foundpropanal in such for suggested accor- by this as Jardine plant. methylgyoxal et (Holzinger But al. other et (2010) would compounds al., also 2007) be reasonable. or 2-methyl 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , ) 1 1 − − Cis- h h 1 1 − − emitted with 1.77 -humulene α 1 µgg Cistus mon- 0.1 µgg < Buxus semper- < Pinus halepensis and erences between ff Chamaerops humilis and Ficus carica Quercus coccifera and erent sesquiterpene species ff . In the case of ) were found in the case of 1 (-)E-caryophyllene was the most − h Ceratonia siliqua 1 erence was the higher number of − 0.05) than those detected for tropical ff 0.2) emissions from Mediterranean and for isoprene and monoterpenes, respec- traces of this terpenoid ( p < 1 = − Buxus sempervirens p h ). For some species acetone emissions were 1 15296 15295 1 − − Quercus coccifera . A total of eight di h 1 Brachipodium retusum -bourbonene (15 %) and Quercus coccifera − and β and Olea europaea emitted and 25.6 µgg and 1 Cistus albidus − h 0.07) and isoprene ( 1 , respectively. − 1 = − p h Olea europaea 1 − For Olea europaea species erent plant species was very high compared to tropical vegetation. Next in ranking were methanol, acetone and mass 73. Emissions of methanol were However, not only isoprenoids were emitted from Mediterranean plants. Oxygenated (-)E-caryophyllene was the most frequently occurring sesquiterpene species and Low emissions of sesquiterpenes (0.1–1.0 µgg ff -cubebene (8 %) (Fig. 5). Emissions by and probably inpected. the In growth addition, period, acetonewhereas such emissions five a were from found high the onlyInterestingly, emission investigated in methanol Mediterranean of one and species tropical methanol acetone emitted plantgated could emissions this species, in be of VOC this species. ex- the studyvegetation. Mediterranean were significantly species lower investi- ( did not detect any sesquiterpeneAmazonian emissions forest from air tropical has vegetation, been their recently existence demonstrated in (Jardine et al.,found 2011). to be widely distributeda in consequence plants of of growth both (Fall, ecosystems. 2003). This Since can the be investigated understood plants as were still saplings, teen out of 16emitters. plants. Isoprene Five standard species emissionemission were factors factors classified in were plants as from usually high bothplants ecosystems, higher and of with than mean four 33.9 µgg values monoterpene as bytively. the low Furthermore, high isoprene emitting the monoterpenetropical plants species was quite pattern constant,species in emitted pattern contrast observed from to among the the Mediterranean great plants.only variation investigated Sesquiterpenes of in were the emissions detected monoterpene from Mediterranean vegetation. However, although our experiments tropical plant species.monoterpene emitters However, in of thegated, Mediterranean isoprene striking emitters vegetation. equaled di Of the monoterpene thewere emitters. tropical Four isoprene tropical plants plant emitting species investi- speciescontrast, monoterpene and emitters another predominated the four Mediterranean species vegetation with emitted four- monoterpenes. In monoterpenes ( Most of the investigatedemissions. tropical and ANOVA Mediterranean results plants exhibited reflect substantial no VOC quantitatively significant di all investigated plant species emittedlarge methanol. (between The 1.04 range and ofdetected, 13.5 emission µgg but rates was at very lowexcept rates for (Fig. acetone 2). emissions Mostand from 4.17 of µgg these emission rates were 3.3 Comparison of VOC emissions from tropical and Mediterranean plant (67 %) and germacrene D (75 %),were respectively. A found great in variety of case sesquiterpenewere of species detected (Fig. 5). VOCs such as methanol and acetone were also found. Except for be more sensitive for these compounds than the PTR-MS. was the solespeliensis. compound emitted inabundant the sesquiterpene emitted case (78 of D and (22 %). 77 %, respectively)α followed by germacrene were composed by (-)E-caryophyllene (33 and 25 %, respectively) and by di tus albidus, Cistus monspeliensis virens, Ceratonia siliqua were observed, but only detectable by GC-FID, indicating that the GC-FID method may monoterpene species. Furthermore, the variability of monoterpene species among the 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | from reported ´ arzea, which erences. In con- ff from v species Kesselmeier Ficus carica, Spartium erences could be due to Vatairea guianensis ff in earlier studies (Benjamin Chamaerops humilis Quercus Salix martiana and and ) were found. High isoprene emissions for erent Mediterranean areas, suggesting ge- ff 15298 15297 Ficus carica (Geron et al., 2006b; Klinger et al., 2002; Wang Brachypodium retusum and Laetia corymbulosa Brachypodium retusum, Buxus semprevirens, Chamaerops Spartium junceum were in close accordance with Owen et al. (2001). In contrast to and Hevea brasiliensis ´ o as well as ects on atmospheric chemistry/physics and the carbon budget. For this ff erences. However, uncertain species identification, missing normalization of ff erent origins of the plants within di ff Besides isoprene, monoterpenes make one of largest contributions to the global The most substantial isoprene emissions were found for In both ecosystems we found plants that emit isoprene, monoterpenes, methanol ´ arzea and igap emissions (Guenther et al., 1995). During our experiments with tropical vegetation, et al., 1996; Owenthe et di al., 2001;netic Pio di et al., 1993).the data, These and di othercases technical no aspects direct in emission previousthe was studies case reported, cannot of the be but isoprene ignored. assigned,by emission In based Benjamin from some et on al. genus (1996) average or as from in several tropical plantVOC species flux. Together, (Harley isoprene et and al., monoterpenes 2004). make up 55 % of the estimated global isoprene emitting species ( humilis, Ficus carica Buxus sempervirens our results, no isoprenejunceum, emissions Chamaerops are humilis reported in the case of one more species wasmonoterpene emitter. identified by Kuhn et al. (2002b,v 2004) as areached light values dependent similar toand those Staudt, measured 1999. forspecies several The are results consistent obtained(Harley with et here al., emission 2004; for rates Padhy the and reported Varshney, rest 2005). for Also of other in the the tropical Mediterranean isoprene tree area high emitting species and by Geron etbut not al. of (2006b) Amazonia.ters which A few among concentrated tree them on specieset were tropical al., identified plant 2007). earlier species Additionally, as Wilskecal of monoterpene et tree emit- China al. species as (2007) monoterpene identified emitters, six though out at of low eight rates. For SE the Asia Amazon tropi- region been answered with the exception of the screenings performed by Klinger et al. (2002) ever, the question of how many trees emit monoterpenes and other volatiles has not trast to the set of Amazonianranean plants, monoterpene plant emissions predominated species. for This Mediter- emissions from is plants in of Mediterranean close ecosystemsmonoterpenes accordance known (Owen to et with release al., earlier high 2001). amounts Investigationsmentary investigations of of in Amazonian of terms plant VOC of species are areas,2009). frag- plant Several species and screenings analytical of techniques(Harley VOC (Kesselmeier et et al., emissions al., 2003), from from(Harley Asia tropical (Oku et plant et al., species al., 2004; 2008), fromraro Lerdau or et Africa and from al., America Keller, 2006) including 1997; have Amazonia Lerdau been and made Throop, but concentrated 1999, only 2000; on Pego- isoprene emissions. How- et al., 2009; Karlor et less al., by 2004). chance and Forindicate the our a small screening trend numbers and study cannot will we lead at chose to least a plant improve final data species view bases. and/or more but acetone the as results the do main compounds. But there were qualitative di ies covering larger terrains misshigh substantial reactivity. Therefore, amounts this of study emitted contributesemissions to VOC from the because plant description of species of their plant ofthe specific two VOC Mediterranean such special area. ecosystems, Investigationand i.e. demonstrate of the the Amazonian Mediterranean domination and of planting monoterpene species emitting of species. are tropical In numerous contrast, plantrare, screen- species though compounds for such the as isoprene, identificationpreviously monoterpenes, been methanol of detected and VOCs acetone above have on Amazonian forests the in species high level concentrations (Eerdekens is still A robust assessment of regional andstand global VOC their emissions is e needed inpurpose, order to we under- need moreand information to at contribute the to the plant understanding species on level the to ecosystem deal level, especially with as processes flux stud- 4 Discussion 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | , . 1 Pi- − He- and 1.7, s 1 Coro- ± − (Llusia ) emis- Prunus 1 1 ) or even Coronilla − − 1 h and h − 1 1 h − , though − 1 Quercus coc- 0.1, 2.0 . Monoterpene − , and was dominated Buxus semper- ± species. The rub- Cistus albidus, Pi- Hevea guianensis 1 µgg cinalis Cistus monspeliensis of 0.2 ffi Hevea brasiliensis < Hevea of 10.9 to 38.1 µgg species investigated so far s erences reflecting the com- E ff cinalis ´ arzea exhibited lower emission ffi Hevea brasiliensis Chamaerops humilis ) were found with Hevea Hevea brasiliensis 1 − Rosmarinus o from v h 1 . Nearly all monoterpene emitting trop- have been reported (Blanch, 2007; Llu- − ). We found low ( was a low monoterpene emitting species could be classified as non monoterpene 1 1 , and − − ) as well as higher (11–45 µgg h h 1 Prunus persica, Brachipodium retusum, Cis- (Pio et al., 2005; Staudt et al., 2008, 2004). 1 Rosmarinus o 1 2 µgg − -pinene (Wang et al., 2007). Further investiga- 15300 15299 − − 1 h β < and the terra firme species − 1 h − and 1 were found for the first time. − have been reported (Hansen and Seufert, 1996; Pio , respectively, as reported by Owen et al. (2001). -pinene followed by limonene and sabinene. In con- 1 1 (Llusia et al., 2002; Owen et al., 2001). Similarly, − − α Hevea spruceana 1 h h − 1 Hevea guianensis 1 h − − were in close accordance with other reports that showed showed a total monoterpene are already described as monoterpene emitters in the liter- 1 , which corroborates more recent literature, showing typical -pinene and − 1 Spartium junceum ´ o and α − erences were observed for the monoterpene species emitted h ff 1 and − has been identified previously as a non isoprenoid emitter tree cinalis 0.3 µgg Scleronema micranthum Hevea spruceana (Fig. 3). No bibliography data were found about the VOC emission ffi ± was found to emit high quantities of monoterpenes and low amounts emitted monoterpenes in the range previously observed (Llusia and from igap no monoterpene emission was reported previously. Low, but still de- ) with a monoterpene emission pattern similar to Buxus sempervirens 1 species except 5.5 µgg − species. Our data show that these species are also strong monoterpene similar, lower (0.2–1 µgg s ± 1 though with PTR-MS only. For Ceratonia siliqua − Hevea brasiliensis Ficus carica was observed in the range reported earlier between 1 and 5.5 µgg Hevea 2.3 and 2.2 Hevea Rosmarinus o Quercus suber ± 1 µgg This study gives an impression of the domination of monoterpene emitting species < ature with high emission (3.6–11.7 µgg tus albidus sion rates were reorted inLlusia earlier studies and (Arey et Penuelas, al., 2000;1993; 1991; Benjamin Ormeno Staudt and et Winer, et 1998; nilla al., al., 2007a–d; valentina 2010; Owen Winertectable et et emissions al., al., of 2001; monoterpenes 1992).virens, Pio ( Cistus For monspeliensis, et Olea europaea al., emissions by and sia and Penuelas, 1998; Ormeno et2005). al., 2007c; Penuelas and Llusia, 1999;emitters, Simon et whereas al., low monoterpenepersica, emissions Brachipodium were retusum, detectedvalentina Chamaerops in humilis, the Cistus case of albidus and Penuelas, 2000; Ormeno ethigher al., rates of 2007a,c,d, 11 2009; to Owenet 14 et µgg al., al., 1993; Staudt 2001), and though Lhoutellier,study also 2011). for Monoterpene emissions as measuredemissions in of our 1.1–6.9 µgg nus halepensis Penuelas, 2000; Ormeno ethigher emissions al., between 2007a,b; 14.8–86 µgg Owen et al., 2001). But also in this case tor of 35.6 summertime values of 10–30Quercus µgg afares of isoprene (seecifera also Welter et al., 2012). Monoterpene emission by (Seufert et al., 1997; Steinbrecher et al., 1997), but this study found an emission fac- ple pattern of this important tree of the Central Amazonianin forest. the Mediterraneanof area aromatic which plants. iscomparable In supported to a literature by data, few the e.g.nus cases, the halepensis, existence observed monoterpene Quercus of emission emission coccifera 5.7 from a rates large of number monoterpeneBut in were general, thereplex were background quantitative for and the qualitative emission di and detection of this isoprenoid group. For exam- Nevertheless, it is of specialbelong interest to to the note group thatterra of all firme monoterpene species emitters. In( addition, this study revealedHevea that spruceana the vea spruceana rates. No qualitative di by all ical trees of thistrast, work the emitted emission patternby reported sabinene followed previously by for tion is needed forfloodplain a species better understanding of these emission patterns of the dominant ber tree even exceeding the high emissions reported2002; earlier Wang (Geron et et al., al.,ting 2007). 2006b; Klinger No et information al., wasemitters found with for emissions the in other monoterpene the emit- order of magnitude of monoterpene emission was found to dominate in the group of 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | - E Quer- Cistus erent than ff Rosmarinus is one of the -ocimene in our -ocimene and E in contrast to other Z erent sampling and has been described ff -pinene, coincided with cult to use such data for β ffi Pinus halepensis -ocimene, the latter compound Ficus carica and similar ranges as reported E or ects must be taken into account (Geron -ocimene) was completely di ff E Buxus sempervirens -pinene, limonene, sabinene, etc. (Blanch, -pinene, respectively. Our results with β α 15302 15301 -ocimene and Z -ocimene. On the other hand, we could not detect -pinene emission which was the only monoterpene -pinene, camphene and Z α α -ocimene, Spartium junceum -pinene, erent monoterpene species were found in our study Cistus monspeliensis Z ff -pinene, myrcene, limonene, camphene and eucalyptol α β we found (Hansen et al., 1997; Lenz et al., 1997; Llusia and Penue- were in close accordance with reports by Owen et al. (2001), (myrcene, cinalis ffi -phellandrene and , i.e. emissions of α Olea europaea , emissions of 15 di -pinene, sabinene, -pinene and limonene or only confirmed the high variability of emissions as reported earlier (Hansen et al., α α Rosmarinus o Ceratonia siliqua Quercus coccifera cinalis Today we understand that the variability of isoprenoid emissions is a consequence In contrast to the rather homogenous emission patterns as found for the tropical -phellandrene only. Furthermore, we could identify myrcene and ffi Investigations performed with conifers demonstrated that the geographical variation of many factors triggering plantfactors, secondary which metabolism. can Seasonality influence ispene one the of species amount the of composition main emissions (Llusiaand and and Llusia, perhaps Penuelas, also 1997; 2000; the Staudtthe Owen monoter- developmental et et stage of al., al., plants 2001; 2000,data and Penuelas ecosystems. obtained 2002) However, even during resulting if we similar indominance, only besides seasonal reports technical compare triggers, stages on the otherof genetic dependency variability, origin factors the on as chemotype of well at similar as theet hybridisation, site or al., and even stress 2000; e higher Guenther et al., 1993; Niinemets et al., 2011; Staudt et al., 2010, 2004). emissions of any monoterpene emission from authors who detected low monoterpeneet emissions al., (Benjamin 1997, 2001; and Pio Winer, et 1998; al., Owen 1993; Seufert et al., 1997). (Fig. 4) contrasting withsuch as other reports(Pio with et only al., about 1993, 4o 2005; to Staudt 7 et monoterpene1997; al., Olivier species, et 2008, al., 2004). 2011a;et Measurements Ormeno al., et 1997) from al., coinciding only 2007b,c,d,species 2009; in the Owen reported et in al., 2002; allas Seufert a studies. non The monoterpene shrub emitter by Owen et al. (2001) but our measurements show low 2007; Llusia and Penuelas, 1998;by Owen et al., 2001). MonoterpeneHansen species emissions and Seufert (1996),2009), Llusia Olivier et and al. Penuelascus (2000), (2011b) suber and Ormeno Staudt et and al. Lhoutellier (2007a,c,d, (2011). In the case of were reported previously, like gation. On the other hand a variety of compounds that were not detected in our study also reported by Areypattern et reported al. in (1991)2002; several Owen but et other this al., reports 2001; completelymost Pio (Benjamin intensively disagreed et investigated and al., with conifers 1993; of the Winer,emission Winer, the 1983). emission 1998; Mediterranean patterns area Llusia (Benjamin with and a etLlusia large Winer, and al., variety 1998; Penuelas, of Blanch, 1998,Penuelas 2000; 2007; and Ormeno Corchnoy Llusia, et et 1999; al., al., Simonocimene 2007a–d; et were 1992; also Owen al., observed 2005). et in2001), As al., previous in but 2001, work our the 2002; (Ormeno studies, monoterpene et terpinene-4-ol al., 2007a,b,c; was Owen found et for al., the first time in our investi- sions of monspeliensis Owen et al.α (2002) but notstudy. For with Llusia et al. (1998) who reported an emission of analytical methods, plant origin, planttions developmental or stages and even environmental questionable condi- emission plant models identification, (Niinemets et making al., it 2011). di plants species inmonoterpene our species study, composition. thefor The Mediterranean monoterpene plants emission showedthat reported pattern a by high found Owen here variability et of al. (2001) or by Llusia et al. (2002), who reported emis- for las, 1998; Olivier etshould al., be 2011a; noted, Ormeno however, et thatthe al., Owen amount 2007b,c,d, et 2009; as al. Owen found (2001)be et by reports al., understood us. some 2002). This to emission It observed result rates variability twice from of a monoterpene variety emissions of may influences, such as di no monoterpene emissions for 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | most Cistus and Rosmarinus and -caryophyllene by cinalis β erences in analysis Cistus albidus ffi ff were quantitatively but , in contrast to observa- could be reported for the cinalis ffi Rosmarinus o -ocimenes are light dependent (Si- were in concordance with Ormeno , it has been demonstrated that the ects may also contribute. Sesquiter- β 1 -cubebene. Sesquiterpene emissions ff − erent genetics due to evolutionary vari- β h ff -caryophyllene emissions, whereas a va- 1 Quercus coccifera Olea europaea − β - and and α 15304 15303 Rosmarinus o Pinus pinea culties depending on the VOC detection method. 0.32 µgg and ffi ± and erentiation in monoterpene composition. In the study ff Pinus halepensis, Cistus monspeliensis ine gas chromatographic methods as compared to online PTR- disagrees with the findings by Llusia et al., 1998. Such variation ffl culty of PTR-MS for the measurements of sesquiterpenes, reporting as low as 0.63 Pinus halepensis ffi (Owen et al., 2002) seem to support such an approach. But for example Pinus halepensis . Considerable emissions in darkness for cinalis Cistus albidus The sesquiterpenes were detected only in the case of Mediterranean vegetation ffi pene emissions are known to be induced by a variety of stresses including heat and of et al. (2007a,d) but contrasted significantlysia higher emissions and found in Penuelas, other 1998; studiesemissions Ormeno (Llu- from et al., 2007b,c).tions We reported did by not Ormeno find etCistus al. any monspeliensis (2007a–d, sesquiterpene 2009). Thein emission the of sesquiterpene emissionsprotocols in and the sampling literature and plant maysons, enclosure be techniques. measuring due But conditions to other and factors di such overall as stress sea- e riety of sesquiterpene species were reported2009; in Staudt other studies and (Ormeno Lhoutellier, et 2011). al.,of It 2007a,c,d, the is important sesquiterpene to speciesstudies note that performed identified for in here the wereet Mediterranean al., partially 2007a–d) region in except (Llusia for accordance emissions and of with Penuelas, other 1998; Ormeno sesquiterpenes (Ciccioli et al., 1999;1998; Hansen Ormeno and et Seufert, al., 2007b,d; 1999;In Staudt Llusia the et and al., course Penuelas, 2008; of Staudtthese our and work compounds Lhoutellier, 2007, on in 2011). Mediterranean2009; close vegetation Llusia accordance we et found with al., aBuxus other 1998; high sempervirens, Duhl variability reports Ceratonia et for (Ormeno siliqua al.,first time et 2008). here. Sesquiterpene However, al. emissions sesquiterpene from 2007a–d, not emissions qualitatively from comparable. We found only MS methods are observed, theconfirmed latter the being di less specific,high however. fragmentation Other patterns studies (Demarcke have etization al., of 2009; sesquiterpene Tani et emissionsand al., in only 2003). the The a character- case few of oaks, the birches Mediterranean and area pines is typical sparse for this region are reported to emit Higher sensitivity by o Nunez et al. (2011) reflect the di in the case of emission of some monoterpenemon species et such al., as 2005), thoughand potentially Bertin, supported 1998; Staudt by et high al., temperature 1997, exposure 2000, (Staudt 2003). and not with tropical plants.sure Due and to emission their rates, these highet compounds reactivity are al., and easily relatively 2008). missed low Special oret vapour underestimated analytical al., pres- (Duhl 2004; adaptations Merfort, can 2002; Tholl facilitate et their al., quantification 2006). Results (Helmig previously published by Bracho- temperature only or temperature andbased light on may be the of solepene importance. storage temperature Some organs such estimates normalization as are o for plants species thatmonspeliensis have monoter- standard light and temperaturemathematical conditions algorithms which such as should themalization be G93 was normalized (Guenther not if et performed al., possibleMoreover, in 1995). by the all However, such emission studies nor- responses andvary cannot to considerably be temperature with applied and for time lighttions all depending are among compounds. on not environmental constant prevailing driversthe weather but normalization (Staudt can conditions to and and common standard interac- Lhoutellier,discussed conditions carefully. 2011). Furthermore, a However, the quantitative without choice comparison between has an to algorithm be taking into account (Hanover, 1992), leading to aof di Hanover (1992), plant species fromcompared the with studies South performed East in French the Mediterraneangal Italian area and and were California’s Spanish Central Mediterranean Valley area, supposing Portu- di ation. Another possible source of variability can be expected by measurements outside and population dynamics can exert genetic variations in trees within the same species 5 5 25 15 20 10 25 20 10 15 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | er- He- and ff Quer- has been ¨ uller et al., . Thus it has to be Coronilla glauca , are known to be cyanogenic Hevea brasiliensis erence as being due to di ff 0.05) than those detected for our data for our measurements are not Pinus halepensis p < Olea europaea x . Furthemore, the emissions of acetone ¨ uve et al., 2007; Isidorov et al., 1985; and appears to be a potentially relevant source in June, whereas lower emission rates were x 15306 15305 Hevea brasiliensis -glucoside linamarin (Lieberei, 1986), but acetone and cinalis β ffi which has been reported earlier to emit methanol and Cistus albidus Hevea spruceana Rosmarinus o as already speculated by Bracho-Nunez et al. (2011). On the other , Staudt and Lhoutellier (2011) observed that sesquiterpene emissions Pinus halepensis -pinene, in the presence of NO ¨ oschl et al., 2001). In our study, emissions of methanol and acetone were β Despite their importance in plant physiology, ecology, and also in air chemistry (Fall, - and plants containing the cyanogenic emissions were found only in could be inferred from the cyanogenicPrunus pathway persica in hand, it isα known that theof atmospheric acetone OH-oxidation (Wisthaler of etavailable, a several al., contribution 2001). monoterpenes, of Though this like tions oxidation NO pathway could to not the be measured acetone excluded, concentra- particularly in the case of all tropical plant species and acetone emitters. The metabolic pathway of acetonepothesised has that not acetone yet been is proven. produced Ittoacetate was in (MacDonald hy- spruce and needles Fall, by 1993b),tion the whereas was decarboxylation found a in of cyanohydrin-lyase cyanogenic ace- catalysed plantvea reac- species spruceana, (Fall, Hevea 2003) guianensis leading to acetone release. sions in this case.investigated Interestingly, in emissions this of study were methanol significantlytropical by lower vegetation the ( species. Mediterranean We species mayent understand developmental that stages di of thethan plants. the The tropical Mediterranean plantsmature plant investigated leaves species, were were younger although measured. Onsions in the found both in other this hand, experiments study the aretropical fully light supposed plant expanded to dependent released be acetone, acetone direct whereas emis- emissions seven Mediterranean from plants the were leaves; only found to one be 2006; P demonstrated for the chosenranean plant tree species foracetone the (Filella first et time,described al., except as 2009). for an acetone the Though emitter Mediter- the by Geron tropical et tree al. (2006b) we did not find acetone emis- forested areas (Geron et al., 2002; Helmig et al., 1998; Karl et al., 2003; M et al., 2004) as well as high concentrations of this compound in the troposphere above Seco et al., 2007). Methanolformation is a and product is of the producedNemecek-Marshall demethylation by et of al., pectin leaf during 1995). growth, cellthe The for wall plants growing example we period (Galbally investigated andphysiological were and background a young Kirstine, for plants significant methanol 2002; still emission emissionet in is of al., still 2008). methanol a In matter wasemissions the of found. discussion case from However, (Folkers of the vegetation acetone,et (Cojocariu several al., studies et 2006; have al., reported Holzinger2002; leaf et 2005; MacDonald level al., Geron acetone and 2000; et Fall, Janson 1993b; and al., Nemecek-Marshall de 2006a,b; et Serves, Grabmer 2001; al., Kreuzwieser 1995; et Villanueva-Fierro al., (Eerdekens et al., 2009).cilitated The the technological study improvement of ofVOCs short-chain using like oxygenated methanol a VOCs. and PTR-MS The acetoneGouw exchange has has of fa- et been the detected al., oxygenated forKirstine 1999; a et variety Holzinger of al., et plant 1998; species al., (De MacDonald 2000; and H Fall, 1993a,b; Nemecek-Marshall et al., 1995; found in March or Januaryand oxidative suggesting stress a occurring seasonal under trend Mediterraneanilar summer possibly trends conditions. associated However, were sim- with reported heat noted that for the variability ofmonoterpenes. sesquiterpene emissions is even more striking than that for 2003) our informationsparse, on and oxygenated their VOC compounds contribution emission to the from global vegetation VOC is budget has been poorly described cus coccifera become boosted during exposureperatures to sesquiterpene heat emissions and were highline low radiation, with or this, while even field at undetectable studiesdard moderate in by emissions tem- this Ormeno of species. et al. In (2007d; 2009) observed the highest stan- oxidative stress (Loreto and Schnitzler, 2010). For example in a recent study on 5 5 25 15 20 10 25 15 20 10 Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | and -pinene. β - and α , 2011. ects on Physiology and Emissions of ff . This mass might be considered to , Physiol. Plantarum, 131, 211–225, 2007. 15308 15307 10.1029/2010JD015521 Quercus ilex is a high isoprene emitter, formation of such an oxidation Cistus monspeliensis, Quercus afares, Quercus suber Garcinia macrophylla , that emitted relevant quantities of This work was supported by the Max Planck Society, the European ˆ onia, Manaus (INPA) and the assistance of the PACE and TE platform cinalis ffi Garcinia macrophylla in Montpellier. We thank Tracey W. Andreae for help with the manuscript. ff Geophys. Res., 116, D16304, doi: Piedade, M. T. 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SE-Asia, South of Tropical South America a , d Tropical South America, Central America , d Tropical South America d , i, j Tropical South America, Central Amer- d d , c Tropical South America, Western Africa , c Tropical South America , d Tropical South America d , c, d, e Tropical South America , c, d, i Tropical South America, South-East , c, i Tropical South-America, Central Amer- d d d , b, d Tropical South America d , b d d d ), specific leaf weight (SLW), family, d a , b d n , c, d, e, f, g, h Tropical South and Central America d www.worldagroforestrycentre.org and c 15322 15321 evergreen treeevergreen tree a, b b, c evergreen treedeciduous/brevideciduous tree brevi-deciduous - tree b, c a /evergreen tree brevi-deciduous treeevergreen tree a deciduous tree a evergreen treeevergreen tree a c a brevi-deciduous a deciduous tree a Fabaceae Fabaceae Lauraceae Malvaceae Malvaceae Malvaceae Clusiaceae Sapotaceae Euphorbiaceae Euphorbiaceae Euphorbiaceae Euphorbiaceae http://data.gbif.org e e ) type 2 − , 23.6 , 26.1 f f SLW Family Functional Ecosystem (gm 42.9 36.4 e e 3 142 3 33.4 33 65.0 76.9 n , 2 , 2 f f 3 (Willd. Aubl. 2 (Miq.) 3 67.7 Kunth 3 76.0 (Benth.) Aubl. 2 39.6 (Sw.) 3 46.0 L. 3 45.2 ¨ (Harms) 3 41.9 ull. Arg. Plant species, number of individuals measured ( ¨ ull. Arg. Plant species Garcinia macrophylla (Mart.) Planch. and Triana Hevea brasiliensis ex A. Juss.) M Hevea guianensis Hura crepitans Hevea spruceana M Pachira insignis Sw. ex Savigny Pouteria glomerata Radlk. Pseudobombax munguba (Mart. and Zucc.) Dugand Scleronema micranthum L. Rico Ocotea cymbarum Ducke Vatairea guianensis Zygia juruana ´ o of Central Amazonian ´ ¨ o ongart et al., 2002. ´ arzea of Central Amazonian ´ arzea of acetone and otherby gas proton-transfer-reaction mass phase spectrometry product (PTR-MS),2001. yields Atmos. from Environ., the 35, OH-initiated 6181–6191, oxidation of terpenes Indicates the plant’s environment selectedV for the measurement. Missouri Bot Garden, New Bot. Garden, Royal Bot. Gardens Kew,Global INPA-Herbarium and Biodiversity F. Informations Wittmann, Facility: Sch Igap b) Igap c) Amazonian Terra Firme d) Orinoco basin e) Atlantic rainforest (non-flooded) f) Brazilian Pantanal (non-flooded) g) Brazilian Pantanal (flooded) h) Cerrado i) Central America j) West Africa, Asia f a) V d e c a personal communication, 2011. b functional type, ecosystem and distribution of the 12 investigated tropical plant species. Table 1. Wisthaler, A., Jensen, N. R., Winterhalter, R., Lindinger, W., and Hjorth, J.: Measurements Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | ´ o)

46 d (i) n n ´ arzea and (i) igap ) várzea a ) várzea v v Morocco, Portugal, East Greece Africa Mediterranean Region ranean Region,and Lebanon, the maritime Syria parts ofnor Asia and Northern Mi- Iran atend the of south the Caspian Sea Africa, Mediterranean Region North-West Africa,Asia South-West systems (( systems o o ), specific leaf weight (SLW), family, n palm tree Western Mediterranean Region evergreen tree Westernevergreen tree Mediterranean region, South-West Europe, North -West evergreen tree Mediterranean region evergreen tree Coastal Areas of Eastern Mediter- evergreen tree Mediterranean Region deciduous tree Algeria and Tunisia deciduous tree China, Iran, Mediterranean region deciduous tree South-West Asia and the Eastern evergreen herb Mediterranean Region evergreen herb Mediterranean Region tropical ec evergreen shrub Mediterranean Region evergreen shrub South Westevergreen shrub Europeevergreen shrub South to West Europe North Mediterranean Region evergreen shrub Western and Southern Europe, 15324 15323 cies of the e given. r r e e Poaceae Pinaceae Oleaceae Fabaceae Fagaceae Fagaceae Fagaceae Fabaceae Fabaceae Moraceae Cistaceae Cistaceae Buxaceae Rosaceae Arecaceae Lamiaceae ars a ) type b

2 r − 2 plant sp rro SLW Family Functional Distribution

1 1 e e (gm n itted from itted from . Standard -1 mm h Pers. 3 85 -1 L. 3 215 L. 3 110 (L.) Cav. 3 240 L. 3 291 Pall. ex Bieb. 3 73 L. 3 135 L. 3 163 VOC e Mill. 3 143 L. 3 149 1. n µg g Pomel 3 114 i i (L.) Batsch. 3 70 L. 3 121 cinalis L. 3 352 L. 3 91 ffi . Standard error bars are given. L. 3 66 ure 1 g − Plant species, number of individuals measured ( Fi

igapó) h 1 VOC emitted from 12 plant species of the tropical ecosystems ((v) v − Quercus suber Rosmarinus o Spartium junceum Quercus coccifera Quercus afares Prunus persica Olea europaea Pinus halepensis Cistus monspeliensis Chamaerops humilis Cistus albidus Coronilla valentina Ficus carica Ceratonia siliqua Brachypodium retusum Plant species Buxus sempervirens in µgg Fig. 1. functional type and occurrence of the 16 investigated Mediterranean plant species. Table 2. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper |

- d γ 48 (myrcene and tol an n plant ene and carene) e and -ol, cis- -ol, nd allo- cies ((v)

p p a a 47 3 3 n n a 4 e a 4 e m m rror e e . Standard error bars 1 (eucaly (myrce − editerrane l plant sp l plant m ene, p-cy (linalol (linalol lis terpinene- drene and t d h a a s u n s u n a a M n M 1 − . Standard -phellandrene and 3 carene) -1 -terpi h S. micranthum α

-1 -phellan α . officin Q. afare α l, -cymene, -cymene, R .

, rom tropic rom . micranth ed from o ) o ) o t o f t f e n e n S S n µg g i i e) and in , eucalypt e-4-ol), i e-4-ol), s emitted s emitted ) (myrcen enes emit enes ellandrene nene) for for nene) pinolene, -phellandrene). n i e n i nt species nt species n n e i e i r r (i) (myrcene, p p h h a a ( α -p -terpinene) for α γ -terp γ -terpine γ (terpine 15326 15325 rranean pl rranean ruceana

e and onoterpen e enthol, te e and hellandren is f monoter d d n n p p sp s sp m m m m H. H. spruceana 16 Medit (myrce (myrcene and m m de for n (%) of thujene, . halepens sis ion (%) o hujene, ß- rpinene an rpinene e, 3 carene e, - - t t t t u u o o n n e e P P - α α -t ( α ( r mitted fro mitted . brasilie thers incl thers compositi rneol, rneol, clude in . sube ccifera v) (myrcen e composi HH OO o nn oo ( QQ bo VOCs e H. brasiliensis given. 2. Q. c e e (v) (myrcene, 3 carene and ure Relativ

Relative g Others i ruceana ). ars ar ), in 4. e) and for ´

3. (i) igapó). ene), in ene), ehydrat, o). Others include for Fi b

e e . . n n sp sp or o n n n n H. ure ure g g -terpi ocimen γ sabine camph Fi Fi terpine

species várzea, for Relative composition (%) of monoterpenes emitted from tropical plant species ((v) VOCs emitted from 16 Mediterranean plant species in µgg H. spruceana -terpinene) and for ´ arzea, (i) igap for v Fig. 3. γ Fig. 2. are given. Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Q.

- d γ

48 49 tol an n plant ene and carene) carene) e and -ol, cis- -ol, nd allo- cies ((v) cies ((v) p p a a -terpinene), in n plant 3 3 n n a 4 e a 4 e m m a γ (eucaly (myrce editerrane l plant sp l plant m ene, p-cy (linalol (linalol lis terpinene- drene and drene and t d a a editerrane s u n s u n a a M n M M M -terpi

-phellan α . officin Q. afare α l, (linalol and allo-ocimene), in -cymene, -cymene, R .

, rom tropic rom . micranth ed from o ) o ) o t o f t f e n e n S S ed from t t (eucalyptol and camphor). e) and in , eucalypt e-4-ol), i e-4-ol), s emitted s emitted ) (myrcen enes emit enes ellandrene nene) for for nene) pinolene, i n e n i n n Q. afares e i e i r r p p h h -terpinene, p-cymene and enes emit ( p p α -p α cinalis -terp γ ffi -terpine γ (terpine ruceana

e and 15328 15327 onoterpen enthol, te hellandren and is f monoter d d n n p p sp s sp R. o sesquiter m m m m f f H. (myrce de for n (%) of n (%) thujene, . halepens sis ion (%) o hujene, ß- rpinene an rpinene e, 3 carene 3 e, - - t t t t u u o o n n e e P P - ion (%) o α (terpinene-4-ol), in t t α -t ( α ( r . brasilie thers incl thers compositi rneol, rneol, clude in . sube ccifera v) (myrcen e composi HH OO composi o -terpinene) and in nn oo -phellandrene, eucalyptol, ( QQ ee bo γ β Q. c P. halepensis Relativ

Relativ Relative Relative Others i ruceana ). ), in 4. e) and for

3. (i) igapó). (i) igapó). ene), in ene), ehydrat, e e . . n n sp 5. sp or o n n n n

. . -thujene, -thujene, menthol, terpinolene, o-cymene, terpinene-4-ol, cis-sabinenehydrat, bor- H. ure ure g g α ure α ( -terpi ( g Fi ocimen γ sabine camph terpine Fi

species várzea, várzea, for Fi

species Relative composition (%) of monoterpenes emitted from Mediterranean plant species. Relative composition (%) of sesquiterpenes emitted from Mediterranean plant species. -terpinene and α Fig. 5. Fig. 4. Others include in coccifera Q. suber neol,