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Seasonal Variations of Isoprene Emissions from Deciduous Trees Zhang Xiaoshan*, Mu Yujing, Song Wenzhi, Zhuang Yahui

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Seasonal Variations of Isoprene Emissions from Deciduous Trees Zhang Xiaoshan*, Mu Yujing, Song Wenzhi, Zhuang Yahui Atmospheric Environment 34 (2000) 3027}3032 Seasonal variations of isoprene emissions from deciduous trees Zhang Xiaoshan*, Mu Yujing, Song Wenzhi, Zhuang Yahui Research Center for Eco-Environmental Sciences, Academia Sinica, Beijing 100085, People's Republic of China Received 18 November 1998; accepted 23 June 1999 Abstract Isoprene emission #uxes were investigated for 12 tree species in and around Beijing city. Bag-enclosure method was used to collect the air sample and GC-PID was used to directly analyze isoprene. Ginkgo and Magnolia denudata had negligible isoprene emissions, while signi"cant emissions were observed for Platanus orientalis, Pendula loud, Populus simonii, and Salix matsudana koidz, and other remaining trees showed no sign of isoprene emission. Variations in isoprene emission with changes in light, temperature and season were investigated for Platanus orientalis and Pendula loud. Isoprene emission rates strongly depended on light, temperature and leaf age. The maximum emission rates for the two trees were observed in summer with values of about 232 and 213 lgg\ dw h\, respectively. The measured emission #uxes were used to evaluate `Guenthera emission algorithm. The emission #uxes predicted by the algorithm were in relatively good agreement with "eld measurements. However, there were large di!erences for the calculated median emission factors during spring, summer and fall. The 25}75 percentiles span of the emission factor data sets ranged from !33 to #15% of the median values. ( 2000 Elsevier Science Ltd. All rights reserved. Keywords: Isoprene; Emission factors; Emission rates; Diurnal variation 1. Introduction gases such as methane by depleting OH radicals and producing CO; (2) contribute to aerosol back-scattering It is known that plants contain a number of volatile by the formation of aerosols and of cloud condensation organic compounds (VOC) including isoprene, mono- nuclei; (3) enhance acidic deposition in remote areas by and sesquiterpenes, alcohols, aldehydes, ketones and the formation of organic acids; (4) control tropospheric esters which may be widely distributed through plant ozone formation; (5) in#uence global carbon budgets. To organs. It appears that these compounds may be impor- assess the impact of reactive VOC on local, regional and tant in many functions, including defense against herbi- global ozone formation and its possible impact on the vory (Farentinos et al., 1981). The emissions of VOC annual temperature increase, accurate estimates of natu- from the vegetation contribute signi"cantly to the VOC ral VOC emission #uxes are necessary. budget in the troposphere (Steinbrecher, 1997; Guenther The two most abundant and best-studied VOC are et al., 1995). Guenther et al. (1995) estimated that vegeta- isoprene and monoterpenes because of their high reactiv- tion emitted over 90% of the global VOC emissions. ity and importance in determining the OH mixing ratios VOC play a key role in the short-term chemistry of the (Anderani-Aksoyoglu and Keller, 1995). In China, how- lower atmosphere and have an important impact on ever, there are few reports on the emission pattern and global change, including climate change (Hewitt and quantity of VOC from plant species. Street, 1992; Steinbrecher et al., 1997; Lerdau et al., 1997). Both isoprene and terpene emissions are sensitive to They may (1) increase the lifetime of radiative active temperature; only isoprene emission is strongly a!ected by the light intensity (Lerdau et al., 1997). Isoprene emis- sion which takes place mainly during the daytime, is * Corresponding author. Tel.: #86-10-62925511-3190; fax: suggested to be associated with the photosynthetic activ- #86-10-629-23563. ities (Delwiche and Sharkey, 1993). Other factors which E-mail address: [email protected] (Z. Xiaoshan). have been reported to a!ect the emission of biogenic 1352-2310/00/$- see front matter ( 2000 Elsevier Science Ltd. All rights reserved. PII: S 1 3 5 2 - 2 3 1 0 ( 9 9 ) 0 0 3 1 1 - 8 3028 Z. Xiaoshan et al. / Atmospheric Environment 34 (2000) 3027}3032 VOC are plant age, water de"cit and air pollution within the enclosure (g), and < is the volume of the (Anderani-Aksoyoglu and Keller, 1995; Kesselmeier and enclosure system (m). Studt, 1999). The investigations presented in this paper, focus on the in#uence of environmental parameters on 2.2. Analytical method the isoprene emission rate from two typical tree species in and around Beijing city. The emission algorithm for- VOC were usually measured by GC-FID methods in mulated by Guenther et al. (1993) has been tested for most laboratories. Since the concentration of VOC in the isoprene emission from Platanus orientalis and Pendula enclosure system is lower than the detection limit of FID; loud. preconcentration was needed. These processes are rela- tively complex and will cause contamination and loss for VOC (O can react with VOC because of their reactivity, 2. Experimental methods Larsen et al., 1997). Photoionization detector and re- duction detector were also used for analyzing isoprene 2.1. Sampling method (Lerdau and Keller, 1997; Monson et al., 1994). These analytical techniques do not require any preconcentra- The 5.24 l cuboid enclosure (14.2;14.2;26 cm) used tion for isoprene mixing ratios above 1 ppbv. for the measurement of isoprene emission, was construc- In this study, photoionization detector (PID-100C, ted of a Velton "lm over a wire-supported frame. The made by the Institute of RCEES) was employed for losses of isoprene in the enclosure system were tested by directly analyzing isoprene. using standard isoprene gas (350 ppbv). The average A packed Te#on column of 5% b,b-Oxydipropionit- losses of isoprene in the system for 20 min are about vile coating on Chromosorb P NAN (60}80 mesh) was 1.6% (the injection interval is about 20 min, and 12 used to separate the air sample. The column is 3 m long, injections). Because the enclosure time in our experiment and with an inner diameter of 3 mm. Compressed air is less than 10 min, the losses of isoprene in the system is which passed through dry Molecular Sieve and Active less than 0.8% during our experiment. This value is Carbon was selected as the carrier gas. The #ow rate was within the precision of the analytical system. about 10 ml per min. The column and injection temper- The twigs investigated were generally exposed on the atures were room temperature (&253C). The quantity of south side. The enclosure system was vibrated for mixing the injection was 1 ml. The column can e$ciently separ- the air volume in it before sampling. During a given time ate isoprene from other biogenic VOC compounds (e.g. interval (1}2 min for daytime, and 20 min for night), Butane, n-butene, butadiene and monoterpenes). 10}20 ml of the air sample in the bag was collected using The standard gas of isoprene (74.7 ppmv, provided by a glass syringe. After collection, the syringes were stored the Institute of Standard Material, Beijing) was diluted to in the dark, to prevent photochemical reactions. The di!erent concentrations using N and was used to test contents of the syringe were quickly analyzed by GC- the linear relationship of PID. The results are shown in PID within half an h of collection. The loss of isoprene in Fig. 1. There is a good linear correlation for isoprene the syringe was tested by using samples of known iso- from 3.73 to 4500 ppbv, the correlation coe$cient (R)is prene content, there was almost no loss for at least 1 h. higher than 0.98. The accuracy of the GC-PID system for To isolate the main controlling factors for isoprene isoprene was about 2.4% (standard deviation of the emission, a set of environmental parameters (photosyn- mean; n"15) and the time resolution of the analytical thetic active radiation [PAR] and temperature) were cycle was 10 min. Hence GC-PID is an easy, quick and determined simultaneously from the emission measure- reliable method for analyzing isoprene. ments. The temperatures inside and outside the bag were measured using mercury thermometers. PAR (Li 190SB 2.3. Emission parameterization Quantum Sensor Lincoln, NB) was measured outside the bag. Light and temperature are the main controlling factors The dry weight was determined after drying the col- for isoprene emission. To predict isoprene emission from lected leaves at 1003C for 24 h. The isoprene emission vegetation, Guenther et al. (1993) developed an algorithm rates, E (lgg\ h\), for individual branches were cal- based on leaf-temperature and light. Isoprene emission culated as rate E* can be calculated by the following equation: (C !C ) < " ; ; E" G ; , E* S C* C2, (1) ! (tG t) = where S is the isoprene emission factor at a standard ! ¹ where (CG C) is the di!erence in the concentrations of temperature of 303 K, and a standard PAR of l \ ! l isoprene for a given time interval ( gm ), (tG t) is the 1000 E, C* and C2 are the correction terms for light and given time interval (h), = is the dry weight of the leaves temperature relative to standard conditions, respectively. Z. Xiaoshan et al. / Atmospheric Environment 34 (2000) 3027}3032 3029 Table 1 Isoprene emission rates of Beijing tree species in May, and comparison of the results of this study with others for the same genera. n is the number of emission rate measurements by this study, N represent negligible or no isoprene emission, Eiso (lgCg\ h\) are representative of leaf temperature of 303C and PAR #ux of 1000 lmol m\ s\ Eiso (lgCg\ h\) Fig. 1. The linear range of PID for isoprene. Genus species n ab c Platanus orientalis 13 25.2 20 10.9}27.5 Guenther et al. formulate these terms as Pendula loud 36.3** Populus simonii 222.64037}100 aC ¸ Salix matsudana Koidz 2 19.2 20 12.5}115 " * C* , (2) Ginkgo biloloa 1 (0.1 (0.1 N, or (1 (1#a¸ Paulownia tomentosa 1N** Magnolia denudata 1 (0.1 (0.1 N a where (0.0027) and C* (1.066) are empirical constants Cedrus deodara 1N(0.1 N ¸ l and is the PAR( E).
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