1、API PUBL*309 92 W 0732290 0529644 2T2 = CURRENTSTATUSANDRESEARCH NEEDS RELATED TO BIOGENIC HYDROCARBONS HEALTH AND ENVIRONMENTAL AFFAIRS API PUBLICATION NUMBER 309 JUNE 1992 American Petroleum Institute 1220 L Street. Northwest 11 Washington: D.C. 20005 API PUBL+309 92 = 0732290 0527645 139 = CURREN
2、TSTATUSANDRESEARCHNEEDS RELATED TO BIOGENIC HYDROCARBONS HEALTH AND ENVIRONMENTAL AFFAIRS DEPARTMENT API PUBLICATION NUMBER 309 JUNE 1992 PREPARED BY: INDACO AIR QUALITY SERVICES, INC. RESEARCH ANDTECHNOLOGYPARK 1345 TERREVIEW DRIVE PULLMAN, WA 99163 American Petroleum Institute API PUBL+309 92 0732
3、290 0529646 075 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT U“G TO MEET THE DUTIES OFEMPLOm, MANUFAC- TURERS, OR SUPPLIERS To WARN AND PROPERLY TRAI
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5、RE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PAmNT. NEITHER SHOULD ANYTHING CONTAINED IN THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINSTLIABIL- lTY FOR INFRINGEMEN“ OF LETTERS PAm. API PUBL*309 92 O732290 O529647 TO1 Executive Summary 1. O Literature Compilation
6、 11 TABLE OF CONTENTS 1.1 Introduction 1.2 Methods: Literature Sources and Data Bases 1.3 Overview of Biogenic Emissions Measurements 1.3.1 Vegetation Species, Identified Compounds, and Emission Rates 1.3.2 Emission Patterns and Environmental Effects 1.4 Ambient Biogenic VOC Concentration Measuremen
7、ts 1.5 Biogenic Emission Inventones 1.6 Atmospheric Chemistry of Biogenic VOCs 1.7 Current Biogenic Studies Critical Review of the Literature 2.1 Introduction 2.0 2.2 Emission Inventory Systems 2.3 Emission Rate Measurements 2.4 Atmospheric Chemistry 2.5 Summary of the SOW-EE Biogenic Emission Works
8、hop 1v 2 10 12 13 14 18 21 21 26 29 31 API PUBL*Pinene Mpne 3-Carene 1 -Pheilandrene B -Phellandrene CI -Terpinene -Terpinene y -Tapinene Limonene Terpinolene knchone ujone . Camphor 1,8-Cineol PCymene Menthane .6 .5 I,11 b10,15 I- 17 r,8*,9-10 ?,lo, 13-17 3,(7,8,11,12,14)* 9,10,13,15,17) * * , 16 2
9、,12 7-17 7-10,12 j,10,12 3,(7,9,10,12)*,*(8,11)* 12,13,15,17 ,( 14,16) * 13-17 3,7-11,15 7-13,14*,15-17 7*,8-10,12-15,16*, 17 3,8-11 8-1 1,14 8-10,17 3,8-10,13- 15 9.1 3-1 5,17 3,7- 17 9-17 3,8,14 16* 16* 8 7-17 #1. Bay-ieavedwillow; 2. Aspen; 3. Balsam poplar; 4. European oak; 5. European birch; 6.
10、 Sorb; 7. Eutopean larch; 8. European e, 9. Scots pine; 10. Siberian pine; 11. Silver fx; 12. Common juniper, 13. Zeravshan juniF, 14. Pend 16. Nwthern white Trainer et al., 1987; Chameides et al., 1988). Methods have ranged from the use of simple box models to Lagrangian chemical reactor models to
11、fully three dimensional Eulerian grid models. The influence of biogenic hydrocarbons in the Regional Acid Deposition Model (RADM) (Chang et al., 1988) and the Regional Oxidant Model (ROM) (Roselle and Schere, 1990) have been of parbcular interest. Similar concern for the importance of biogenic VOC s
12、 in formation of CO and tropospheric ozone on a global basis has been addressed through tropospheric chemical models (Lopez et al., 1989; Jacob and Wofsy, 1988; and Atherton and Penner, 1990). Lin et ai. (1988) employed a photochemical box model to investigate the nonlinear dependence of ozone forma
13、tion upon precursor concentrations. The results indicated that the composition of hydrocarbons, the ratio of VOC/NO, and the background concentrations of biogenic VOCs, CO, and CHq all are important in determining the nonlinearity of ozone formation with respect to NOx loss. Atherton and Penner (199
14、0) performed a similar study using a photochemical box model to investigate the importance of odd nitrogen species beyond those normally included in models: NO, Ne, PAN, “03, and NO3- (particulate nitrate). The shortfall of odd nitrogen was defmed as the ratio of other nitrogen species to the sum of
15、 the above compounds. For cases with biogenic VOCs, the nitrogen shortfall was 0.25 with background isoprene and pinene emissions and 0.45 with high pinene emissions. In comparison, the shortfall varied between 0.02 to 0.33 for various urban simulations. The implications from this work are that inco
16、rrect specification of odd nitrogen chemistry may be a significant source of error in chemical modeling studies of biogenic emissions. Jacob and Wofsy (1988) compared photochemical model predictions against isoprene and ozone concentrations measured over the Amazon forest. The results were in good a
17、greement with observations and showed that biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. In agreement with the suggestion made previously API PUBL+30 92 m 0732290 0529bb8 73b m 18 about the dry deposition of isoprene at night, the model comparison with observ
18、ations indicated the importance of dry deposition. Lopez et al. (1989) modeled the vertical profiles of photochemical species in a Lagrangian air parcel moving over homogeneous land cover. For cases with terpene emissions into an air mass with low NOx, ozone was depleted, while emissions into an air
19、 mass with high NOx caused an enhancement of ozone. The degree of change was larger for alpha-pinene emissions than for isoprene emissions. The effects of biogenic emissions upon the urban plume of London was investigated by MacKenzie et al. (1991) using a detailed photochemical expanding air parcel
20、 model. The results seemed quite similar to the early work by Lunnann et al. (1984) since the predicted effect of adding biogenic emissions increased the ozone concentrations by about 8 ppb. The sum of these modeling studies have provided insight into the role of biogenic VOCs in atmospheric chemist
21、ry. However, until a better understanding of the biogenic emission fluxes is obtained, the identity of important biogenic species is clarified, and more complete chemical mechanisms are compiled, the modeling results provide an incomplete and uncertain picture of biogenic VOCs in the atmosphere. 1.7
22、 CURRENT BIOGENIC STUDIES The NOAA ROSE (Rural Oxidants in a southeastern Environment) program recently completed a 2 month field study in an Alabama pine plantation designed to measure precursors and products related to ozone formation in the Southeastern U.S. The programs included sampling of biog
23、enic emissions, measurements of VOC reactant and product concentrations, and performance of vertical prole tracer flux studies. Similar work was performed in the predecessor to ROSE which was conducted in Scotia, Pennsylvania, in 1988 (see Martin et al., 1991). The unique feature of the ROSE program
24、 is the combined measurement of essentially all carbon and nitrogen species thought to be important in ozone air chemistry along with detailed boundary layer meteorological measurements and vertid transport tracer studies. In ROSE 1990, this included diurnal sampling of VOC emissions using a vegetat
25、ion enclosure method of all the dominant vegetation types in the area as well as diurnal sampling of the concentrations of isoprene, the terpenes, and their expected oxidation products in the atmosphere. More than 200 enclosure samples were collected along with measurements of pertinent environmenta
26、l parameters during the study. Compound fingerprints from each species sampled were obtained using a GUMS system located on site. A data meeting of all participants was held in January, 1991. Initial presentation of results occurred in a special session at the fall 1991 meeting of the American Geoph
27、ysical Union. The SOS (Southeast Oxidant Studies) program is a broad plan under development by a consortium of universities and EPA laboratories. A large aspect of SOS will deal with biogenic emissions (Southern Oxidants Research Program on Emissions and Effects, SORP- EE) while other parts of SOS a
28、re directed at intensive field studies of ambient reactant and product gases. The proposed SOW-EE emissions activities are extremely broad at this point. API PUBL1309 92 0732290 0529669 672 m 19 As one component of the work, the NCAR Trace Gas Biogeochemical section has proposed to measure biogenic
29、emission rates and perform biomass surveys at a number of sites. Measurements of vertical profiles of hydrocarbon concentrations will be made at each site using the NCAR tethered balloon sampling system. The OTER (Oregon Transect Ecosystem Research) project is a NASA effort to use ecosystem models w
30、ith remotely sensed observations of ecosystem variables as a way to predict ecosystem response and feedback to global warming. The OTER project covers six sites along a line from coastal Oregon over the Cascade Mountains to the high central desert of Oregon. Initial EPA plans to incorporate biogenic
31、 emission measurements by Washington State University (WSU) within the OTER framework have been eliminated. However, alternate funding were obtained for a scaled back set of measurements during 1991 at one of the OTER sites. The emphasis in the emissions measurements was to collect diurnal emission
32、profiles during two field visits through the growing season in conjunction with careful measurement of key photosynthesis and environmental variables. As a predecessor to the WSU OTER study, Dilts et al. (1990) have completed a one year study of emissions from English oak in Pullman, WA where enclos
33、ure samples were collected on an hourly basis through a diurnal pend and environmental parameters were measured continuously (photosynthesis rate, leaf and air temperature, moisture level, and photosynthetic active radiation). These diurnal sampling profiles were repeated approximately twice weekly
34、during the growing season beginning in the fall, 1989, and continuing through the fall, 1W2. The BOREAS (Boreal Ecosystem-Atmosphere Study) sponsored by NASA is an extensive multi-year field measurement and modeling program that is designed to improve our understanding of carbon cycling in boreal fo
35、rests and to investigate how the fluxes of datively active trace gases from terrestrial ecosystems will influence future climate scenarios. The study area will be at two boreal forest sites in central Canada. Preliminary field measurements will be made during 1993 and several intensive study periods
36、 will be completed during 1994. The SJVAQS/AUSPEX are two joint projects being conducted in the San Joaquin valley of California. Like SOS, these are broad field measurement and modeling efforts to obtain quantitative information about ozone formation and transport. In terms of biogenic emissions, t
37、he unique feature of this work is the importance of emissions from a variety of agricultural craps. Winer et al. (1 989) recently completed a comprehensive survey of emissions from crops and natural vegetation in the San Joaquin valley. These data and results from additional measurements will be use
38、d as the basis for a gridded emission inventory of emissions being developed by the Desert Research Institute RI) for the project. The inventory will make use of satellite data to map vegetation cover, and it will include methods to predict emissions for specific times using emission models with mea
39、sured meteorologicai conditions. The EPA Air and Energy Engineering Research Laboratory (AREEL) is funding work to improve biogenic hydrocarbon emission inventories. The NCAR TGB section will be involved in reviewing the Tampa Bay emissions data to identify compounds lumped into the API PUBL*309 92
40、0732290 0529b70 394 m 20 “other hydmcarbon“ categories more specifically. Results from the ROSE sampling program will be used along with the laboratory measurements by Guenther et ai. (1990) to test and improve the physiological emission rate model. In addition, the use of satellite data to determin
41、e biomass distributions over time will also be investigated through this program. Together, these current programs represent a substantial effort to improve our understanding of biogenic emissions. Many of the uncertainties associated with estimating biogenic emission rates and identifying important
42、 VOC species should be resolved as these programs proceed, and new methods for the development of inventories will be available. API PUBLS309 92 m 0732290 0529671 220 m 21 2.0 CRITICAL REVIEW OF THE LITEIUTURE 2.1 INTRODUCTION As a result of the Clean Air Act of 1990, development of plans to control
43、 ozone formation in non-attainment regions must account for the emission of reactive hydrocarbons from vegetation, and models used to test control strategies must address the photochemistry of these biogenic gases. However, the inventory models used to estimate biogenic emissions contain large uncer
44、tainties and there is still an incomplete understanding of the oxidation mechanisms of biogenic hydrocarbons in the atmosphere. In this chapter, selected papers from the literature are critically reviewed. These papers were selected as representative of the state- of-the-art in each of severa areas
45、including biogenic emissions modeling, emission rate measurements, and atmospheric chemistry related to biogenic hydrocarbons. The purpose of this critical review is to highlight the major areas of uncertainty in each area and to identify gaps where additional information or work is needed. This ana
46、lysis will thus provide a basis for the development of a detailed research plan to answer the major questions concerning the role of biogenic hydrocarbons in the formation of photochemical oxidants. There are several current large-scale studies underway which have a significant biogenic VOC componen
47、t. Because reports and papers from these efforts, the Lake Michigan Oxidant Study and the San Joaquin Valley Air Quality Study, are not yet available, these studies are not considered at this time. This review includes available papers and reports selected as being representative of current studies.
48、 The review is designed to be critical in the sense that it identifies key assumptions, lack of data, or incomplete understanding that limits our confidence in emission estimates, emission measurements, or predictions of atmospheric fate. 2.2 EMISSION INVENTORY SYSTEMS The centrai emission inventory
49、 model being used for owne control purposes in the U.S. was developed as part of the National Acid Precipitation Assessment Program (NAPAP) by Washington State University (WSU) (Placet et. al., 1990; Lamb et al., 1991). This model was subsequently compiled for implementation on a personal computer as PC-BEIS (Biogenic Emission inventory System) by Pierce and Waldruff (1991) (see also Pierce et al., 1990, and the users guide, Pierce, 1990). This system is being used as the starting point for inventory systems now eiig developed as part of the Lake Michigan Oxidant Study (LM
