BOREAS TGB-08 Monoterpene Concentration Data over the SSA-OBS and the SSA-OJP Summary: The TGB-08 team collected data to investigate the controls over non-methane hydrocarbon (NMHC) fluxes from boreal forest tree species. This data set contains measurements of monoterpene concentrations in collected foliar gas emissions and foliar samples. The data were collected at the Old Jack Pine (OJP) and Old Black Spruce(OBS) tower-flux sites in the SSA and were the locus for the monoterpene emission measurements. These areas contained mature stands of jack pine and black spruce and were the focal sites in the BOREAS program for studies of biosphere/atmosphere exchange from these two habitat types. The OBS site is situated in a black spruce/sphagnum bog with the largest trees 155 years old and 10-15 m. tall. The OJP site is in a jack pine forest, 80 to 120 years old, which lies on a sandy bench of glacial outwash with the largest tree standing 15 m. tall. Temporally, the data cover the period of 24-May-94 to 19- Sep-94. The data are stored in tabular ASCII files. Table of Contents * 1 Data Set Overview * 2 Investigator(s) * 3 Theory of Measurements * 4 Equipment * 5 Data Acquisition Methods * 6 Observations * 7 Data Description * 8 Data Organization * 9 Data Manipulations * 10 Errors * 11 Notes * 12 Application of the Data Set * 13 Future Modifications and Plans * 14 Software * 15 Data Access * 16 Output Products and Availability * 17 References * 18 Glossary of Terms * 19 List of Acronyms * 20 Document Information 1. Data Set Overview 1.1 Data Set Identification BOREAS TGB-08 Monoterpene Concentration Data over the SSA-OBS and the SSA-OJP 1.2 Data Set Introduction 1.3 Objective/Purpose The objective of this data set was to measure the Monoterpene Concentration in 1st fully expanded (2nd year needles) from the SSA-OBS and SSA-OJP sites. 1.4 Summary of Parameters Monterpene concentration and Monoterpene emission. 1.5 Discussion The research was ordered around three general questions: (1) To what extent are leaf carbon balance and isoprene synthase activity (the enzyme responsible for isoprene emission predictors of NMHC flux, (2) How do leaf carbon balance and isoprene synthase activity depend on nitrogen/water availability and carbon source/sink parameters, and (3) How do we modify the FORES-BGC ecosystem model based on question 1 and 2, to predict canopy-level NMHC fluxes. Studies included seasonal monitoring of NMHC emissions and its relationship to plant phenology, photosynthesis, respiration, isoprene synthase activity, and leaf starch concentrations. 1.6 Related Data Sets BOREAS TGB-08 Photosynthetic Rate Data over the SSA-OBS and the SSA-OJP BOREAS TGB-08 Starch Concentration Data over the SSA-OBS and the SSA-OJP BOREAS TGB-09 Tower Non Methane Hydrocarbons Mixing Ratio BOREAS TGB-10 Tower Non Methane Hydrocarbons Mixing Ratio BOREAS TGB-10 Oxidant Concentration BOREAS TGB-10 Oxidant Flux 2. Investigator(s) 2.1 Investigator(s) Name and Title Manuel Lerdau 2.2 Title of Investigation The Relationship Between Non-Methane Hydrocarbon Emission and Leaf Carbon Balance in the Boreal Forest: An Approach for Mechanistic Ecosystem Modeling. 2.3 Contact Information Contact 1 --------- Dr. Manuel Lerdau Ecology and Evolution SUNY Stony Brook, NY (516)632-6633 (516)632-7626 (fax) mlerdau@life.bio.sunysb.edu Contact 2 --------- Sara K. Conrad Raytheon STX Corporation NASA/GSFC Greenbelt, MD (301)286-2624 Sara.Golightly@gsfc.nasa.gov 3. Theory of Measurements Sample selection For the photosynthesis/hydrocarbon measurements, ten trees of each species were chosen that had sunlit leaves accessible within 3 m of the ground. All measurements were conducted on sunlit leaves that had developed the previous year. Tissue chemistry and gas exchange sampling on sunlit leaves from branches much higher in the canopy showed that there was no significant effect of branch height on photosynthetic rate or on tissue composition (ANOVA, p>0.05, data not shown). The black spruce trees used in the bog transect/tissue chemistry sampling were chosen on the basis of having sunlit leaves accessible within 2m of the ground. All hydrocarbon measurements were made on fully expanded needles that had developed during the previous growing season. Needles were placed in the cuvette so that only those needles that expanded during the previous growing season were included. Needle age in all cases was determined unambiguously by marking needle cohorts before leaf expansion in the spring and by examining the branches for twig color change and bud scarring associated with each year's growth. The bog transect measurements were also all made on last year's fully expanded needles. Sample procedure Hydrocarbon emissions: Samples were collected by enclosing branches in a temperature- and light-controlled cuvette connected to plant gas exchange system (Campbell MPH 1000, Campbell Scientific, Logan, UT) and flowing hydrocarbon-free air over the needles. Temperature was controlled by use of thermoelectric coolers provided by Campbell Scientific, and light intensity was controlled by mounting a projector bulb at a right angle to the top of the glass-topped cuvette. The light was then reflected off of a cold mirror (458 cold mirror, 15-33233, OCLI, Santa Rosa, CA) mounted at a 458 angle to cuvette. The mirror transmitted light at wavelengths >720nm and reflected light of shorter wavelengths. Hydrocarbon-free air was produced by pumping ambient air through a clean-air generator (Aadco 5L, AADCO Instruments, Silver Springs, FL) and adding CO2 back to the entering air stream. All flows and environmental conditions were monitored by the sensors and mass flow controllers of the Campbell MPH 1000.Hydrocarbon emission samples were collected by diverting a fraction of the air exiting the leaf cuvette through a sampling tube packed with a solid sorbent. Supelco Carbotrap 300 cartridges (Bellafonte, PA) with dimensions of 7 in length and 1/4 in outer diameter were used in this work. The sampling tubes were conditioned before each use via a Tekmar Thermo Trap unit (Cincinnati, OH) at 220 8C for a minimum of four hours at a flow of approximately 10 mL/min of ultrahigh purity nitrogen. A blank from each set of conditioned cartridges was analyzed to ensure that they had been properly cleaned. The flow rate and volume of air passing over the sampling tube was controlled with a low flow pump (SKC Model-222, SKC, Inc. Eighty-Four, PA). This sample volume was variable but kept well below the typical breakthrough volumes for terpenes on this sampling tube (Anon., 1986). Foliar chemistry: After the emissions samples were collected, we separated the branchlet and needles from the main branch. Total needle biomass was measured on fresh needles. We then separated the total needle biomass into two parts, half of which we placed in a 60 8C drying oven and weighed daily until no further change in weight was observed. These dried needles were hen stored for nitrogen analysis. The remaining needles were ground in liquid nitrogen and stored in 20 mL scintillation vials filled with pentane until they were analyzed for monoterpene concentrations. The pentane storage was never less than seven days and was more than sufficient to allow for complete solvent extraction of the monoterpenes (Lerdau et al. 1995). The fresh weight / dry weight ratio from the needles used in the nitrogen analyses was applied to each monoterpene sample to provide an estimated dry weight for the sample. All analyses are reported on a dry-weight basis. Analysis Hydrocarbon emissions: Samples were analyzed by thermal desorption followed by gas chromatography/mass spectrometry (GC/MS) using a modified form of the EPA TO-1 method (Anon., 1984). A Tekmar AeroTRAP unit (Cincinnati, OH), Tekmar Cryofocusing unit (Cincinnati, OH), and ultrahigh purity helium purge gas were used to thermally desorb hydrocarbons off the cartridges via a multi-step process. Cartridges were heated to 220 8C to desorb the sample onto an internal glass-bead-packed trap cooled with liquid nitrogen to -165 8C. Next, the sample was desorbed off the internal trap at 220 8C, passed through a moisture control system to remove water, and re-focused onto the head of the column which was held at -165 8C using liquid nitrogen. Finally, the sample was injected onto the column by flash heating the head of the column to 220 8C.A Finnigan model ITS40 gas chromatograph/ion trap mass spectrometer/data system (San Jose, CA) was used to analyze the hydrocarbons in the samples. A 25 m, 0.25 mm ID DB-5ms column from J&W Scientific (Folsom, CA) was used to separate the terpenes. The temperature of the column was programmed to separate the terpenes of interest. This entailed holding the column at 408C for 5 minutes, increasing the temperature at 88 C/min to 2208 C, and then holding the temperature at 2208 C for 4 minutes. The transfer line to the ion trap mass spectrometer was held at 2508 C, and the ion trap manifold was set to 1008 C. The ion trap mass spectrometer was run through a daily auto-tune sequence prior to data acquisition on samples, standards, and blanks. This auto-tune sequence involved calibrating the mass scale and setting emission current, multiplier voltage, automatic gain control target value to proper values. Mass spectra were acquired under electron ionization (EI) conditions using a scan range of m/z 50 to 200 and a scan rate of 1 scan/second. Terpenes were identified using both retention time confirmation and matching experimental mass spectra against a custom library of mass spectra derived from a series of terpene standards. Terpenes were quantified against external standards, in which the most intense ion for the individual terpene (quantitation ion) was compared to the same ion from analyses of known amounts of neat terpene standards in hexane. Method blanks were used to correct for any response for terpenes on the conditioned cartridges. All emission rates are reported on a dry weight basis. Foliar chemistry: Monoterpenes were separated on a HP 5890 Series II gas chromatograph equipped with a split/splitless injector, flame ionization detector (FID) and a 30 m DB-1 capillary column (0.32 mm i.d., 1 µm film thickness, J & W Scientific, Folsom CA), 2 ?L of sample was injected in the split mode (80:1 split) using a HP 7673 Auto Sampler, He as the carrier gas at a flow rate of 2.2 mL min-1. Column temperature was programmed to stay at 508 C for five minutes, then increase 68 C/min to 2508 C and held for 5 minutes. Detector temperature was 3008 C and injector temperature was2758 C. Individual monoterpenes were identified by comparison of their retention times with authentic monoterpene standards (purchased from Sigma/Aldrich Chemical CO, St. Louis, MO) that were analyzed under conditions identical to those used for the unknown samples. Monoterpenes were quantified using fenchone as an internal standard. Fenchone was added to the extract 24 hours prior to analysis. The results are expressed as mg terpene per gram of needle dry weight. Needle nitrogen concentration was measured as total Kjeldahl nitrogen (TKN; calculated as a percentage of needle dry mass) using the digestion and measurement protocol described by Jaeger and Monson (1992). Needles were ground and digested in sulfuric acid with a copper sulfate catalyst at3608 C for three hours and then analyzed colorometrically using a flow injection analyzer (LACHAT Inst., Mequon, WI). 4. Equipment: 4.1 Sensor/Instrument Description 4.1.1 Collection Environment Samples were collected under ambient environmental conditions. 4.1.2 Source/Platform Trees. 4.1.3 Source/Platform Mission Objectives The purpose of the trees and branches for this experiment were to support the measurement equipment. 4.1.4 Key Variables Monoterpene concentration and Monoterpene Emission. 4.1.5 Principles of Operation None given. 4.1.6 Sensor/Instrument Measurement Geometry None given. 4.1.7 Manufacturer of Sensor/Instrument Campbell Scientific AADCO Instruments Silver Springs, FL Supelco Bellafonte, PA Tekmar Cincinnati, OH SKC, Inc. Eighty Four, PA Finnigan San Jose, CA J&W Scientific Folsom, CA Hewlett Packard LACHAT Inst. Mequon, WI 4.2 Calibration 4.2.1 Specifications Terpenes were identified using both retention time confirmation and matching experimental mass spectra against a custom library of mass spectra derived from a series of terpene standards. Terpenes were quantified against external standards, in which the most intense ion for the individual terpene (quantitation ion) was compared to the same ion from analyses of known amounts of neat terpene standards in hexane. Method blanks were used to correct for any response for terpenes on the conditioned cartridges. Monoterpenes were quantified using fenchone as an internal standard. 4.2.1.1 Tolerance None Given. 4.2.2 Frequency of Calibration The ion trap mass spectrometer was run through a daily auto-tune sequence prior to data acquisition on samples, standards, and blanks. This auto-tune sequence involved calibrating the mass scale and setting emission current, multiplier voltage, automatic gain control target value to proper values. 4.2.3 Other Calibration Information None Given. 5. Data Acquisition Methods Samples were collected by enclosing branches in a temperature- and light- controlled cuvette connected to plant gas exchange system (Campbell MPH 1000, Campbell Scientific, Logan, UT) and flowing hydrocarbon-free air over the needles. Temperature was controlled by use of thermoelectric coolers provided by Campbell Scientific, and light intensity was controlled by mounting a projector bulb at a right angle to the top of the glass-topped cuvette. The light was then reflected off of a cold mirror (458 cold mirror, 15-33233, OCLI, Santa Rosa, CA) mounted at a 458 angle to cuvette. The mirror transmitted light at wavelengths >720nm and reflected light of shorter wavelengths. Hydrocarbon- free air was produced by pumping ambient air through a clean-air generator (Aadco 5L, AADCO Instruments, Silver Springs, FL) and adding CO2 back to the entering air stream. All flows and environmental conditions were monitored by the sensors and mass flow controllers of the Campbell MPH 1000.Hydrocarbon emission samples were collected by diverting a fraction of the air exiting the leaf cuvette through a sampling tube packed with a solid sorbent. Supelco Carbotrap 300 cartridges (Bellafonte , PA) with dimensions of 7 in length and 1/4 in outer diameter were used in this work. The sampling tubes were conditioned before each use via a Tekmar Thermo Trap unit (Cincinnati, OH) at 220 8C for a minimum of four hours at a flow of approximately 10 mL/min of ultrahigh purity nitrogen. A blank from each set of conditioned cartridges was analyzed to ensure that they had been properly cleaned. The flow rate and volume of air passing over the sampling tube was controlled with a low flow pump (SKC Model-222, SKC, Inc. Eighty Four, PA). This sample volume was variable but kept well below the typical breakthrough volumes for terpenes on this sampling tube (Anon., 1986). After the emissions samples were collected, we separated the branchlet and needles from the main branch. Total needle biomass was measured on fresh needles. We then separated the total needle biomass into two parts, half of which we placed in a 60 8C drying oven and weighed daily until no further change in weight was observed. These dried needles were hen stored for nitrogen analysis. The remaining needles were ground in liquid nitrogen and stored in 20 mL scintillation vials filled with pentane until they were analyzed for monoterpene concentrations. The pentane storage was never less than seven days and was more than sufficient to allow for complete solvent extraction of the monoterpenes (Lerdau et al. 1995). The fresh weight / dry weight ratio from the needles used in the nitrogen analyses was applied to each monoterpene sample to provide an estimated dry weight for the sample. All analyses are reported on a dry-weight basis. 6. Observations 6.1 Data Notes None Given. 6.2 Field Notes None Given. 7. Data Description 7.1 Spatial Characteristics 7.1.1 Spatial Coverage The North American Datum 1983 (NAD83) coordinates for the sites are: SSA-OBS 53.98717°N, 105.11779°W SSA-OJP 53.91634°N, 104.69203°W 7.1.2 Spatial Coverage Map None Given. 7.1.3 Spatial Resolution These data are point source measurements taken near the given coordinates. 7.1.4 Projection Not Applicable. 7.1.5 Grid Description Not applicable. 7.2 Temporal Characteristics 7.2.1 Temporal Coverage The data were collected from 24-May-94 to 19-Sep-94. 7.2.2 Temporal Coverage Map None given. 7.2.3 Temporal Resolution Monthly averages of the data were calculated for 24-May-94 to 19-Sep-94. 7.3 Data Characteristics Data characteristics are defined in the companion data definition file (tgb8mono.def). 7.4 Sample Data Record Sample data format shown in the companion data definition file (tgb8mono.def). 8. Data Organization 8.1 Data Granularity All of the Monoterpene Concentration Data over the SSA-OBS and the SSA-OJP are contained in one dataset. 8.2 Data Format(s) The data files contain numerical and character fields of varying length separated by commas. The character fields are enclosed with a single apostrophe marks. There are no spaces between the fields. Sample data records are shown in the companion data definition file (tgb8mono.def). 9. Data Manipulations 9.1 Formulae 9.1.1 Derivation Techniques and Algorithms None given. 9.2 Data Processing Sequence 9.2.1 Processing Steps None given. 9.2.2 Processing Changes None given. 9.3 Calculations 9.3.1 Special Corrections/Adjustments None given. 9.3.2 Calculated Variables None. 9.4 Graphs and Plots None. 10. Errors 10.1 Sources of Error None given. 10.2 Quality Assessment 10.2.1 Data Validation by Source None given. 10.2.2 Confidence Level/Accuracy Judgement None given. 10.2.3 Measurement Error for Parameters None given. 10.2.4 Additional Quality Assessments None given. 10.2.5 Data Verification by Data Center The data were examined for general consistency and clarity. 11. Notes 11.1 Limitations of the Data None given. 11.2 Known Problems with the Data None given. 11.3 Usage Guidance None. 11.4 Other Relevant Information None. 12. Application of the Data Set None given. 13. Future Modifications and Plans None given. 14. Software 14.1 Software Description None given. 14.2 Software Access None given. 15. Data Access 15.1 Contact Information MS. Beth Nelson BOREAS Data Manager NASA GSFC Greenbelt, MD (301) 286-4005 (301) 286-0239 (fax) Elizabeth.Nelson@gsfc.nasa.gov 15.2 Data Center Identification See 15.1. 15.3 Procedures for Obtaining Data Users may place requests by telephone, electronic mail, or FAX. 15.4 Data Center Status/Plans The TGB-08 monoterpene data are available from the EOSDIS ORNL DAAC (Earth Observing System Data and Information System) (Oak Ridge National Laboratory) (Distributed Active Archive Center). The BOREAS contact at ORNL is: ORNL DAAC User Services Oak Ridge National Laboratory (865) 241-3952 ornldaac@ornl.gov ornl@eos.nasa.gov 16. Output Products and Availability 16.1 Tape Products None. 16.2 Film Products None. 16.3 Other Products Comma delimited ACSII Data Files 17. References 17.1 Platform/Sensor/Instrument/Data Processing Documentation None. 17.2 Journal Articles and Study Reports Sellers, P., F. Hall. 1994. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1994-3.0, NASA BOREAS Report (EXPLAN 94). Sellers, P., F. Hall, H. Margolis, B. Kelly, D. Baldocchi, G. den Hartog, J. Cihlar, M.G. Ryan, B. Goodison, P. Crill, K.J. Ranson, D. Lettenmaier, and D.E. Wickland. 1995. The boreal ecosystem-atmosphere study (BOREAS): an overview and early results from the 1994 field year. Bulletin of the American Meteorological Society. 76(9):1549-1577. Sellers, P., F. Hall, K.F. Huemmrich. 1996. Boreal Ecosystem-Atmosphere Study: 1994 Operations. NASA BOREAS Report (OPS DOC 94). Sellers, P., F. Hall. 1996. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1996-2.0, NASA BOREAS Report (EXPLAN 96). Sellers, P., F. Hall, K.F. Huemmrich. 1997. Boreal Ecosystem-Atmosphere Study: 1996 Operations. NASA BOREAS Report (OPS DOC 96). Sellers, P. J., F. G. Hall, R. D. Kelly, A. Black, D. Baldocchi, J. Berry, M. Ryan, K. J. Ranson, P. M. Crill, D. P. Lettenmaier, H. Margolis, J. Cihlar, J. Newcomer, D. Fitzjarrald, P. G. Jarvis, S. T. Gower, D. Halliwell, D. Williams, B. Goodison, D. E. Wickland, and F. E. Guertin. 1997. BOREAS in 1997: Experiment Overview, Scientific Results and Future Directions. Journal of Geophysical Research 102 (D24): 28,731-28,770. 17.3 Archive/DBMS Usage Documentation None. 18. Glossary of Terms None given. 19. List of Acronyms BOREAS - BOReal Ecosystem-Atmosphere Study BORIS - BOREAS Information System DAAC - Distributed Active Archive Center EOS - Earth Observing System EOSDIS - EOS Data and Information System GSFC - Goddard Space Flight Center NASA - National Aeronautics and Space Administration ORNL - Oak Ridge National Laboratory URL - Uniform Resource Locator 20. Document Information 20.1 Document Revision Date Written: 28-Jul-1997 Last updated: 14-Sep-1998 20.2 Document Review Date(s) BORIS Review: 28-Aug-1998 Science Review: 20.3 Document ID 20.4 Citation Manuel Lerdau: Department of Ecology and Evolution, State University of New York, Stony Brook, NY 11794-5245 Marcy Litvak and Russell Monson: Department of Environmental, population and Organismic Biology, University of Colorado, Boulder, CO 80309-033 20.5 Document Curator 20.6 Document URL Keywords: Monoterpene, Terpene, NMHC, Photosynthesis, Starch. TGB08_Monoterpene_Conc.doc 09/14/98