Isoprene emission capacity measurements are presented from 18 North American oak (Quercus) species and species from six other genera previously found to emit significant quantities of isoprene. Sampling was conducted at physiographically diverse locations in North Carolina, Central California, and Northern Oregon. Emissions from several sun leaves of each species were measured at or near standard conditions (leaf temperature of 30°C and photosynthetically active radiation of 1000 μmol m-2s-1) using environmentally controlled cuvette systems and gas chromatography with reduction gas detectors. Species mean emission capacity ranged from 39 to 158 μg Cg-1h-1 (mean of 86), or 22 to 79 nmol m-2s-1 (mean of 44). These rates are 2-28 times higher than those previously reported from the same species, which were summarized in a recent study where isoprene emission rates were assigned based on published data and taxonomy. These discrepancies were attributed to differences in leaf environment during development, measurement technique (branch or plant enclosure versus leaf enclosure), and lack of environmental measurements associated with some of the earlier branch enclosure measurements. Mass-based emission capacities for 15 of 18 oak species, sweetgum (Liquidambar styraciflua), and poplars (Populus trichocarpa and P. deltoides) were within ranges used in current biogenic volatile organic compound (BVOC) emission models, while measured rates for the remaining three oak species, Nyssa sylvatica, Platanus occidentalis, Robinia pseudoacacia, Salix nigra, and Populus hybrids (Populus trichocarpa × P. deltoides) were considerably higher. In addition, mean specific leaf mass of the oak species was 30% higher than assumed in current emission models. Emission rates reported here and in other recent studies support recent conclusions that isoprene emission capacities for sun leaves of high emitting species may be better represented by a value of 100 ± 50 μg Cg-1h-1 during hot summer conditions. We also find that intermediate isoprene emission rates previously suggested for some tree species may not represent their true emission capacities, and that broadleaf plant species may have either low (< 1.0 μg Cg-1h-1) or very high (∼ 100 μg Cg-1h-1) genetic capacity to emit isoprene when mature foliage is exposed to a high ambient temperature and light environment.

In February 2001, as part of the Southern African Regional Science Initiative (SAFARI 2000), isoprene fluxes were measured for 8 days using the relaxed eddy accumulation technique from a 21‐m tower in a Combretum‐Acacia savanna in Kruger National Park, 13 km from Skukuza, RSA. Despite warm and sunny conditions, midday isoprene concentrations were low, averaging 0.39 nL/L. Fluxes of isoprene increased through the morning hours, with midday fluxes averaging 0.34 mg m−2 h−1 and a maximum measured flux of approximately 1.0 mg m−2 h−1. Consistent with these low fluxes, leaf enclosure measurements of woody species within the tower footprint determined that only one isoprene‐emitting species, Acacia nigrescens, was present in significant numbers, comprising less than 10% of the woody biomass. Combining enclosure data with species composition and leaf area index data from the site, we estimated that the isoprene emission capacity of the vegetation within the vicinity of the tower was very low, approximately 0.47 mg m−2 h−1, and patchy. Under these circumstances, low and variable fluxes are expected. Additional leaf enclosure measurements, for a total of 121 species, were made at other locations, and approximately 35% of the species was found to emit significant amounts of isoprene. Important isoprene emitting plant families included Caesalpinaceae, Mimosaceae, Papilionaceae, Euphorbiaceae, Moraceae, and Myrtaceae. Twelve members of the important savanna genus Acacia were measured, of which five species, all belonging in Subgenus Aculeiferum, Section Aculeiferum, were found to emit significant amounts of isoprene. In contrast, the plant family, Combretaceae, dominant in many savanna ecosystems, was found to contain no species which emit isoprene.

Terpenoid emissions from ponderosa pine (Pinus ponderosa subsp. scopulorum) were measured in Colorado, USA over two growing seasons to evaluate the role of incident light, needle temperature, and stomatal conductance in controlling emissions of 2-methyl-3-buten-2-ol (MBO) and several monoterpenes. MBO was the dominant daylight terpenoid emission, comprising on average 87% of the total flux, and diurnal variations were largely determined by light and temperature. During daytime, oxygenated monoterpenes (especially linalool) comprised up to 75% of the total monoterpenoid flux from needles. A significant fraction of monoterpenoid emissions was dependent on light and 13CO2 labeling studies confirmed de novo production. Thus, modeling of monoterpenoid emissions required a hybrid model in which a significant fraction of emissions was dependent on both light and temperature, while the remainder was dependent on temperature alone. Experiments in which stomata were forced to close using abscisic acid demonstrated that MBO and a large fraction of the monoterpene flux, presumably linalool, could be limited at the scale of seconds to minutes by stomatal conductance. Using a previously published model of terpenoid emissions, which explicitly accounts for the physicochemical properties of emitted compounds, we were able to simulate these observed stomatal effects, whether induced experimentally or arising under naturally fluctuation conditions of temperature and light. This study shows unequivocally that, under naturally occurring field conditions, de novo light-dependent monoterpenes comprise a significant fraction of emissions in ponderosa pine. Differences between the monoterpene composition of ambient air and needle emissions imply a significant non-needle emission source enriched in Δ-3-carene.

Diurnal branch-level emission rates of biogenic volatile organic compounds (BVOC) including isoprene, monoterpenes (MT), and sesquiterpenes (SQT) were determined at the University of Michigan Biological Station for the tree species red maple (Acer rubrum), red oak (Quercus rubra), paper birch (Betula papyrifera), white pine (Pinus strobus), and big tooth aspen (Populus grandidentata). These emission rates were combined with detailed biomass distribution and meteorological data and incorporated into the canopy model, model of emissions of gasses and aerosols from nature (MEGAN), for estimating whole-canopy fluxes of isoprene. The modeled half-hour fluxes (mg C m- 2 h- 1) and cumulative seasonal fluxes (mg C m- 2) compared favorably with results from direct, canopy-level eddy covariance (EC) isoprene measurements; modeled cumulative seasonal flux deviated less than 30% from the EC results. Significant MT emissions were found from four of the five tree species. MT emissions from three of these were both light- and temperature-dependent and were approximately one order of magnitude greater than light-independent MT emissions. SQT emissions were identified from three of the five tree species. The model was modified to incorporate SQT and both light-dependent and light-independent MT emissions for determining fluxes. Isoprene comprised > 95 % of the total terpenoid flux with MT and SQT comprising 4% and 0.3%, respectively. The average cumulative fluxes (in mg C m- 2) from June through September were 2490 for isoprene, 105 for MT, and 7 for SQT. A simple box model analysis was used to estimate the contribution of the isoprene, MT, and SQT emissions to the total OH reactivity. These results confirm that isoprene dominates OH reactions especially during daytime hours. Emissions of reactive MT and SQT increase the BVOC+OH reactivity, but are still lower than estimates of BVOC fluxes at this site necessary for affecting OH reactivity to the significant degree suggested by recent reports. © 2007 Elsevier Ltd. All rights reserved.

The magnitudes, distributions, controlling processes and uncertainties associated with North American natural emissions of oxidant precursors are reviewed. Natural emissions are responsible for a major portion of the compounds, including non-methane volatile organic compounds (NMVOC), carbon monoxide (CO) and nitric oxide (NO), that determine tropospheric oxidant concentrations. Natural sources include soil microbes, vegetation, biomass burning, and lightning. These sources are strongly influenced by human activities that have led to significant changes in the magnitude and distribution of natural emissions in the past two centuries. The total NMVOC flux of about 84 × 1012 g of carbon (Tg C) is comprised primarily of isoprene (35%), 19 other terpenoid compounds (25%) and 17 non-terpenoid compounds (40%). Vegetation is predicted to contribute about 98% of the total annual natural NMVOC emission. The estimated annual natural NO emission of 2.1 × 1012 g of nitrogen (Tg N) from North America is primarily due to soils and lightning, while the estimated 10 Tg C of CO arises from biomass burning and vegetation. Field measurements of ambient concentrations and above canopy fluxes have validated emission estimates for a few compounds from some important landscapes. The uncertainty associated with natural emission estimates ranges from less than 50% for midday summer isoprene emission from some locations to about a factor of 10 for some compounds and landscapes.

A global three-dimensional (3-D) chemistry and transport model was used to demonstrate that a factor of 2 decrease in isoprene and monoterpene emissions results in significant (10-30%) changes in predicted concentration distributions of compounds such as OH, MPAN, NOx, H2O2, O3, and CO. Isoprene and monoterpenes were predicted to have a particularly strong impact on tropical regions, including central Africa. The 1996 Experiment for Regional Sources and Sinks of Oxidants (EXPRESSO) study included a number of experiments that improved our ability to predict isoprene and monoterpene emissions from central Africa. The results of these experiments have been incorporated into an isoprene emission model that predicts hourly emissions on a spatial scale of about 1 km2. The model uses procedures that are suitable for estimating global emissions but use's regional measurements to accurately parameterize the model. Comparisons with above-canopy aircraft and tower flux measurements demonstrate that the model can estimate emissions within a factor of 2 for regions where ground measurements of model inputs are available. The annual central African isoprene emission predicted by our revised model (35 Tg C) is only 14% less than that predicted by our earlier model, but there are considerable differences in estimates of individual model variables. The models differ by more than a factor of 5 for specific times and locations, which indicates that .there are large uncertainties in emission estimates for at least some locations and seasons. The good agreement obtained for the EXPRESSO study field sites, however, suggests that the model can predict reasonable estimates if representative field measurements are used to parameterize the model. Copyright 1999 by the American Geophysical Union.

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m(-2)  h(-1) at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The meganv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.

Total OH reactivity was measured during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen-Southern Rocky Mountain 2008 field campaign (BEACHON-SRM08) held at Manitou Experimental Forest (MEF) in Colorado USA in August, 2008. The averaged total OH reactivity was 6.7s-1, smaller than that measured in urban (33.4s-1, Yoshino etal., 2012) and suburban (27.7s-1, Yoshino etal., 2006) areas in Tokyo in the same season, while sporadically high OH reactivity was also observed during some evenings. The total OH reactivity measurements were accompanied by observations of traces species such as CO, NO, NOy, O3 and SO2 and Volatile Organic Compounds (VOCs). From the calculation of OH reactivity based on the analysis of these trace species, 46.3% of OH reactivity for VOCs came from biogenic species that are dominated by 2-methyl-3-buten-2-ol (MBO), and monoterpenes. MBO was the most prominent contribution to OH reactivity of all trace species. A comparison of observed and calculated OH reactivity shows that the calculated OH reactivity is 29.5% less than the observed value, implying the existence of missing OH sinks. One of the candidates of missing OH is thought to be the oxidation products of biogenic species. © 2013 Elsevier Ltd.

Biogenic volatile organic compound (BVOC) emissions were studied using vegetation enclosure experiments. Particular emphasis was given to sesquiterpene compounds (SQT), although monoterpenes (MT) were also characterized. SQT were detected in emissions from seven (out of eight) pine species that were examined. Thirteen SQT compounds were identified; the most abundant ones were beta-caryophyllene, alpha-bergamotene, beta-farnesene, and alpha-farnesene, with emission rates increasing exponentially with temperature. Regression analysis yielded exponential dependencies of both MT and SQT emissions on temperature of the form E = E0 x exp(beta(T - T0)). This resulted in SQT basal emission rates (E0 defined at T0 = 30 degrees C) ranging between <4 and 620 ng (carbon) gdw(-1) h(-1) (gdw = gram dry weight). The average value of the exponential temperature response factor beta for SQT emissions, taken from all experiments, was 0.17 degree C(-1), whereas the value for monoterpenes was 0.11 degrees C(-1). The average, total SQT emissions from pines were estimated to be 9, 16, and 29% of the MT emissions at 20, 30, and 40 degrees C respectively. The emission factors and beta-factors determined from these measurements were used to estimate pine tree MT and SQT emission distributions for the contiguous United States using MEGAN (model of emissions of gases and aerosols from nature, Guenther et al., 2006). SQT fluxes reaching 10-40 mg m(-2) for the month of July were estimated for extensive areas of most western and southern U.S. states.

Biogenic emission of sesquiterpene (SQT) and oxygenated SQT (OSQT) were measured from the dominant vegetation in a desert shrubland and urban area (Las Vegas, Nevada, U.S.A.), and at temperate forest sites at Niwot Ridge, Colorado, U.S.A., Tomakomai, Hokkaido, Japan and Tumbarumba, New South Wales, Australia. Additional measurements were conducted using greenhouse grown plants. The sampling technique, based on solid adsorbent preconcentration and liquid extraction, is suitable for measuring high molecular weight and low volatility compounds such as OSQTs. Fourteen SQT and OSQT (10 SQT and 4 OSQT) were identified in the field experiments. Total emission rates of SQTs and OSQTs varied from the detection limit to 7.6 μgC g-1h-1 (average: 0.74) and 3.7 μgC g-1h-1 (average: 0.31), respectively, and varied with plant species and location. Environmental conditions, including temperature and precipitation, appeared to influence emission rates. Canopy level emission of SQT and OSQT in Tomakomai were also estimated using an emission model. The emission rate of SQT and OSQT ranged from 72 to 710 μgC m-2h-1 (average, 460 in daytime) and from 38 to 370 μgC m-2h-1 (average, 240 in daytime), respectively. Their contributions can be very high in specific regions and seasons. Given the relatively high reactivity and secondary organic aerosol yields of SQTs and OSQTs, it is likely that these compounds influence atmospheric constituents in at least some areas. Copyright © 2009 by The Geochemical Society of Japan.