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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.

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.

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 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.

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.

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

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

The Ozarks Isoprene Experiment (OZIE) was conducted in July 1998 in Missouri, Illinois, Indiana, and Oklahoma. OZIE was designed to investigate the presumed strong isoprene emission rates from the Missouri Ozarks, where there is a high density of oak trees that are efficient isoprene emitters. Ground, balloon, and aircraft measurements were taken over a three-week study period; 0-D and 3-D chemical models were subsequently used to better understand the observed isoprene emissions from the Ozarks and to investigate their potential regional-scale impacts. Leaf-level measurements for two oak tree species yielded normalized average isoprene emission capacities of 66 mgC g-1 h-1, in good agreement with values used in current biogenic emissions models. However, the emission capacities exhibited a temperature dependence that is not captured by commonly used biogenic emission models. Isoprene mixing ratios measured aloft from tethered balloon systems were used to estimate isoprene fluxes. These measurement-derived fluxes agreed with BEIS3 estimates within the relatively large uncertainties in the estimates. Ground-level isoprene mixing ratios exhibited substantial spatial heterogeneity, ranging from

As part of the Large Scale Biosphere-Atmosphere Experiment in Amazônia (LBA), we have developed a bottom-up approach for estimating canopy-scale fluxes of isoprene. Estimating isoprene fluxes for a given forest ecosystem requires knowledge of foliar biomass, segregated by species, and the isoprene emission characteristics of the individual tree species comprising the forest. In this study, approximately 38% of 125 tree species examined at six sites in the Brazilian Amazon emitted isoprene. Given logistical difficulties and extremely high species diversity, it was possible to screen only a small percentage of tree species, and we propose a protocol for estimating the emission capacity of unmeasured taxa using a taxonomic approach, in which we assign to an unmeasured genus a value based on the percentage of genera within its plant family which have been shown to emit isoprene. Combining this information with data obtained from 14 tree censuses at four Neotropical forest sites, we have estimated the percentage of isoprene-emitting biomass at each site. The relative contribution of each genus of tree is estimated as the basal area of all trees of that genus divided by the total basal area of the plot. Using this technique, the percentage of isoprene-emitting biomass varied from 20% to 42% (mean = 31%; SD = 8%). Responses of isoprene emission to varying light and temperature, measured on a sun-adapted leaf of mango (Mangifera indica L.), suggest that existing algorithms developed for temperate species are adequate for tropical species as well. Incorporating these algorithms, estimates of isoprene-emitting biomass, isoprene emission capacity, and site foliar biomass into a canopy flux model, canopy-scale fluxes of isoprene were predicted and compared with the above-canopy fluxes measured at two sites. Our bottom-up approach overestimates fluxes by about 50%, but variations in measured fluxes between the two sites are largely explained by observed variation in the amount of isoprene-emitting biomass. © 2004 Blackwell Publishing Ltd.

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.

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.

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.

During the summer of 1992, isoprene emissions were measured in a mixed deciduous forest near Oak Ridge, Tennessee. Measurements were aimed at the experimental scale‐up of emissions from the leaf level to the forest canopy to the mixed layer. Results from the scale‐up study are compared to different canopy models for determining the leaf microclimate as input to isoprene emission algorithms. These include (1) no canopy effects, (2) a simple vertical scaling canopy model with a leaf energy balance, and (3) a numerical canopy model which accounts for leaf‐sun geometries, photosynthesis, respiration, transpiration, and gas transport in the canopy. Initial evaluation of the models was based upon a standard emission rate factor of 90 μgC g−1 hr−1 (0.42 nmol g−1 s−1) taken from leaf cuvette measurements and a biomass density factor of 203 g m−2 taken from biomass surveys and a flux footprint analysis. The results indicated that predicted fluxes were consistent among the models to within approximately ±20%, but that the models overestimated the mean flux by about a factor of 2 and overestimated the maximum observed flux by 30 to 50%. Adjusting the standard emission factor and biomass density each downward by 20% yielded predicted means approximately 20% greater than the observed means and predicted maxima approximately 25% less than the observed maxima. Accounting for changes in biomass density as a function of direction upwind of the tower improved the overall model performance.

Isoprene fluxes were estimated using eight different measurement techniques at a forested site near Oak Ridge, Tennessee, during July and August 1992. Fluxes from individual leaves and entire branches were estimated with four enclosure systems, including one system that controls leaf temperature and light. Variations in isoprene emission with changes in light, temperature, and canopy depth were investigated with leaf enclosure measurements. Representative emission rates for the dominant vegetation in the region were determined with branch enclosure measurements. Species from six tree genera had negligible isoprene emissions, while significant emissions were observed for Quercus, Liquidambar, and Nyssa species. Above‐canopy isoprene fluxes were estimated with surface layer gradients and relaxed eddy accumulation measurements from a 44‐m tower. Midday net emission fluxes from the canopy were typically 3 to 5 mg C m−2 h−1, although net isoprene deposition fluxes of −0.2 to −2 mg C m−2 h−1 were occasionally observed in early morning and late afternoon. Above‐canopy CO2 fluxes estimated by eddy correlation using either an open path sensor or a closed path sensor agreed within ±5%. Relaxed eddy accumulation estimates of CO2 fluxes were within 15% of the eddy correlation estimates. Daytime isoprene mixing ratios in the mixed layer were investigated with a tethered balloon sampling system and ranged from 0.2 to 5 ppbv, averaging 0.8 ppbv. The isoprene mixing ratios in the mixed layer above the forested landscape were used to estimate isoprene fluxes of 2 to 8 mg C m−2 h−1 with mixed layer gradient and mixed layer mass balance techniques. Total foliar density and dominant tree species composition for an approximately 8100 km2 region were estimated using high‐resolution (30 m) satellite data with classifications supervised by ground measurements. A biogenic isoprene emission model used to compare flux measurements, ranging from leaf scale (10 cm2) to landscape scale (102 km2), indicated agreement to within ±25%, the uncertainty associated with these measurement techniques. Existing biogenic emission models use isoprene emission rate capacities that range from 14.7 to 70 μg C g−1 h−1 (leaf temperature of 30°C and photosynthetically active radiation of 1000 μmol m−2 s−1) for oak foliage. An isoprene emission rate capacity of 100 μg C g−1 h−1 for oaks in this region is more realistic and is recommended, based on these measurements.

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. -from Authors