In summer 1992, isoprene emission was measured on intact leaves and branches of Quercus alba (L.) at two heights in a forest canopy. Isoprene emission capacity (measured at 30 degrees C and a photosynthetic photon flux density of 1000 micro mol m(-2) s(-1)) was significantly higher in sun leaves than in shade leaves when expressed on a leaf area basis (51 versus 31 nmol m(-2) s(-1); P < 0.01). Because leaf mass per unit area (LMA, g m(-2)) was higher in sun leaves than in shade leaves, emissions of sun and shade leaves expressed on a dry mass basis did not differ significantly (99 versus 89 micro g C g(DW) (-1) h(-1); P = 0.05). Similar measurements in 1995 were consistent with the 1992 data, but data from leaves in more shaded locations demonstrated that isoprene emission capacity decreased with decreasing growth irradiance, irrespective of units of expression. Isoprene emission capacity in leaves of Q. coccinea Muenchh. and Q. velutina Lam. also declined steeply with canopy depth. Emission capacity, on a dry mass basis, showed no obvious pattern with canopy position in Q. prinus L. There was no difference in the temperature response of sun versus shade leaves of Q. alba, but shade leaves exhibited a greater quantum efficiency and saturated at lower irradiance than sun leaves. Rates of isoprene emission measured on branches of Q. alba were approximately 60% of those measured on individual leaves, as a result of self-shading within branch enclosures. It is recommended that within-canopy variation in isoprene emission capacity be incorporated into regional emission models.

In June 1993, net photosynthetic rates, stomatal conductance and isoprene emission rates of sweetgum leaves (Liquidambar styraciflua L.) were measured at the top of the forest canopy (sun leaves) and within the canopy at a height of 8-10 m above ground level (shade leaves). Large differences in net photosynthetic rates and stomatal conductance were found between sun and shade leaves. Mean rates of isoprene emission, expressed on a leaf area basis, were significantly lower in shade leaves than in sun leaves (4.1 versus 17.1 nmol m(-2) s(-1)); however, because specific leaf area of sun leaves was lower than that of shade leaves (0.0121 versus 0.0334 m(2) g(-1)), the difference between sun and shade leaves was less, though still significant, when isoprene emissions were expressed on a dry mass basis (45.5 versus 29.0 micro g C g(-1) h(-1)). Saturation of both net photosynthesis and isoprene emission occurred at lower PPFDs in shade leaves than in sun leaves. The effect of leaf temperature on isoprene emissions also differed between sun and shade leaves. Sun leaves lost a significantly greater percentage of fixed carbon as isoprene than shade leaves. The leaf-level physiological measurements were used to derive parameters for a canopy-level isoprene flux model. The importance of incorporating differences between sun- and shade-leaf properties into existing models is discussed.

The light, temperature and stomatal conductance dependencies of volatile organic compound (VOC) emissions from ten plant species commonly found in the Mediterranean region were studied using a fully controlled leaf cuvette in the laboratory. At standard conditions of temperature and light (30°C and 1000μmolm-2s-1 PAR), low emitting species (Arbutus unedo, Pinus halepensis, Cistus incanus, Cistus salvifolius, Rosmarinus officinalis and Thymus vulgaris) emitted between 0.1 and 5.0μg (C) (total VOCs) g-1 dwh-1, a medium emitter (Pinus pinea) emitted between 5 and 10μg (C)g-1 dwh-1 and high emitters (Cistus monspeliensis, Lavendula stoechas and Quercus sp.) emitted more than 10μg (C)g-1 dwh-1. VOC emissions from all of the plant species investigated showed some degree of light dependency, which was distinguishable from temperature dependency. Emissions of all compounds from Quercus sp. were light dependent. Ocimene was one of several monoterpene compounds emitted by P. pinea and was strongly correlated to light. Only a fraction of monoterpene emissions from C. incanus exhibited apparent weak light dependency but emissions from this plant species were strongly correlated to temperature. Data presented here are consistent with past studies, which show that emissions are independent of stomatal conductance. These results may allow more accurate predictions of monoterpene emission fluxes from the Mediterranean region to be made. © 2002 Elsevier Science Ltd. All rights reserved.

High rates of emission of 2-methyl-3-buten-2-ol (MBO) were measured from needles of several pine species. Emissions of MBO in the light were 1 to 2 orders of magnitude higher than emissions of monoterpenes and, in contrast to monoterpene emissions from pines, were absent in the dark. MBO emissions were strongly dependent on incident light, behaving similarly to net photosynthesis. Emission rates of MBO increased exponentially with temperature up to approximately 35°C. Above approximately 42°G, emission rates declined rapidly. Emissions could be modeled using existing algorithms for isoprene emission. We propose that emissions of MBO from lodgepole and ponderosa pine are the primary source of high concentrations of this compound, averaging 1-3 ppbv, found in ambient air samples collected in Colorado at an isolated mountain site approximately 3050 m above sea level. Subsequent field studies in a ponderosa pine plantation in California confirmed high MBO emissions, which averaged 25 μg C g-1 h-1 for 1-year-old needles, corrected to 30°C and photon flux of 1000 μmol m-2 s-1. A total of 34 pine species growing at Eddy Arboretum in Placerville, California, were investigated, of which 11 exhibited high emissions of MBO (>5 μg C g-1 h-1), and 6 emitted small but detectable amounts. All the emitting species are of North American origin, and most are restricted to western North America. These results indicate that MBO emissions from pines may constitute a significant source of reactive carbon and a significant source of acetone, to the atmosphere, particularly in the western United States. Copyright 1998 by the American Geophysical Union.

Biogenic emissions of volatile organic compounds (VOC) from forests play an important role in regulating the atmospheric trace gas composition including global tropospheric ozone concentrations. However, more information is needed on VOC emission rates from different forest regions of the world to understand regional and global impacts and to implement possible mitigation strategies. The mixed deciduous and coniferous forests of northern Wisconsin, USA, were predicted to have significant VOC emission rates because they are comprised of many genera (i.e. Picea, Populus, Quercus, Salix) known to be high VOC emitters. In July 1993, a study was conducted on the Chequamegon National Forest near Rhinelander, WI, to identify and quantify VOC emitted from major trees, shrubs, and understory herbs in the mixed northern forests of this region. Emission rates were measured at various scales - at the leaf level with cuvettes, the branch level with branch enclosures, the canopy level with a tower based system, and the landscape level with a tethered balloon air sampling system. Area-average emission rates were estimated by scaling, using biomass densities and species composition along transects representative of the study site. Isoprene (C5H8) was the primary VOC emitted, although significant quantities of monoterpenes (C10H16) were also emitted. The highest emission rates of isoprene (at 30°C and photosynthetically active radiation of 1000 μmol m-2 s-1) were from northern red oak (Quercus rubra, > 110 μg(C) g-1 h-1); aspen (Populus tremuloides, > 77); willow (Salix spp., > 54); and black spruce (Picea mariana, > 10). Emission rates of hybrid poplar clones ranged from 40 to 90 μg(C) g-1 h-1 at 25°C; those of Picea provenances were generally < 10, and emission rates of a hybrid between North American and European spruces were intermediate to parental rates. More than 30 species of plants were surveyed from the sites, including several from previously unstudied genera such as Alnus, Chamaedaphne, Ledum, Tilia, Rubus, and Sphagnum. Based on the measured isoprene concentrations in the daytime atmospheric surface layer and mixed layer, area-averaged fluxes of isoprene were estimated to be about 1 mg(C)m-2 h-1. This estimate agrees reasonably well with model predictions. Our results indicate that mixed forests in the Lake States region of the USA are a significant source of reactive VOC to the atmosphere. Accurate estimates of these emissions are required for determining appropriate regulatory air pollution control strategies. Future studies are needed to extrapolate these estimates to other landscapes and to better understand the factors controlling observed variations in VOC emissions.

Natural volatile organic compound (VOC) fluxes were measured in three U.S. woodlands in summer 1993. Fluxes from individual leaves and branches were estimated with enclosure techniques and used to initialize and evaluate VOC emission model estimates. Ambient measurements were used to estimate above canopy fluxes for entire stands and landscapes. The branch enclosure experiments revealed 78 VOCs. Hexenol derivatives were the most commonly observed oxygenated compounds. The branch measurements also revealed high rates of isoprene emission from three genera of plants (Albizia, Chusqua and Mahonia) and high rates of monoterpene emission from three genera (Atriplex, Chrysthamnus and Sorbus) for which VOC emission rates have not been reported. Measurements on an additional 34 species confirmed previous results. Leaf enclosure measurements of isoprene emission rates from Quercus were substantially higher than the rates used in existing emission models. Model predictions of diurnal variations in isoprene fluxes were generally within +/- 35% of observed flux variations. Measurements with a fast response analyzer demonstrated that 60 min is a reasonable time resolution for biogenic emission models. Average daytime stand scale (hundreds of m) flux measurements ranged from about 1.3 mg C m(-2) h(-1) for a shrub oak stand to 1.5-2.5 mg C m(-2) h(-1) for a mixed forest stand. Morning, evening and nighttime fluxes were less than 0.1 mg C m(-2) h(-1). Average daytime landscape scale (tens of km) flux measurements ranged from about 3 mg C m(-2) h(-1) for a shrub oak-aspen and rangeland landscape to about 7 mg C m(-2) h(-1) for a deciduous forest landscape. Fluxes predicted by recent versions (BEIS2, BEIS2.1) of a biogenic emission model were within 10 to 50% of observed fluxes and about 300% higher than those predicted by a previous version of the model (BEIS).

Reactive gases and aerosols are produced by terrestrial ecosystems, processed within plant canopies, and can then be emitted into the above-canopy atmosphere. Estimates of the above-canopy fluxes are needed for quantitative earth system studies and assessments of past, present and future air quality and climate. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) is described and used to quantify net terrestrial biosphere emission of isoprene into the atmosphere. MEGAN is designed for both global and regional emission modeling and has global coverage with ∼1 km2 spatial resolution. Field and laboratory investigations of the processes controlling isoprene emission are described and data available for model development and evaluation are summarized. The factors controlling isoprene emissions include biological, physical and chemical driving variables. MEGAN driving variables are derived from models and satellite and ground observations. Tropical broadleaf trees contribute almost half of the estimated global annual isoprene emission due to their relatively high emission factors and because they are often exposed to conditions that are conducive for isoprene emission. The remaining flux is primarily from shrubs which have a widespread distribution. The annual global isoprene emission estimated with MEGAN ranges from about 500 to 750 Tg isoprene (440 to 660 Tg carbon) depending on the driving variables which include temperature, solar radiation, Leaf Area Index, and plant functional type. The global annual isoprene emission estimated using the standard driving variables is ∼600Tg isoprene. Differences in driving variables result in emission estimates that differ by more than a factor of three for specific times and locations. It is difficult to evaluate iso prene emission estimates using the concentration distributions simulated using chemistry and transport models, due to the substantial uncertainties in other model components, but at least some global models produce reasonable results when using isoprene emission distributions similar to MEGAN estimates. In addition, comparison with isoprene emissions estimated from satellite formaldehyde observations indicates reasonable agreement. The sensitivity of isoprene emissions to earth system changes (e.g., climate and land-use) demonstrates the potential for large future changes in emissions. Using temperature distributions simulated by global climate models for year 2100, MEGAN estimates that isoprene emissions increase by more than a factor of two. This is considerably greater than previous estimates and additional observations are needed to evaluate and improve the methods used to predict future isoprene emissions.

Biogenic volatile organic compound (BVOC) emissions were measured in a mopane woodland near Maun, Botswana in January–February 2001 as part of SAFARI 2000. This landscape is comprised of more than 95% of one woody plant species, Colophospermum mopane (Caesalpinaceae). Mopane woodlands extend over a broad area of southern Africa. A leaf cuvette technique was used to determine the emission capacities of the major vegetation and the temperature and light dependence of the emissions. In addition, relaxed eddy accumulation (REA) measurements of BVOC fluxes were made on a flux tower, where net CO2 emissions were also measured simultaneously. Large light‐dependent emissions of terpenes (mostly α‐pinene and d‐limonene) were observed from the mopane woodland. The diurnal BVOC emissions were integrated and compared with the CO2 flux. Monoterpene flux exceeded 3000 μg C m−2 h−1 during the daytime period, comparable to isoprene fluxes and much higher than terpene fluxes measured in most areas. The terpene flux constituted approximately 25% of the diurnal net carbon exchange (CO2) during the experimental period. Other BVOC emissions may also contribute to the carbon exchange.

Two proton-transfer-reaction mass spectrometry systems were deployed at the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H₂O, Organics and Nitrogen-Southern Rocky Mountain 2008 field campaign (BEACHON-SRM08; July to September, 2008) at the Manitou Forest Observatory in a ponderosa pine woodland near Woodland Park, Colorado USA. The two PTR-MS systems simultaneously measured BVOC emissions and ambient distributions of their oxidation products. Here, we present mass spectral analysis in a wide range of masses (m/z 40⁺ to 210⁺) to assess our understanding of BVOC emissions and their photochemical processing inside of the forest canopy. The biogenic terpenoids, 2-methyl-3-butene-2-ol (MBO, 50.2%) and several monoterpenes (MT, 33.5%) were identified as the dominant BVOC emissions from a transmission corrected mass spectrum (PTR-MS), averaged over the daytime (11 a.m. to 3 p.m., local time) of three days. To assess contributions of oxidation products of local BVOC, we calculate an oxidation product spectrum with the OH- and ozone-initiated oxidation product distribution mass spectra of two major BVOC emissions at the ecosystem (MBO and β-pinene) that were observed from laboratory oxidation experiments. The majority (~76%) of the total signal in the transmission corrected PTR-MS spectra could be explained by identified compounds. The remainder are attributed to oxidation products of BVOC emitted from nearby ecosystems and transported to the site, and oxidation products of unidentified BVOC emitted from the ponderosa pine ecosystem.

Using new in-situ field observations of the most abundant oxygenated VOCs (methanol, acetaldehyde, acetone, C3/C4 carbonyls,MVK+MAC and acetic acid) we were able to constrain emission and deposition patterns above and within a loblolly pine (Pinus taeda) plantation with a sweetgum (Liquidambar styraciflua) understory. During the day canopy scale measurements showed significant emission of methanol and acetone, while methyl vinyl ketone and methacrolein, acetaldehyde and acetic acid were mainly deposited during the day. All oxygenated compounds exhibited strong losses during the night that could not be explained by conventional dry deposition parameterizations. Accompanying leaf level measurements indicated substantial methanol and acetone emissions from loblolly pine. The exchange of acetaldehyde was more complex. Laboratory measurements made on loblolly pine needles indicated that acetaldehyde may be either emitted or taken up depending on ambient concentrations, with the compensation point increasing exponentially with temperature, and that mature needles tended to emit more acetaldehyde than younger needles. Canopy scale measurements suggested mostly deposition. Short-term (approx. 2h) ozone fumigation in the laboratory had no detectable impact on post-exposure emissions of methanol and acetone, but decreased the exchange rates of acetaldehyde. The emission of a variety of oxygenated compounds (e.g. carbonyls and alcohols) was triggered or significantly enhanced during laboratory ozone fumigation experiments. These results suggest that higher ambient ozone levels in the future might enhance the biogenic contribution of some oxygenated compounds. Those with sufficiently low vapor pressures may potentially influence secondary organic aerosol growth. Compounds recently hypothesized to be primarily produced in the canopy atmosphere via ozone plus terpenoid-type reactions can also originate from the oxidation reaction of ozone with leaf surfaces and inside the leaf. This needs to be taken into account when scaling up very reactive biogenic compounds. © 2005 Author(s). This work is licensed under a Creative Commons License.