Search

Semivolatile oxygenated organic compounds (SV-OVOCs) are important atmospheric species, in particular for the production and chemistry of atmospheric particulate matter and related impacts on air quality and climate. In this study, SV-OVOCs were collected in the horizontal plane of the roughness layer over the tropical forest in the central Amazon during the wet season of 2018. A sampler mounted to a coptertype, hovering unmanned aerial vehicle was used. Underlying the collection region, a plateau forest transitioned into a slope forest across several hundred meters. The concentrations of pinonic and pinic acids, which are monoterpene oxidation products, had no statistical difference over the two forests. By comparison, across the study period, differences in the concentration of 2-methyltetrols, which are products of isoprene oxidation, ranged from _70% to +480% over the two forests. The chemical lifetime of 2-methyltetrols in the atmosphere is sufficiently long that heterogeneity in the isoprene emission rate from the two forests followed by atmospheric oxidation does not explain the concentration heterogeneity of 2-methyltetrols. Standing waves and local meteorology also cannot account for the heterogeneity. Of the possibilities considered, the most plausible explanation is the direct emission from the forest of 2-methyltetrols produced through biological processes within the plants. Under this explanation, the rate of direct SV-OVOC emissions should be modulated by forest type and related environmental stressors. Direct emissions of SV-OVOCs should be more broadly considered for constraining and improving models of atmospheric composition, transport, and chemistry over tropical forests.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

Emissions of Biogenic Volatile Organic Compounds (BVOCs) observed during 2007 from an experimental Pinus taeda plantation in Central North Carolina are compared with model estimates from the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.1. Relaxed eddy accumulation (REA) estimates of 2-methyl-3-buten-2-ol (MBO) fluxes are a factor of 3-4 higher than MEGAN estimates. MEGAN monoterpene emission estimates were a factor of approximately two higher than REA flux measurements. MEGAN β-caryophyllene emission estimates were within 60% of growing season REA flux estimates but were several times higher than REA fluxes during cooler, dormant season periods. The sum of other sesquiterpene emissions estimated by MEGAN was several times higher than REA estimates throughout the year. Model components are examined to understand these discrepancies. Measured summertime leaf area index (LAI) (and therefore foliar biomass) is a factor of two higher than assumed in MEGAN for the P. taeda default. Increasing the canopy mean MBO emission factor from 0.35 to 1.0mgm(-2)h(-1) also reduces MEGAN vs. REA flux differences. This increase is within current MBO emission factor uncertainties. The algorithm within MEGAN which adjusts isoprene emission estimates as a function of the temperature and light of the previous 24h seems also to improve the seasonal MEGAN MBO correlation with REA fluxes. Including the effects of the previous 240h, however, seems to degrade temporal model correlation with fluxes. Monoterpene and sesquiterpene composition data from the REA are compared with MEGAN2.1 estimates and also branch enclosure and needle extract data collected at this site. To our knowledge, the flux data presented here are the first reported for MBO and sesquiterpenes from a P. taeda ecosystem.

Emissions of Biogenic Volatile Organic Compounds (BVOCs) observed during 2007 from an experimental Pinus taeda plantation in Central North Carolina are compared with model estimates from the Model of Emissions of Gases and Aerosols from Nature (MEGAN) version 2.1. Relaxed eddy accumulation (REA) estimates of 2-methyl-3-buten-2-ol (MBO) fluxes are a factor of 3-4 higher than MEGAN estimates. MEGAN monoterpene emission estimates were a factor of approximately two higher than REA flux measurements. MEGAN β-caryophyllene emission estimates were within 60% of growing season REA flux estimates but were several times higher than REA fluxes during cooler, dormant season periods. The sum of other sesquiterpene emissions estimated by MEGAN was several times higher than REA estimates throughout the year. Model components are examined to understand these discrepancies. Measured summertime leaf area index (LAI) (and therefore foliar biomass) is a factor of two higher than assumed in MEGAN for the P. taeda default. Increasing the canopy mean MBO emission factor from 0.35 to 1.0mgm(-2)h(-1) also reduces MEGAN vs. REA flux differences. This increase is within current MBO emission factor uncertainties. The algorithm within MEGAN which adjusts isoprene emission estimates as a function of the temperature and light of the previous 24h seems also to improve the seasonal MEGAN MBO correlation with REA fluxes. Including the effects of the previous 240h, however, seems to degrade temporal model correlation with fluxes. Monoterpene and sesquiterpene composition data from the REA are compared with MEGAN2.1 estimates and also branch enclosure and needle extract data collected at this site. To our knowledge, the flux data presented here are the first reported for MBO and sesquiterpenes from a P. taeda ecosystem.

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.

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.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to the level of isoprene, the level of MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide), was synthesized and tentatively proposed to explain this enhancement. In this study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosol. Major SOA constituents, 2,3-dihydroxyisopentanol and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosol collected from the BEACHON-RoMBAS field campaign during the summer of 2011, where MBO emissions are substantial. Our results support the idea that epoxides are potential products of MBO photooxidation leading to the formation of atmospheric SOA and suggest that reactive uptake of epoxides may explain acid enhancement of SOA observed from other biogenic hydrocarbons.

Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to the level of isoprene, the level of MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide), was synthesized and tentatively proposed to explain this enhancement. In this study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosol. Major SOA constituents, 2,3-dihydroxyisopentanol and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosol collected from the BEACHON-RoMBAS field campaign during the summer of 2011, where MBO emissions are substantial. Our results support the idea that epoxides are potential products of MBO photooxidation leading to the formation of atmospheric SOA and suggest that reactive uptake of epoxides may explain acid enhancement of SOA observed from other biogenic hydrocarbons.

The Estate of Castelporziano (Rome, Italy) hosts many ecosystems representative of Mediterranean vegetation, especially holm oak and pine forests and dune vegetation. In this work, basal emission factors (BEFs) of biogenic volatile organic compounds (BVOCs) obtained by Eddy Covariance in a field campaign using a proton transfer reaction-time-of-flight-mass spectrometer (PTR-TOF-MS) were compared to BEFs reported in previous studies that could not measure fluxes in real-time. Globally, broadleaf forests are dominated by isoprene emissions, but these Mediterranean ecosystems are dominated by strong monoterpene emitters, as shown by the new BEFs. The original and new BEFs were used to parametrize the model of emissions of gases and aerosols from nature (MEGAN v2.1), and model outputs were compared with measured fluxes. Results showed good agreement between modeled and measured fluxes when a model was used to predict radiative transfer and energy balance across the canopy. We then evaluated whether changes in BVOC emissions can affect the chemistry of the atmosphere and climate at a regional level. MEGAN was run together with the land surface model (community land model, CLM v4.0) of the community earth system model (CESM v1.0). Results highlighted that tropospheric ozone concentration and air temperature predicted from the model are sensitive to the magnitude of BVOC emissions, thus demonstrating the importance of adopting the proper BEF values for model parametrization.

The Estate of Castelporziano (Rome, Italy) hosts many ecosystems representative of Mediterranean vegetation, especially holm oak and pine forests and dune vegetation. In this work, basal emission factors (BEFs) of biogenic volatile organic compounds (BVOCs) obtained by Eddy Covariance in a field campaign using a proton transfer reaction-time-of-flight-mass spectrometer (PTR-TOF-MS) were compared to BEFs reported in previous studies that could not measure fluxes in real-time. Globally, broadleaf forests are dominated by isoprene emissions, but these Mediterranean ecosystems are dominated by strong monoterpene emitters, as shown by the new BEFs. The original and new BEFs were used to parametrize the model of emissions of gases and aerosols from nature (MEGAN v2.1), and model outputs were compared with measured fluxes. Results showed good agreement between modeled and measured fluxes when a model was used to predict radiative transfer and energy balance across the canopy. We then evaluated whether changes in BVOC emissions can affect the chemistry of the atmosphere and climate at a regional level. MEGAN was run together with the land surface model (community land model, CLM v4.0) of the community earth system model (CESM v1.0). Results highlighted that tropospheric ozone concentration and air temperature predicted from the model are sensitive to the magnitude of BVOC emissions, thus demonstrating the importance of adopting the proper BEF values for model parametrization.

Biogenic volatile organic compound (BVOC) emissions from six coniferous tree species, i.e. Pinus ponderosa (Ponderosa Pine), Picea pungens (Blue Spruce), Pseudotsuga menziesii (Rocky Mountain Douglas Fir) and Pinus longaeva (Bristlecone Pine), as well as from two deciduous species, Quercus gambelii (Gamble Oak) and Betula occidentalis (Western River Birch) were studied over a full annual growing cycle. Monoterpene (MT) and sesquiterpene (SQT) emissions rates were quantified in a total of 1236 individual branch enclosure samples. MT dominated coniferous emissions, producing greater than 95% of BVOC emissions. MT and SQT demonstrated short-term emission dependence with temperature. Two oxygenated MT, 1,8-cineol and piperitone, were both light and temperature dependent. Basal emission rates (BER, normalized to 1000μmolm(-2)s(-1) and 30°C) were generally higher in spring and summer than in winter; MT seasonal BER from the coniferous trees maximized between 1.5 and 6.0μgg(-1)h(-1), while seasonal lows were near 0.1μgg(-1)h(-1). The fractional contribution of individual MT to total emissions was found to fluctuate with season. SQT BER measured from the coniferous trees ranged from

Biogenic volatile organic compound (BVOC) emissions from six coniferous tree species, i.e. Pinus ponderosa (Ponderosa Pine), Picea pungens (Blue Spruce), Pseudotsuga menziesii (Rocky Mountain Douglas Fir) and Pinus longaeva (Bristlecone Pine), as well as from two deciduous species, Quercus gambelii (Gamble Oak) and Betula occidentalis (Western River Birch) were studied over a full annual growing cycle. Monoterpene (MT) and sesquiterpene (SQT) emissions rates were quantified in a total of 1236 individual branch enclosure samples. MT dominated coniferous emissions, producing greater than 95% of BVOC emissions. MT and SQT demonstrated short-term emission dependence with temperature. Two oxygenated MT, 1,8-cineol and piperitone, were both light and temperature dependent. Basal emission rates (BER, normalized to 1000μmolm(-2)s(-1) and 30°C) were generally higher in spring and summer than in winter; MT seasonal BER from the coniferous trees maximized between 1.5 and 6.0μgg(-1)h(-1), while seasonal lows were near 0.1μgg(-1)h(-1). The fractional contribution of individual MT to total emissions was found to fluctuate with season. SQT BER measured from the coniferous trees ranged from

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

UnlabelledThe impact of climate change on surface-level ozone is examined through a multiscale modeling effort that linked global and regional climate models to drive air quality model simulations. Results are quantified in terms of the relative response factor (RRF(E)), which estimates the relative change in peak ozone concentration for a given change in pollutant emissions (the subscript E is added to RRF to remind the reader that the RRF is due to emission changes only). A matrix of model simulations was conducted to examine the individual and combined effects offuture anthropogenic emissions, biogenic emissions, and climate on the RRF(E). For each member in the matrix of simulations the warmest and coolest summers were modeled for the present-day (1995-2004) and future (2045-2054) decades. A climate adjustment factor (CAF(C) or CAF(CB) when biogenic emissions are allowed to change with the future climate) was defined as the ratio of the average daily maximum 8-hr ozone simulated under a future climate to that simulated under the present-day climate, and a climate-adjusted RRF(EC) was calculated (RRF(EC) = RRF(E) x CAF(C)). In general, RRF(EC) > RRF(E), which suggests additional emission controls will be required to achieve the same reduction in ozone that would have been achieved in the absence of climate change. Changes in biogenic emissions generally have a smaller impact on the RRF(E) than does future climate change itself The direction of the biogenic effect appears closely linked to organic-nitrate chemistry and whether ozone formation is limited by volatile organic compounds (VOC) or oxides of nitrogen (NO(x) = NO + NO2). Regions that are generally NO(x) limited show a decrease in ozone and RRF(EC), while VOC-limited regions show an increase in ozone and RRF(EC). Comparing results to a previous study using different climate assumptions and models showed large variability in the CAF(CB).ImplicationsWe present a methodology for adjusting the RRF to account for the influence of climate change on ozone. The findings of this work suggest that in some geographic regions, climate change has the potential to negate decreases in surface ozone concentrations that would otherwise be achieved through ozone mitigation strategies. In regions of high biogenic VOC emissions relative to anthropogenic NO(x) emissions, the impact of climate change is somewhat reduced, while the opposite is true in regions of high anthropogenic NO(x) emissions relative to biogenic VOC emissions. Further, different future climate realizations are shown to impact ozone in different ways.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

UnlabelledThe impact of climate change on surface-level ozone is examined through a multiscale modeling effort that linked global and regional climate models to drive air quality model simulations. Results are quantified in terms of the relative response factor (RRF(E)), which estimates the relative change in peak ozone concentration for a given change in pollutant emissions (the subscript E is added to RRF to remind the reader that the RRF is due to emission changes only). A matrix of model simulations was conducted to examine the individual and combined effects offuture anthropogenic emissions, biogenic emissions, and climate on the RRF(E). For each member in the matrix of simulations the warmest and coolest summers were modeled for the present-day (1995-2004) and future (2045-2054) decades. A climate adjustment factor (CAF(C) or CAF(CB) when biogenic emissions are allowed to change with the future climate) was defined as the ratio of the average daily maximum 8-hr ozone simulated under a future climate to that simulated under the present-day climate, and a climate-adjusted RRF(EC) was calculated (RRF(EC) = RRF(E) x CAF(C)). In general, RRF(EC) > RRF(E), which suggests additional emission controls will be required to achieve the same reduction in ozone that would have been achieved in the absence of climate change. Changes in biogenic emissions generally have a smaller impact on the RRF(E) than does future climate change itself The direction of the biogenic effect appears closely linked to organic-nitrate chemistry and whether ozone formation is limited by volatile organic compounds (VOC) or oxides of nitrogen (NO(x) = NO + NO2). Regions that are generally NO(x) limited show a decrease in ozone and RRF(EC), while VOC-limited regions show an increase in ozone and RRF(EC). Comparing results to a previous study using different climate assumptions and models showed large variability in the CAF(CB).ImplicationsWe present a methodology for adjusting the RRF to account for the influence of climate change on ozone. The findings of this work suggest that in some geographic regions, climate change has the potential to negate decreases in surface ozone concentrations that would otherwise be achieved through ozone mitigation strategies. In regions of high biogenic VOC emissions relative to anthropogenic NO(x) emissions, the impact of climate change is somewhat reduced, while the opposite is true in regions of high anthropogenic NO(x) emissions relative to biogenic VOC emissions. Further, different future climate realizations are shown to impact ozone in different ways.

Isoprene and monoterpene emissions were characterized using flow and enclosure sampling method and GC-MS in USA for 158 species of plants growing in Shenzhen, China. This survey was designed to include all of the dominant plants within the Shenzhen region as well as unique plants such as Cycads. These are the first measurements in a subtropical Asian metropolis. Substantial isoprene emissions were observed from thirty-one species, including Caryota mitis, Adenanthera pavonina var. microsperma, Mangifera indica and Excoecoria agalloch. Monoterpene emissions were observed from fifty-two species, including Passiflora edulis, Bambusa glaucescens cv. silverstripe as well as some primitive and rare Cycadaceae and Cyatheaceae plants. For the first time some of red plants have been measured, most of them have the ability of releasing terpene. These results will be used to develop biogenic emission model estimates for Shenzhen and the surrounding region that can be used as inputs for regional air quality models.

Isoprene and monoterpene emissions were characterized using flow and enclosure sampling method and GC-MS in USA for 158 species of plants growing in Shenzhen, China. This survey was designed to include all of the dominant plants within the Shenzhen region as well as unique plants such as Cycads. These are the first measurements in a subtropical Asian metropolis. Substantial isoprene emissions were observed from thirty-one species, including Caryota mitis, Adenanthera pavonina var. microsperma, Mangifera indica and Excoecoria agalloch. Monoterpene emissions were observed from fifty-two species, including Passiflora edulis, Bambusa glaucescens cv. silverstripe as well as some primitive and rare Cycadaceae and Cyatheaceae plants. For the first time some of red plants have been measured, most of them have the ability of releasing terpene. These results will be used to develop biogenic emission model estimates for Shenzhen and the surrounding region that can be used as inputs for regional air quality models.

We explore the potential role of atmospheric carbon dioxide (CO₂) on isoprene emissions using a global coupled land-atmosphere model [Community Atmospheric Model-Community Land Model (CAM-CLM)] for recent (year 2000, 365 ppm CO₂) and future (year 2100, 717 ppm CO₂) conditions. We incorporate an empirical model of observed isoprene emissions response to both ambient CO₂ concentrations in the long-term growth environment and short-term changes in intercellular CO₂ concentrations into the MEGAN biogenic emission model embedded within the CLM. Accounting for CO₂ inhibition has little impact on predictions of present-day global isoprene emission (increase from 508 to 523 Tg C yr⁻¹). However, the large increases in future isoprene emissions typically predicted in models, which are due to a projected warmer climate, are entirely offset by including the CO₂ effects. Projected global isoprene emissions in 2100 drop from 696 to 479 Tg C yr⁻¹ when this effect is included, maintaining future isoprene sources at levels similar to present day. The isoprene emission response to CO₂ is dominated by the long-term growth environment effect, with modulations of 10% or less due to the variability in intercellular CO₂ concentration. As a result, perturbations to isoprene emissions associated with changes in ambient CO₂ are largely aseasonal, with little diurnal variability. Future isoprene emissions increase by more than a factor of two in 2100 (to 1242 Tg C yr⁻¹) when projected changes in vegetation distribution and leaf area density are included. Changing land cover and the role of nutrient limitation on CO₂ fertilization therefore remain the largest source of uncertainty in isoprene emission prediction. Although future projections suggest a compensatory balance between the effects of temperature and CO₂ on isoprene emission, the enhancement of isoprene emission due to lower ambient CO₂ concentrations did not compensate for the effect of cooler temperatures over the last 400 thousand years of the geologic record (including the Last Glacial Maximum).

Emissions of volatile organic compounds (VOC) from vegetation are believed to be a major source of secondary organic aerosol (SOA), which in turn comprises a large fraction of fine particulate matter in many areas. Sesquiterpenes are a class of biogenic VOC with high chemical reactivity and SOA yields. Sesquiterpenes have only recently been quantified in emissions from a wide variety of plants. In this study, a new sesquiterpene emission inventory is used to provide input to the Models-3 Community Multiscale Air Quality (CMAQ) model. CMAQ is used to estimate the contribution of sesquiterpenes and monoterpenes to SOA concentrations over the contiguous United States. The gas-particle partitioning module of CMAQ was modified to include condensable products of sesquiterpene oxidation and to update values of the enthalpy of vaporization. The resulting model predicts July monthly average surface concentrations of total SOA in the eastern U.S. ranging from about 0.2-0.8 microg m(-3). This is roughly double the amount of SOA produced in this region when sesquiterpenes are not included. Even with sesquiterpenes included, however, the model significantly underpredicts surface concentrations of particle-phase organic matter compared to observed values. Treating all SOA as capable of undergoing polymerization increases predicted monthly average surface concentrations in July to 0.4-1.2 microg m(-3), in closer agreement with observations. Using the original enthalpy of vaporization value in CMAQ in place of the values estimated from the recent literature results in predicted SOA concentrations of about 0.3-1.3 microg m(-3).

Emissions of volatile organic compounds (VOC) from vegetation are believed to be a major source of secondary organic aerosol (SOA), which in turn comprises a large fraction of fine particulate matter in many areas. Sesquiterpenes are a class of biogenic VOC with high chemical reactivity and SOA yields. Sesquiterpenes have only recently been quantified in emissions from a wide variety of plants. In this study, a new sesquiterpene emission inventory is used to provide input to the Models-3 Community Multiscale Air Quality (CMAQ) model. CMAQ is used to estimate the contribution of sesquiterpenes and monoterpenes to SOA concentrations over the contiguous United States. The gas-particle partitioning module of CMAQ was modified to include condensable products of sesquiterpene oxidation and to update values of the enthalpy of vaporization. The resulting model predicts July monthly average surface concentrations of total SOA in the eastern U.S. ranging from about 0.2-0.8 microg m(-3). This is roughly double the amount of SOA produced in this region when sesquiterpenes are not included. Even with sesquiterpenes included, however, the model significantly underpredicts surface concentrations of particle-phase organic matter compared to observed values. Treating all SOA as capable of undergoing polymerization increases predicted monthly average surface concentrations in July to 0.4-1.2 microg m(-3), in closer agreement with observations. Using the original enthalpy of vaporization value in CMAQ in place of the values estimated from the recent literature results in predicted SOA concentrations of about 0.3-1.3 microg m(-3).

The focus of the studies presented in the preceding companion paper (Part A: Review) and here (Part B: Applications) is on defining representative emission rates from vegetation for determining the roles of biogenic volatile organic compound (BVOC) emissions in atmospheric chemistry and aerosol processes. The review of previously published procedures for identifying and quantifying BVOC emissions has revealed a wide variety of experimental methods used by various researchers. Experimental details become increasingly critical for quantitative emission measurements of low volatility monoterpenes (MT) and sesquiterpenes (SQT). These compounds are prone to be lost inadvertently by uptake to materials in contact with the sample air or by reactions with atmospheric oxidants. These losses become more prominent with higher molecular weight compounds, potentially leading to an underestimation of their emission rates. We present MT and SQT emission rate data from numerous experiments that include 23 deciduous tree species, 14 coniferous tree species, 8 crops, and 2 shrubs. These data indicate total, normalized (30 degrees C) basal emission rates from

The focus of the studies presented in the preceding companion paper (Part A: Review) and here (Part B: Applications) is on defining representative emission rates from vegetation for determining the roles of biogenic volatile organic compound (BVOC) emissions in atmospheric chemistry and aerosol processes. The review of previously published procedures for identifying and quantifying BVOC emissions has revealed a wide variety of experimental methods used by various researchers. Experimental details become increasingly critical for quantitative emission measurements of low volatility monoterpenes (MT) and sesquiterpenes (SQT). These compounds are prone to be lost inadvertently by uptake to materials in contact with the sample air or by reactions with atmospheric oxidants. These losses become more prominent with higher molecular weight compounds, potentially leading to an underestimation of their emission rates. We present MT and SQT emission rate data from numerous experiments that include 23 deciduous tree species, 14 coniferous tree species, 8 crops, and 2 shrubs. These data indicate total, normalized (30 degrees C) basal emission rates from

The quantification of atmospheric additions of nitrogen (N) to an ecosystem is often desirable, but difficult for many locations including many ecological manipulation experiments. Ideal methodologies for the complete and chemically speciated quantification of dry N deposition (e.g. tunable diode laser absorption spectrometer, thermal-dissociation laser-induced fluorescence) are expensive, technologically challenging to maintain, and rarely colocated with important global change manipulation experiments. Here we present an alternative method for obtaining an approximation of total N deposition using short-term eddy flux and concentration measurements, annual regional concentration estimates, and modeling for the Duke Experimental Forest. The motivation for generating estimates for this location was to inform the long-term elevated CO₂ experiment conducted at Duke Forest. We estimated the total annual atmospheric N deposition to the forest to be 13.7 kg N ha⁻¹. Of this total, ~58% was in dry-deposited forms. Surprisingly, and contrary to some previous predictions, nitric acid (HNO₃) was not the dominant portion of the total dry-deposited N, implying strongly that other forms of gaseous N like organic peroxy and alkyl nitrate compounds are a significant portion of the total flux. Furthermore, this study sheds light on the completeness of the estimates derived from Clean Air Status and Trends Network (CASTNet) and other dry deposition networks. CASTNet does not measure organic forms of dry deposition. In fact, CASTNet only quantifies HNO₃ in the gas phase and may significantly underestimate total N deposition in many environments.

Most work on methane (CH(4)) emissions from natural ecosystems has focused on wetlands because they are hotspots of CH(4) production. Less attention has been directed toward upland ecosystems that cover far larger areas, but are assumed to be too dry to emit CH(4). Here we review CH(4) production and emissions in upland ecosystems, with attention to the influence of plant physiology on these processes in forests. Upland ecosystems are normally net sinks for atmospheric CH(4) because rates of CH(4) consumption exceed CH(4) production. Production of CH(4) in upland soils occurs in microsites and may be common in upland forest soils. Some forests switch from being CH(4) sinks to CH(4) sources depending on soil water content. Plant physiology influences CH(4) cycling by modifying the availability of electron donors and acceptors in forest soils. Plants are the ultimate source of organic carbon (electron donor) that microbes process into CH(4). The availability of O(2) (electron acceptor) is sensitive to changes in soil water content, and therefore, to transpiration rates. Recently, abiotic production of CH(4) from aerobic plant tissue was proposed, but has not yet been verified with independent data. If confirmed, this new source is likely to be a minor term in the global CH(4) budget, but important to quantify for purposes of greenhouse gas accounting. A variety of observations suggest that our understanding of CH(4) sources in upland systems is incomplete, particularly in tropical forests which are stronger sources then expected.

Biogenic volatile organic compounds (BVOC) contribute significantly to the formation of ozone and secondary organic aerosol (SOA). The Model of Emissions of Gases and Aerosols from Nature (MEGANv2.02) is used to estimate emissions of isoprene, monoterpenes (MT), and sesquiterpenes (SQT) across the United States. Compared to the Biogenic Emission Inventory System (BEIS3.0), MEGANv2.02 estimates higher isoprene but lower MT emissions for July 2001 and January 2002. A sensitivity study of SQT and MT emission factors and algorithm parameters was conducted by assigning values to four plant functional types (PFTs) using both recent measurements and literature values. The standard deviations of the emissions factors within these PFTs were two to four times the averages because of the variation in experimental basal emissions rate data. More recently published SQT and MT basal emission rates are generally lower than those reported in the literature through 2004. With the new emissions factors, monthly average SQT emission rates for the contiguous United States are equal to 16% of the MT emissions during July and 9% of the emissions during January. The SQT emissions distribution is strongly influenced by the grass and crop PFT, for which SQT emissions data are quite limited.

Biogenic volatile organic compounds (BVOC) contribute significantly to the formation of ozone and secondary organic aerosol (SOA). The Model of Emissions of Gases and Aerosols from Nature (MEGANv2.02) is used to estimate emissions of isoprene, monoterpenes (MT), and sesquiterpenes (SQT) across the United States. Compared to the Biogenic Emission Inventory System (BEIS3.0), MEGANv2.02 estimates higher isoprene but lower MT emissions for July 2001 and January 2002. A sensitivity study of SQT and MT emission factors and algorithm parameters was conducted by assigning values to four plant functional types (PFTs) using both recent measurements and literature values. The standard deviations of the emissions factors within these PFTs were two to four times the averages because of the variation in experimental basal emissions rate data. More recently published SQT and MT basal emission rates are generally lower than those reported in the literature through 2004. With the new emissions factors, monthly average SQT emission rates for the contiguous United States are equal to 16% of the MT emissions during July and 9% of the emissions during January. The SQT emissions distribution is strongly influenced by the grass and crop PFT, for which SQT emissions data are quite limited.

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

In this study, a regional dynamical model (WRF) is used to drive biogenic emission models to calculate high resolution (10x10 km) biogenic emissions of isoprene (C(5)H(8)), monoterpenes (C(10)H(16)), and nitric oxide (NO) in China. This high resolution biogenic inventory will be available for the community to study the effect of biogenic emissions on photochemical oxidants in China. The biogenic emissions are compared to anthropogenic emissions to gain insight on the potential impact of the biogenic emissions on tropospheric chemistry, especially ozone production in this region. The results show that the biogenic emissions in China exhibit strongly diurnal, seasonal, and spatial variations. The isoprenoid (including both isoprene and monoterpenes) emissions are closely correlated to tree density and strongly vary with season and local time. During winter (January), the biogenic isoprenoid emissions are the lowest, resulting from lower temperature and solar radiation, and highest in summer (July) due to higher temperature and solar radiation. The biogenic NO emissions are also higher during summer and lower during winter, but the magnitude of the seasonal variation is smaller than the emissions of isoprene and monoterpenes. The biogenic emissions of NO are widely spread out in the northern, eastern, and southern China regions, where high-density agricultural soil lands are located. Both biogenic NO and isoprenoid emissions are very small in western China. The calculated total biogenic emission budget is smaller than the total anthropogenic VOC emission budget in China. The biogenic isoprenoid and anthropogenic VOC emissions are 10.9 and 15.1 Tg year(-1), respectively. The total biogenic and anthropogenic emissions of NO are 5.9 and 11.5 Tg(NO) year(-1), respectively. The study shows that in central eastern China, the estimated biogenic emissions of isoprenoids are very small, and the anthropogenic emissions of VOCs are dominant in this region. However, in northeastern and southern China, there are relatively large biogenic emissions of isoprenoids, leading to an important impact on the ozone production in these regions. Furthermore, the emissions of isoprenoids are highest during summer and noontime, which correlates to the peak of ozone production period. For example, the ratio between summer and winter for the emissions of isoprenoids is about 15 in China. As a result, the biogenic emissions of isoprenoids are significantly larger than the anthropogenic emissions of VOCs in China during daytime in summer. Biogenic NO emissions are mostly produced by agricultural soils which co-exist with large populations and human activity. As a result, the biogenic emissions of NO are mostly overlapped with the anthropogenic emissions of NO, leading to the enhancement in NO concentrations in the high anthropogenic NO emission regions. Finally, the future emissions of isoprene and monoterpenes over China are estimated. The results show that the future biogenic emissions may increase significantly due to land cover changes in central eastern China, which could have a very important impact on ozone formation in this region. However, these estimates are highly uncertain and are presented as a potential scenario to show the importance of possible changes of biogenic emissions in China.

In this study, a regional dynamical model (WRF) is used to drive biogenic emission models to calculate high resolution (10x10 km) biogenic emissions of isoprene (C(5)H(8)), monoterpenes (C(10)H(16)), and nitric oxide (NO) in China. This high resolution biogenic inventory will be available for the community to study the effect of biogenic emissions on photochemical oxidants in China. The biogenic emissions are compared to anthropogenic emissions to gain insight on the potential impact of the biogenic emissions on tropospheric chemistry, especially ozone production in this region. The results show that the biogenic emissions in China exhibit strongly diurnal, seasonal, and spatial variations. The isoprenoid (including both isoprene and monoterpenes) emissions are closely correlated to tree density and strongly vary with season and local time. During winter (January), the biogenic isoprenoid emissions are the lowest, resulting from lower temperature and solar radiation, and highest in summer (July) due to higher temperature and solar radiation. The biogenic NO emissions are also higher during summer and lower during winter, but the magnitude of the seasonal variation is smaller than the emissions of isoprene and monoterpenes. The biogenic emissions of NO are widely spread out in the northern, eastern, and southern China regions, where high-density agricultural soil lands are located. Both biogenic NO and isoprenoid emissions are very small in western China. The calculated total biogenic emission budget is smaller than the total anthropogenic VOC emission budget in China. The biogenic isoprenoid and anthropogenic VOC emissions are 10.9 and 15.1 Tg year(-1), respectively. The total biogenic and anthropogenic emissions of NO are 5.9 and 11.5 Tg(NO) year(-1), respectively. The study shows that in central eastern China, the estimated biogenic emissions of isoprenoids are very small, and the anthropogenic emissions of VOCs are dominant in this region. However, in northeastern and southern China, there are relatively large biogenic emissions of isoprenoids, leading to an important impact on the ozone production in these regions. Furthermore, the emissions of isoprenoids are highest during summer and noontime, which correlates to the peak of ozone production period. For example, the ratio between summer and winter for the emissions of isoprenoids is about 15 in China. As a result, the biogenic emissions of isoprenoids are significantly larger than the anthropogenic emissions of VOCs in China during daytime in summer. Biogenic NO emissions are mostly produced by agricultural soils which co-exist with large populations and human activity. As a result, the biogenic emissions of NO are mostly overlapped with the anthropogenic emissions of NO, leading to the enhancement in NO concentrations in the high anthropogenic NO emission regions. Finally, the future emissions of isoprene and monoterpenes over China are estimated. The results show that the future biogenic emissions may increase significantly due to land cover changes in central eastern China, which could have a very important impact on ozone formation in this region. However, these estimates are highly uncertain and are presented as a potential scenario to show the importance of possible changes of biogenic emissions in China.

Gaseous and particulate semi volatile carbonyls have been measured in urban air using an annular denuder sampling system. Three dicarbonyls, five aliphatic aldehydes and two hydroxy carbonyls were observed. Concentrations of other biogenic and anthropogenic volatile organic compounds (VOCs), SO2, CO, NO2 and particle concentration were also measured. Estimated gasaerosol equilibrium constants for the carbonyls showed an inverse correlation with the concentrations of anthropogenic pollutants such as benzene, isopentane and SO2. This suggests that the increase in the fraction of non-polar anthropogenic particles in the atmosphere could change the average property of the ambient aerosols and drive the gas particle equilibrium of the carbonyls to the gas phase. This trend is uncommon in remote forest air. In this study, we examined the factors controlling the equilibrium in the polluted atmosphere and show that there is a difference in gas-aerosol partition between polluted and clean air. Copyright 2005 by the American Geophysical Union.

Vertical profiles of the concentration of several alkyl halides, as well as isoprene, were made from the surface to 200 m, using a tethered balloon platform, near Mace Head, Ireland in September-October 2003. Profiles indicate a surface source of several alkyl halides. Alkyl halides have been proposed as a source of new particles in the atmosphere. Estimates of emission rates (μg m-2 h-1) were made using a flux-gradient technique for CH2Br2 (0.8), CHBr3 (6), CH2IBr (0.1), CH2I2 (0.1), and isoprene (24). © CSIRO 2005.

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.

A tethered balloon-sampling platform was used to study biogenic volatile organic compounds (BVOCs) in the atmospheric boundary layer in three distinct moist tropical forest ecoregions, as well as an extensive pasture area, in Amazonia. Approximately 2440 soundings, including as many as four VOC samples collected simultaneously at various altitudes, were made at each site. Concentrations in the mixed layer increased during morning hours and were relatively constant midday through afternoon. Since most important meteorological and chemical parameters were very similar among the sites during the measurement periods, a BVOC canopy emission model was used with a model of the chemistry of the boundary layer to reproduce the atmospheric concentrations observed. The simulations indicated significantly different midday landscape isoprene and α-pinene emission rates for the three forest ecoregions (2200, 5300, 9800 μg m-2h-1 isoprene and 90, 120, and 180 μg m-2 h-1 x-pinene for the three moist forest ecoregions studied, respectively). The differences in emissions among the ecoregions may be attributed to the species composition, which were markedly different and in which the percentage of isoprene and terpene emitting species also differed significantly. © 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.

About 2.4 Pg (1 Pg = 10(15) g) of carbon is emitted annually into the atmosphere as reactive compounds and most of it is eventually oxidized to CO2. Isoprene, alpha-pinene, methanol, carbon monoxide and other compounds emitted by terrestrial vegetation contribute about half of the total flux and are estimated to produce about 1 Pg C as CO2 per year. The global average for vegetated surfaces is about 7 g C m(-2) per year but could exceed 100 g m(-2) per year at some tropical locations. The magnitude of these fluxes on both the landscape and global scales are small relative to the total carbon emission or deposition but are significant relative to the net fluxes. Reactive carbon fluxes are very sensitive to landcover and climate change and may vary significantly due to future perturbations. This paper summarizes what is known about reactive carbon emissions from vegetation including the magnitude of local, landscape, and global scale fluxes and their contribution to atmospheric CO2. Reasons for including this term in carbon flux models are presented as well as the potential importance on various spatial scales. Past, present and future reactive carbon emissions are expected to differ significantly and the implications of this are discussed.

About 2.4 Pg (1 Pg = 10(15) g) of carbon is emitted annually into the atmosphere as reactive compounds and most of it is eventually oxidized to CO2. Isoprene, alpha-pinene, methanol, carbon monoxide and other compounds emitted by terrestrial vegetation contribute about half of the total flux and are estimated to produce about 1 Pg C as CO2 per year. The global average for vegetated surfaces is about 7 g C m(-2) per year but could exceed 100 g m(-2) per year at some tropical locations. The magnitude of these fluxes on both the landscape and global scales are small relative to the total carbon emission or deposition but are significant relative to the net fluxes. Reactive carbon fluxes are very sensitive to landcover and climate change and may vary significantly due to future perturbations. This paper summarizes what is known about reactive carbon emissions from vegetation including the magnitude of local, landscape, and global scale fluxes and their contribution to atmospheric CO2. Reasons for including this term in carbon flux models are presented as well as the potential importance on various spatial scales. Past, present and future reactive carbon emissions are expected to differ significantly and the implications of this are discussed.

Canopy level flux measurements of 2-methyl-3-buten-2-ol (MBO), acetone, and methanol were made over a subalpine forest in the Rocky Mountains in Colorado in the summer of 1999. The measurements were carried out using a portable relaxed eddy accumulation system that collected samples on adsorbent cartridges. Midday fluxes of acetone were highest at approximately 2.5 mg of C m-2 h-1. Methanol and MBO fluxes were approximately 1.0 mg of C m-2 h-1 each. These fluxes occurred with average daytime high temperatures of only 18 degrees C. Diurnal fluxes of MBO were strongly correlated with light and temperature. Acetone and methanol did not have simple diurnal patterns. These results indicate that oxygenated volatile organic compounds may make a significant contribution to the flux of reactive carbon to the atmosphere in western U.S. pine forests.

The flux of volatile organic chemicals from natural vegetation influences various atmospheric properties including oxidation state of the troposphere via the hydroxyl radical (OH), photochemical haze production and the concentration of greenhouse gases (CH4, H2O, CO). Because the Volatile Organic Compound (VOC) flux in the present-day world varies markedly with both vegetation cover and with climate, changes in the emission of VOCs may have damped or amplified past climate changes. Here we conduct a preliminary study on possible changes in VOC emission resulting from broad scale vegetation and climate change since the Last Glacial Maximum (LGM). During the general period of the LGM (~25-17,000 years before present {BP}), global forest cover was considerably less than in the present potential situation. The change in vegetation would have resulted in a ~30% reduction in VOC emission at 643 Tg y-1 relative to the present potential vegetation (912.9 Tg y-1). Uncertainty in global vegetation cover during the LGM bounds the VOC estimate by ±15%. In contrast, during the warmer early-to-mid Holocene (8000 and 5000 BP), with greater forest extent and less desert than during the late Holocene (0 BP), emission rates of VOCs seem likely to have been higher than at present. Further modifications in VOC emission may have been mediated by a reduction in mean tropical lowland temperatures (by around 5-6°C) decreasing the LGM VOC emission estimate by 38% relative to the warmer LGM scenario. Increased VOC emissions due to forest expansion and increased tropical temperatures since the LGM may have served as a significant driver of climate change over the last 15 ka y through the influence of VOC oxidation; this can impact tropospheric radiative balance through reductions in the concentration of OH, increasing the concentration of CH4. The error limits on past VOC emission estimates are large, given the uncertainties of present-day VOC emission rates, paleoecosystem distribution, tropical paleoclimatic conditions, and physiological assumptions regarding controls over VOC emission. Nevertheless, the potential significance of changes in natural VOC emission over the last 20 ka and their influence on climate are an important unknown that should at least be borne in mind as a limit on the understanding of past atmospheric conditions. Elucidation of the role of VOCs in climate change through paleoclimatic general circulation model simulations may improve understanding of past and future changes in climate. (C) 2000 Elsevier Science Ltd.

The alteration of climate is driven not only by anthropogenic activities, but also by biosphere processes that change in conjunction with climate. Emission of volatile organic compounds (VOCs) from vegetation may be particularly sensitive to changes in climate and may play an important role in climate forcing through their influence on the atmospheric oxidative balance, greenhouse gas concentration, and the formation of aerosols. Using the VEMAP vegetation database and associated vegetation responses to climate change, this study examined the independent and combined effects of simulated changes in temperature, CO2 concentration, and vegetation distribution on annual emissions of isoprene, monoterpenes, and other reactive VOCs (ORVOCs) from potential vegetation of the continental United States. Temperature effects were modelled according to the direct influence of temperature on enzymatic isoprene production and the vapour pressure of monoterpenes and ORVOCs. The effect of elevated CO2 concentration was modelled according to increases in foliar biomass per unit of emitting surface area. The effects of vegetation distribution reflects simulated changes in species spatial distribution and areal coverage by 21 different vegetation classes. Simulated climate warming associated with a doubled atmospheric CO2 concentration enhanced total modelled VOC emission by 81.8% (isoprene +82.1%, monoterpenes +81.6%, ORVOC +81.1%), whereas a simulated doubled CO2 alone enhanced total modelled VOC emission by only +11.8% (isoprene +13.7%, monoterpenes +4.1%, ORVOC +11.7%). A simulated redistribution of vegetation in response to altered temperatures and precipitation patterns caused total modelled VOC emission to decline by 10.4% (isoprene -11.7%, monoterpenes -18.6%, ORVOC 0.0%) driven by a decline in area covered by vegetation classes emitting VOCs at high rates. Thus, the positive effect of leaf-level adjustments to elevated CO2 (i.e. increases in foliar biomass) is balanced by the negative effect of ecosystem-level adjustments to climate (i.e. decreases in areal coverage of species emitting VOC at high rates).

Landscape flux potentials for biogenic volatile organic compounds (BVOCs) were derived for three ecosystems in the continental U.S. (Fernbank Forest, Atlanta, GA; Willow Creek, Rhinelander, WI; Temple Ridge, CO). Analytical data from branch enclosure measurements were combined with ecological survey data for plant species composition and biomass. Other quantitative flux measurements at the leaf and landscape level were incorporated to scale the results from the enclosure measurements to the landscape level. Flux estimates were derived by using a one week ambient temperature and light record (30 min time resolution) and adjusting all emission rates to these conditions with temperature and light correction algorithms.

Vegetation composition and biomass were surveyed for three specific sites in Atlanta, GA; near Rhinelander, WI; and near Hayden, CO. At each research site emissions of biogenic volatile organic compounds (BVOCs) from the dominant vegetation species were sampled by enclosing branches in bag enclosure systems and sampling the equilibrium head space onto multi-stage solid adsorbent cartridges. Analysis was performed using a thermal desorption technique with gas chromatography (GC) separation and mass spectrometry (MS) detection. Identification of BVOCs covering the GC retention index range (stationary phase DB-1) from approximately 400 to 1400 was achieved (volatilities C4-C14).

Atmospheric concentrations of ozone and other air pollutants, in some regions, are sensitive to surface fluxes of volatile organic compounds (VOCs). Plant foliage is the source of at least half of all VOC emissions in the United States and more than two-thirds of global VOC emissions. Observed spatial and seasonal variations in foliar VOC emissions range over several orders of magnitude. Land characteristics data are an important component of the modeling techniques used to estimate VOC emission rate variations due to seasonal and spatial changes in species composition, foliar density, and other factors. Model techniques and land characteristics databases are compared and evaluated in this paper. Significant differences in VOC fluxes are predicted depending on spatial resolution, procedures used to develop land characteristics databases, and foliar density models. Satellite and ground observations can be combined to generate the accurate estimates of the species composition and foliar density required for natural VOC emission models.

Biogenic nonmethane hydrocarbon (NMHC) emissions were investigated at two field sites in the Republic of South Africa that include five important southern African savanna landscapes. Tropical savannas are a globally important biome with a high potential for biogenic emissions but no NMHC emission measurements in these regions or in any part of Africa have been reported. Landscape average hydrocarbon emissions were estimated by characterizing plant species composition and foliar density at each site, identifying and characterizing NMHC emissions of the most abundant plant species, and identifying and characterizing NMHC emissions of plant species with the highest NMHC emission rates. A hand‐held portable analyzer proved to be a useful tool for identifying plants with high emission rates. A branch enclosure system, with gas chromatography and flame ionization detector, was used to quantify isoprene and monoterpene emission rates. Emission rates were species‐specific and several genera had both high and low emitters. At least some species with high emission rates were identified in most savanna types. High and low emitters were found on both nutrient‐rich and nutrient‐poor soils. Landscape average emission capacities for the five savanna types range from 0.6 to 9 mg C m−2 h−1 for isoprene and about 0.05 to 3 mg C m−2 h−1 for monoterpenes. The savanna emission rates predicted by existing global models are within the range estimated for these five savanna types.

A new, integrated methodology to locate and measure methane emissions from natural gas systems has been developed. Atmospheric methane sources are identified by elevated ambient CH4 concentrations measured with a mobile laser-based methane analyzer. The total methane emission rate from a source is obtained by simulating the source with a sulfur hexafluoride (SF6) tracer gas release and by measuring methane and tracer concentrations along downwind sampling paths using mobile, real-time analyzers. Combustion sources of methane are distinguished from noncombustion sources by concurrent ambient carbon dioxide measurements. Three variations on the tracer ratio method are described for application to (1) small underground vaults, (2) aboveground natural gas facilities, and (3) diffuse methane emissions from an entire town. Results from controlled releases and from replicate tests demonstrate that the tracer ratio approach can yield total emission rates to within approximately ±15%. The estimated accuracy of emission estimates for urban areas with a variety of diffuse emissions is ±50%. © 1995, American Chemical Society. All rights reserved.

Natural biogenic non-methane hydrocarbon (NMHC) emissions significantly influence the concentrations of free hydroxyl and peroxy radicals, carbon monoxide and tropospheric ozone. Present concerns with air pollution and the global carbon balance call for a better understanding of the respective roles of climate dynamics and vegetation succession in determining NMHC emissions. This constitutes the focus of the present paper. The approach consists in coupling the Energy, Water and Momentum Exchange and Ecological Dynamics model, a climatically sensitive, physically based gas phase forest dynamics model, and NMHC trace gas emission algorithms to assess possible changes in NMHC emissions from forests under stationary and changing climatic conditions. In summary, it is possible to follow the temporal evolution of foliar emissions over centuries using a vegetation dynamics model coupled with an NMHC emissions module. -from Authors