Isoprene Fluxes Research Articles

Flux estimates of isoprene, methanol and acetone from airborne PTR-MS measurements over the tropical rainforest during the GABRIEL 2005 campaign

Abstract. Tropical forests are a strong source of biogenic volatile organic compounds (BVOCs) to the atmosphere which can potentially impact the atmospheric oxidation capacity. Here we present airborne and ground-based BVOC measurements representative for the long dry season covering a large area of the northern Amazonian rainforest (6–3° N, 50–59° W). The measurements were conducted during the October 2005 GABRIEL (Guyanas Atmosphere-Biosphere exchange and Radicals Intensive Experiment with the Learjet) campaign. The vertical (35 m to 10 km) and diurnal (09:00–16:00) profiles of isoprene, its oxidation products methacrolein and methyl vinyl ketone and methanol and acetone, measured by PTR-MS (Proton Transfer Reaction Mass Spectrometry), have been used to empirically estimate their emission fluxes from the forest canopy on a regional scale. The mixed layer isoprene emission flux, inferred from the airborne measurements above 300 m, is 5.7 mg isoprene m−2 h−1 after compensating for chemistry and ~6.9 mg isoprene m−2 h−1 taking detrainment into account. This surface flux is in general agreement with previous tropical forest studies. Inferred methanol and acetone emission fluxes are 0.5 mg methanol m−2 h−1 and 0.35 mg acetone m−2 h−1, respectively. The BVOC measurements were compared with fluxes and mixing ratios simulated with a single-column chemistry and climate model (SCM). The inferred isoprene flux is substantially smaller than that simulated with an implementation of a commonly applied BVOC emission algorithm in the SCM.

Estimating Taiwan biogenic VOC emission: Leaf energy balance consideration

The goal of the present study is to provide a comprehensive model to estimate biogenic volatile organic compounds (BVOCs) in Taiwan. In addition to metrological data, the model consists of (1) 83 land-use patterns, (2) emission factors for various vegetations, (3) energy balance equation to account for leaf temperature, and (4) correction terms for photosynthetically active radiation. The model output includes 4 categories of 33 BVOCs [isoprene, methylbutenol (MBO), 14 species of monoterpenes and 17 other BVOCs]. The results of model verification based on several approaches include: (1) predicted isoprene emission flux correlates relatively good with the observed isoprene concentration ( R 2 = 0.66); (2) correlation between leaf temperature and observed isoprene levels is better than that between ambient temperature and isoprene concentrations ( R 2 = 0.63 vs. 0.58); (3) model-predicted isoprene fluxes match well with observed 3-day diurnal isoprene concentration variations; and (4) subsequent model-predicted O 3 concentrations with the BVOC input obtained in the present study match well than that with previous estimated BVOC data with the observed 6-day diurnal O 3 levels in 8 air quality monitoring stations. Based on the meteorological data in 2000, the total emission of BVOCs in Taiwan was simulated to be about 433,000 ton (33% of total VOCs) of which both isoprene and 14 species of monoterpenes account for about 34%, with 17 species of other BVOCs being 31% and <2% contribution from MBO. Total emissions of BVOCs are higher in lower and medium altitude (300–1000 m) mountain areas with an average of around 15–30 ton km −2 y −1. The implication of the other results is also discussed.

On inferring isoprene emission surface flux from atmospheric boundary layer concentration measurements

Abstract. We examine the dependence of the inferred isoprene surface emission flux from atmospheric concentration on the diurnal variability of the convective boundary layer (CBL). A series of systematic numerical experiments carried out using the mixed-layer technique enabled us to study the sensitivity of isoprene fluxes to the entrainment process, the partition of surface fluxes, the horizontal advection of warm/cold air masses and subsidence. Our findings demonstrate the key role played by the evolution of boundary layer height in modulating the retrieved isoprene flux. More specifically, inaccurate values of the potential temperature lapse rate lead to changes in the dilution capacity of the CBL and as a result the isoprene flux may be overestimated or underestimated by as much as 20%. The inferred emission flux estimated in the early morning hours is highly dependent on the accurate estimation of the discontinuity of the thermodynamic values between the residual layer and the rapidly forming CBL. Uncertainties associated with the partition of the sensible and latent heat flux also yield large deviations in the calculation of the isoprene surface flux. Similar results are obtained if we neglect the influence of warm or cold advection in the development of the CBL. We show that all the above-mentioned processes are non-linear, for which reason the dynamic and chemical evolutions of the CBL must be solved simultaneously. Based on the discussion of our results, we suggest the measurements needed to correctly apply the mixed-layer technique in order to minimize the uncertainties associated with the diurnal variability of the convective boundary layer.

Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS)

Abstract. The ability to measure sesquiterpenes (SQT; C15H24) by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) was investigated. SQT calibration standards were prepared by a capillary diffusion method and the PTR-MS-estimated mixing ratios were derived from the counts of product ions and proton transfer reaction constants. These values were compared with mixing ratios determined by a calibrated Gas Chromatograph (GC) coupled to a Flame Ionization Detector (GC-FID). Product ion distributions from soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+), out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+), are accounted for. Considerable fragmentation of bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, cause the accuracy to be reduced to 50% if only the parent ion (m/z 205+) is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport) research station in 2005. Inferred average daytime ecosystem scale mixing ratios (fluxes) of isoprene, sum of monoterpenes (MT), and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1), 1.2 μg m−3 (0.21 mg m−2 h−1), and 0.0016 μg m−3 (0.10 mg m−2 h−1), respectively. A range of MT and SQT reactivities with respect to the OH radical was calculated and compared to an earlier study inferring significantly underestimated OH reactivities due to unknown terpenes above this deciduous forest. The results indicate that incorporating these MT and SQT results can resolve ~30% of missing OH reactivity reported for this site.

The use of disjunct eddy sampling methods for the determination of ecosystem level fluxes of trace gases

Abstract. The concept of disjunct eddy sampling (DES) for use in measuring ecosystem-level micrometeorological fluxes is re-examined. The governing equations are discussed as well as other practical considerations and guidelines concerning this sampling method as it is applied to either the disjunct eddy covariance (DEC) or disjunct eddy accumulation (DEA) techniques. A disjunct eddy sampling system was constructed that could either be combined with relatively slow sensors (response time of 2 to 40 s) to measure fluxes using DEC, or could also be used to accumulate samples in stable reservoirs for later laboratory analysis (DEA technique). Both the DEC and DEA modes of this sampler were tested against conventional eddy covariance (EC) for fluxes of either CO2 (DEC) or isoprene (DEA). Good agreement in both modes was observed relative to the EC systems. However, the uncertainty in a single DEA flux measurement was considerable (~40%) due to both the reduced statistical sampling and the analytical precision of the concentration difference measurements. We have also re-investigated the effects of nonzero mean vertical wind velocity on accumulation techniques as it relates to our DEA measurements. Despite the higher uncertainty, disjunct eddy sampling can provide an alternative technique to eddy covariance for determining ecosystem-level fluxes for species where fast sensors do not currently exist.

Improved simulation of isoprene oxidation chemistry with the ECHAM5/MESSy chemistry-climate model: lessons from the GABRIEL airborne field campaign

Abstract. The GABRIEL airborne field measurement campaign, conducted over the Guyanas in October 2005, produced measurements of hydroxyl radical (OH) concentration which are significantly higher than can be simulated using current generation models of atmospheric chemistry. Based on the hypothesis that this "missing OH" is due to an as-yet undiscovered mechanism for recycling OH during the oxidation chain of isoprene, we determine that an OH recycling of about 40–50% (compared with 5–10% in current generation isoprene oxidation mechanisms) is necessary in order for our modelled OH to approach the lower error bounds of the OH observed during GABRIEL. Such a large amount of OH in our model leads to unrealistically low mixing ratios of isoprene. In order for our modelled isoprene mixing ratios to match those observed during the campaign, we also require that the effective rate constant for the reaction of isoprene with OH be reduced by about 50% compared with the lower bound of the range recommended by IUPAC. We show that a reasonable explanation for this lower effective rate constant could be the segregation of isoprene and OH in the mixed layer. Our modelling results are consistent with a global, annual isoprene source of about 500 Tg(C) yr−1, allowing experimentally derived and established isoprene flux rates to be reconciled with global models.

Effects of large-scale Amazon forest degradation on climate and air quality through fluxes of carbon dioxide, water, energy, mineral dust and isoprene

Loss of large areas of Amazonian forest, through either direct human impact or climate change, could exert a number of influences on the regional and global climates. In the Met Office Hadley Centre coupled climate–carbon cycle model, a severe drying of this region initiates forest loss that exerts a number of feedbacks on global and regional climates, which magnify the drying and the forest degradation. This paper provides an overview of the multiple feedback process in the Hadley Centre model and discusses the implications of the results for the case of direct human-induced deforestation. It also examines additional potential effects of forest loss through changes in the emissions of mineral dust and biogenic volatile organic compounds. The implications of ecosystem–climate feedbacks for climate change mitigation and adaptation policies are also discussed.

Flux estimates and OH reaction potential of reactive biogenic volatile organic compounds (BVOCs) from a mixed northern hardwood forest

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

Biogenic Hydrocarbon Chemistry within and Above a Mixed Deciduous Forest

This manuscript includes findings from field and numerical modeling inves- tigations designed to quantify the degree and rates of biogenic hydrocarbon chemical processing within and above a mixed deciduous forest in the southeastern United States. The study site was under the influences of nitrogen oxide and hydrocarbon emissions from suburban automobile traffic. The most common ambient biogenic hydrocarbons measured within and above the forest included isoprene, α-pinene, and d-limonene. Isoprene was the most abundantly produced biogenic hydrocarbon, with maximum isoprene flux densities reaching 50 nmol m �2 s �1 . Isoprene and its reaction products (methyl vinyl ketone and methacrolein) comprised over 75% of the measured hydrocarbon mass. Substantial nitrate (NO3) and hydroxyl (HO) radical formation occurred within the forest canopy, with maximum NO3 and HO levels approaching 1 part per trillion on a volume basis (pptv) and

The influence of iron fertilization on the fluxes of methyl halides and isoprene from ocean to atmosphere in the SERIES experiment

Abstract As a part of an iron-fertilization experiment in the NE Pacific in July 2002 measurements were made of isoprene and methyl halides both within the fertilized patch and outside. Isoprene showed the response that would be expected of a gas having a source in phytoplankton: its concentration within the patch increased relative to outside, and after 10–14 days its calculated net production rate was about 6-fold higher within the patch. In contrast, the methyl halides showed no clear effect of fertilization, though the production rates of methyl iodide were appreciable. Hence there is no evidence that any of the algal groups present, such as diatoms that were stimulated by the fertilization played a significant role in the net production of methyl halides. The results are not inconsistent with a photochemical source of the gases, though light levels were attenuated by persistent cloud cover.

The biogenic volatile organic compounds emission inventory in France

An inventory describing the fluxes of volatile organic compounds (VOCs), isoprene and monoterpenes, and other VOCs (OVOCs) from the biosphere to the atmosphere, has been constructed within the framework of the ESCOMPTE project (fiEld experimentS to COnstrain Models of atmospheric Pollution and Transport of Emissions). The area concerned, located around Berre-Marseilles, is a Mediterranean region frequently subject to high ozone concentrations. The inventory has been developed using a fine scale land use database for the year 1999, forest composition statistics, emission potentials from individual plant species, biomass distribution, temperature and light intensity. The seasonal variations in emission potentials and biomass were also taken into account. Hourly meteorological data for 1999 were calculated from ALADIN data and these were used to predict the hourly isoprene, monoterpene and OVOC fluxes for the area on a 1 kmx1 km spatial grid. Estimates of annual biogenic isoprene, monoterpene and OVOC fluxes for the reference year 1999 were 20.6, 38.9 and 13.3 kt, respectively, Quercus pubescens, Quercus ilex, Pinus halepensis and garrigue vegetation are the dominant emitting species of the area. VOC emissions from vegetation in this region contribute approximately 94% to the NMVOC (non-methane volatile organic compounds) of natural origin and are of the same order of magnitude as NMVOC emissions from anthropogenic sources. These results complete the global ESCOMPTE database needed to make an efficient strategy for tropospheric ozone reduction policy.

Quantifying the seasonal and interannual variability of North American isoprene emissions using satellite observations of the formaldehyde column

Quantifying isoprene emissions using satellite observations of the formaldehyde (HCHO) columns is subject to errors involving the column retrieval and the assumed relationship between HCHO columns and isoprene emissions, taken here from the GEOS‐CHEM chemical transport model. Here we use a 6‐year (1996–2001) HCHO column data set from the Global Ozone Monitoring Experiment (GOME) satellite instrument to (1) quantify these errors, (2) evaluate GOME‐derived isoprene emissions with in situ flux measurements and a process‐based emission inventory (Model of Emissions of Gases and Aerosols from Nature, MEGAN), and (3) investigate the factors driving the seasonal and interannual variability of North American isoprene emissions. The error in the GOME HCHO column retrieval is estimated to be 40%. We use the Master Chemical Mechanism (MCM) to quantify the time‐dependent HCHO production from isoprene, α‐ and β‐pinenes, and methylbutenol and show that only emissions of isoprene are detectable by GOME. The time‐dependent HCHO yield from isoprene oxidation calculated by MCM is 20–30% larger than in GEOS‐CHEM. GOME‐derived isoprene fluxes track the observed seasonal variation of in situ measurements at a Michigan forest site with a −30% bias. The seasonal variation of North American isoprene emissions during 2001 inferred from GOME is similar to MEGAN, with GOME emissions typically 25% higher (lower) at the beginning (end) of the growing season. GOME and MEGAN both show a maximum over the southeastern United States, but they differ in the precise location. The observed interannual variability of this maximum is 20–30%, depending on month. The MEGAN isoprene emission dependence on surface air temperature explains 75% of the month‐to‐month variability in GOME‐derived isoprene emissions over the southeastern United States during May–September 1996–2001.

Influence of nutrient availability, stand age, and canopy structure on isoprene flux in a Eucalyptus saligna experimental forest

Eucalyptus plantations occupy approximately 10 million ha of land in the tropics and, increasingly, afforestation and reforestation projects are relying on this genus to provide rapid occupation of degraded sites, large quantities of high‐quality wood products, and high rates of carbon sequestration. Members of the genus Eucalyptus are also very high emitters of isoprene, the dominant volatile organic compound emitted by trees in tropical ecosystems, which significantly influences the oxidative capacity of the atmosphere. While fertilization growth response of these trees has been intensively studied, little is known about how fertilization and tree age alter isoprene production from plantations of these trees. Here we examined the effects of fertilization and tree age on leaf‐level isoprene flux from 2‐ and 6‐year‐old trees in a Eucalyptus saligna experimental forest in Hawaii. Leaf‐level emission at a given canopy height did not differ between fertilized and unfertilized 6‐year‐old trees likely because leaf nitrogen content did not vary with fertilization. Across treatments, however, the standardized emission rate of isoprene (emission at a standard light and temperature) followed patterns of leaf N content and declined with canopy depth. Although leaf nitrogen content was similar between 2‐year and 6‐year fertilized trees, leaf‐level emission rates declined with stand age. Surprisingly, despite differences in stand leaf area and leaf area distribution, modeled canopy‐level isoprene flux was similar across stands varying in fertilization and tree age. Model results suggest that leaf area index was high enough in all treatments to absorb most of the light penetrating the canopy, leading to similar canopy flux rates despite the very different sized canopies.

Measurements of hydrocarbon emissions from a boreal fen using the REA technique

Abstract. Fluxes of biogenic volatile organic compounds (VOC) and methane were measured above a boreal fen. Vegetation on the fen is dominated by Sphagnum mosses and sedges. A relaxed eddy accumulation (REA) system with dynamic deadband was designed and constructed for the measurements. Methane, C2-C6 hydrocarbons and some halogenated hydrocarbons were analysed from the samples by gas chromatographs equipped with FID and ECD. A significant flux of isoprene and methane was detected during the growing seasons. Isoprene emission was found to follow the common isoprene emission algorithm. Average standard emission potential of isoprene was 680 µg m-2 h-1. Fluxes of other non-methane hydrocarbons were below detection limit.

Drought effect on isoprene production and consumption in Biosphere 2 tropical rainforest

AbstractIsoprene is the most abundant of the hydrocarbon compounds emitted from vegetation and plays a major role in tropospheric chemistry. Models predict that future climate change scenarios may lead to an increase in global isoprene emissions as a consequence of higher temperatures and extended drought periods. Tropical rainforests are responsible for more than 80% of global isoprene emissions, so it is important to obtain experimental data on isoprene production and consumption in these ecosystems under control of environmental variables. We explored isoprene emission and consumption in the tropical rainforest model ecosystem of Biosphere 2 laboratory during a mild water stress, and the relationship with light and temperature. Gross isoprene production (GIP) was not significantly affected by mild water stress in this experiment because the isoprene emitters were mainly distributed among the large, canopy layer trees with deep roots in the lower soil profile where water content decreased much less than the top 30 cm. However, as found in previous leaf level and whole canopy studies, the ecosystem gross primary production was reduced by (32%) during drought, and as a consequence the percentage of fixed C lost as isoprene tended to increase during drought, from ca. 1% in wet conditions to ca. 2% when soil water content reached its minimum. GIP correlated very well with both light and temperature. Notably, soil isoprene uptake decreased dramatically during the drought, leading to a large increase in daytime net isoprene fluxes.

Volatile organic compounds from vegetation in southern Yunnan Province, China: Emission rates and some potential regional implications

Little information is currently available regarding emissions of biogenic volatile organic compounds (BVOCs) in southern Asia. To address the need for BVOC emission estimates in regional atmospheric chemistry simulations, 95 common plant species were screened for emissions of BVOC in and near the Xishuangbanna Tropical Biological Gardens in southern Yunnan Province, Peoples’ Republic of China in February 2003. In situ measurements with leaf cuvettes and branch bag enclosures were used in combination with portable gas chromatography, flame ionization, photoionization, and mass spectral detection to identify and quantify BVOC emissions. Forty-four of the species examined emitted isoprene at rates exceeding 20 μg C g −1 (leaf dry weight) h −1. An emphasis was placed on the genus Ficus, which is important in the region and occupies a wide range of ecological niches. Several species in the footprint of a nearby flux tower were also examined. Several palm species and an abundant fern ( Cyclosorus parasiticus) emitted substantial amounts of isoprene, and probably accounted for observed daytime mean isoprene fluxes from the understory of a Hevea brasiliensis plantation of 1.0 and 0.15 mg C m −2 h −1 during the wet and dry seasons, respectively. These measurements verify that both the forest floor and canopy in this region can be sources of isoprene. Monoterpene emissions exceeded 1.0 μg-C g −1 (leaf dry weight) h −1 from only 4 of 38 species surveyed, including some Ficus species and H. brasiliensis. However most of the trees of the latter species were sparsely foliated due to dry season senescence, and emission factors are approximately an order of magnitude lower than those reported during the wet season. BVOC emission rates and physiology of many species are impacted by reduced moisture availability, especially Mangifera indica. South Asia is a region undergoing rapid landuse change and forest plantation establishment, with large increases in area of high BVOC-emitting species in the genera Bambusa, Elaeis, Eucalyptus, Hevea, Pinus, and Populus (among others). This could result in profound changes in atmospheric chemistry in these regions, for instance, terpene emissions from H. brasiliensis could increase wet season biogenic organic aerosol burdens by approximately a factor of 2 in the Xishuangbanna region. Increases in plantation area established with high isoprene emitting species, (e.g. Bambusa spp. and Eucalyptus spp.) are also projected for China and other parts of Southeast Asia in the near future. Thus, landcover change in South Asian landscapes is usually associated with large increases in BVOC flux with the potential to alter the atmospheric chemical composition and air quality over this rapidly developing region.

Diurnal variations and vertical gradients of biogenic volatile and semi-volatile organic compounds at the Tomakomai larch forest station in Japan

Volatile and semi-volatile organic compounds (VOCs and SVOCs) in the atmosphere control oxidative capacity of the air and formation of organic aerosols. To investigate sources, variations and fluxes of VOCs and SVOCs in the forest atmosphere, samples were collected in a larch forest at different heights in Tomakomai, Japan, from 3 to 5 September 2003 and were analyzed for VOCs (isoprene and α-pinene) and SVOCs (n-nonanal, n-decanal, glycolaldehyde, hydroxyacetone, glyoxal and methylglyoxal) using GC-FID and GC-MS. Isoprene (8–851 pptv) showed a diurnal variation with a maximum in daytime, whereas diurnal pattern was indistinct for α-pinene (6–145 pptv). SVOCs showed diurnal variations similar to isoprene, suggesting their origin to be biogenic. Denuder samplings of SVOCs demonstrated that up to 60% of SVOCs were present in aerosol particles. n-Nonanal and n-decanal were more abundant at lower altitude, suggesting their primary emissions from vegetations. In contrast, other four SVOCs showed an opposite or no trend and are considered as oxidation products of biogenic precursors such as isoprene. The averaged upward fluxes of isoprene and α-pinene were obtained to be 34.8 and 9.8 ng m-2 s-1, respectively. Magnitudes of SVOC fluxes were comparable to those of α-pinene, indicating that SVOCs affect budgets of organic gases/aerosols over the forest.

A relaxed-eddy-accumulation method for the measurement of isoprenoid canopy-fluxes using an online gas-chromatographic technique and PTR-MS simultaneously

A relaxed-eddy-accumulation set-up using an online gas-chromatographic technique and proton-transfer-reaction mass spectrometry was applied to determine isoprenoid fluxes above a Norway spruce forest in July 2001/2002. The system was quality assured and its suitability for determination of canopy fluxes of isoprenoids was demonstrated. Flux measurements of oxygenated hydrocarbons failed the data quality check due to artefacts presumably arising from line and ozone-scrubber effects. Observations of turbulent fluxes of isoprenoids during the two field experiments show good agreements with primary flux data derived from enclosure measurements and modelling results using a canopy-chemistry emission model (CACHE). For monoterpenes maximum daytime fluxes of more than 2 nmol m - 2 s - 1 were observed, isoprene fluxes reached 1– 1.5 nmol m - 2 s - 1 .

Relationships among canopy scale energy fluxes and isoprene flux derived from long-term, seasonal eddy covariance measurements over a hardwood forest

The flux of isoprene, one of the more reactive biogenic volatile organic compounds, was measured using eddy covariance techniques on a continuous basis during the 2000–2002 growing seasons at a mixed hardwood forest in northern lower MI. Daytime fluxes of isoprene and both sensible ( H) and latent heat flux (LE) were linearly correlated with a positive slope on a daily basis, but the slopes of these relationships varied from one day to the next. Under drought conditions and longer time periods, LE fluxes were suppressed yet isoprene emissions were enhanced; thus, the slope of the isoprene to LE relationship was increased. For example, seasonally averaged LE fluxes were reduced in 2000 as a result of reduced rainfall, and average isoprene fluxes were 1.5 times greater in 2000 compared to years 2001 and 2002. The strong daily correlation between isoprene fluxes and associated energy fluxes is an important relationship that should be accurately reflected in canopy models used for estimating biogenic emissions. In addition, in cases where land surface model output includes latent heat fluxes, the latent heat fluxes may be used as a surrogate for above canopy light and temperature to provide a simple estimate of isoprene emissions. Observed isoprene fluxes are compared to the Biogenic Emission Inventory System (BEIS3) biogenic emission model and to a canopy scale biogenic emission model (WSU-BEIS) that includes a leaf energy budget and accounts for vertical changes in light and temperature through the canopy. Comparison of the emission models with observations showed that the fractional gross errors in isoprene flux estimates were approximately 37% for both models in 2001 and 2002, but increased to approximately 62% in 2000 when less rain occurred and LE fluxes were reduced. The BEIS3 model does not treat sensible or latent heat flux, but the simple scaling and leaf energy budget used in WSU-BEIS yields estimates of LE within approximately 50% of observations. Estimates of sensible heat flux with WSU-BEIS were larger than observed and indicate that the simple scaling approach may not be capable of treating all of the dynamics of canopy energy transfer accurately. Nonetheless, the strong relationships observed between isoprene flux and the energy flux terms provide a basis for testing these and other canopy models used for estimates of biogenic emissions.

Coupled carbon-water exchange of the Amazon rain forest, II. Comparison of predicted and observed seasonal exchange of energy, CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, isoprene and ozone at a remote site in Rondônia

Abstract. A one-dimensional multi-layer scheme describing the coupled exchange of energy and CO2, the emission of isoprene and the dry deposition of ozone is applied to a rain forest canopy in southwest Amazonia. The model was constrained using mean diel cycles of micrometeorological quantities observed during two periods in the wet and dry season 1999. Calculated net fluxes and concentration profiles for both seasonal periods are compared to observations made at two nearby towers. The modeled day- and nighttime thermal stratification of the canopy layer is consistent with observations in dense canopies. The observed and modeled net fluxes above and H2O and CO2 concentration profiles within the canopy show a good agreement. The predicted net carbon sink decreases from 2.5 t C ha-1 yr-1 for wet season conditions to 1 t C ha-1 yr-1 for dry season conditions, whereas observed and modeled midday Bowen ratio increases from 0.5 to 0.8. The evaluation results confirmed a seasonal variability of leaf physiological parameters, as already suggested in a companion study. The calculated midday canopy net flux of isoprene increased from 7.1 mg C m-2 h-1 during the wet season to 11.4 mg C m-2 h-1 during the late dry season. Applying a constant emission capacity in all canopy layers, resulted in a disagreement between observed and simulated profiles of isoprene concentrations, suggesting a smaller emission capacity of shade adapted leaves and deposition to the soil or leaf surfaces. Assuming a strong light acclimation of emission capacity, equivalent to a 66% reduction of the standard emission factor for leaves in the lower canopy, resulted in a better agreement of observed and modeled concentration profiles and a 30% reduction of the canopy net flux compared to model calculations with a constant emission factor. The mean calculated ozone flux for dry season conditions at noontime was ≈12 n mol m-2 s-1, agreeing well with observed values. The corresponding deposition velocity increased from 0.8 cm s-1 to &gt;1.6 cm s-1 in the wet season, which can not be explained by increased stomatal uptake. Considering reasonable physiological changes in stomatal regulation, the modeled value was not larger than 1.05 cm s-1. Instead, the observed fluxes could be explained with the model by decreasing the cuticular resistance to ozone deposition from 5000 to 1000 s m-1.