Chris Geron

A global model of natural volatile organic compound emissions

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5° × 0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.

Natural emissions of non-methane volatile organic compounds, carbon monoxide, and oxides of nitrogen from North America

The magnitudes, distributions, controlling processes and uncertainties associated with North American natural emissions of oxidant precursors are reviewed. Natural emissions are responsible for a major portion of the compounds, including non-methane volatile organic compounds (NMVOC), carbon monoxide (CO) and nitric oxide (NO), that determine tropospheric oxidant concentrations. Natural sources include soil microbes, vegetation, biomass burning, and lightning. These sources are strongly in#uenced by human activities that have led to signicant changes in the magnitude and distribution of natural emissions in the past two centuries. The total NMVOC #ux of about 84]1012 g of carbon (Tg C) is comprised primarily of isoprene (35%), 19 other terpenoid compounds (25%) and 17 non-terpenoid compounds (40%). Vegetation is predicted to contribute about 98% of the total annual natural NMVOC emission. The estimated annual natural NO emission of 2.1]1012 g of nitrogen (Tg N) from North America is primarily due to soils and lightning, while the estimated 10 Tg C of CO arises from biomass burning and vegetation. Field measurements of ambient concentrations and above canopy #uxes have validated emission estimates for a few compounds from some important landscapes. The uncertainty associated with natural emission estimates ranges from less than 50% for midday summer isoprene emission from some locations to about a factor of 10 for some compounds and landscapes. ( 2000 Elsevier Science Ltd. All rights reserved.

A review and synthesis of monoterpene speciation from forests in the United States

Abstract The monoterpene composition (emission and tissue internal concentration) of major forest tree species in the United States is discussed. Of the 14 most commonly occurring compounds ( α -pinene, β -pinene, Δ 3 -carene, d -limonene, camphene, myrcene, α -terpinene, β -phellandrene, sabinene, ρ -cymene, ocimene, α -thujene, terpinolene, and γ -terpinene), the first six are usually found to be most abundant. Expected regional variability based on the monoterpene composition fingerprints and corresponding tree species distribution and abundance is examined. In the southeast, α -pinene and β -pinene seem to dominate monoterpene emissions, while in the northern forests emissions are distributed more evenly among the six major compounds. In some parts of western forests, β -pinene and Δ 3 -carene can be more abundant than α -pinene. Among the other eight compounds, β -phellandrene and sabinene occasionally are significant percentages of expected local monoterpene emissions. Ocimene and ρ -cymene are estimated to be more common in regions dominated by deciduous broadleaf forests, although total emission rates are generally lower for these forests relative to those dominated by conifers. These percentages are compared with monoterpene composition measured in ambient air at various sites. Estimated monoterpene emission composition based on local forest species composition agrees fairly well with ambient measurements for the six major compounds. The past assumption that α -pinene composes approximately 50% of total monoterpene emissions appears reasonable for many areas, except for possibly the northern coniferous forests and some areas in the west dominated by true firs, spruce, and western pines (lodgepole and ponderosa pines). The oxygenated monoterpenes such as camphor, bornyl acetate, and cineole often compose high percentages of the monoterpenes within plant tissues, but are much less abundant in emission samples. Even after adjusting for lower vapor pressures of these compounds, emission rates relative to the hydrocarbon monoterpenes are often lower than would be expected from their internal concentrations. More study is warranted on monoterpene emission rates and composition, especially from the spruces, true firs, hemlocks, cedars, and some deciduous species such as the maples. Non-invasive canopy level and whole ecosystem flux studies are also needed to establish uncertainty estimates for monoterpene emission models.

Exchange processes of volatile organic compounds above a tropical rain forest: Implications for modeling tropospheric chemistry above dense vegetation

[1]xa0Disjunct eddy covariance in conjunction with continuous in-canopy gradient measurements allowed for the first time to quantify the fine-scale source and sink distribution of some of the most abundant biogenic (isoprene, monoterpenes, methanol, acetaldehyde, and acetone) and photooxidized (MVK+MAC, acetone, acetaldehyde, acetic, and formic acid) VOCs in an old growth tropical rain forest. Our measurements revealed substantial isoprene emissions (up to 2.50 mg m−2 h−1) and light-dependent monoterpene emissions (up to 0.33 mg m−2 h−1) at the peak of the dry season (April and May 2003). Oxygenated species such as methanol, acetone, and acetaldehyde were typically emitted during daytime with net fluxes up to 0.50, 0.36, and 0.20 mg m−2 h−1, respectively. When generalized for tropical rain forests, these fluxes would add up to a total emission of 36, 16, 19, 106, and 7.2 Tg/yr for methanol, acetaldehyde, acetone, isoprene, and monoterpenes, respectively. During nighttime we observed strong sinks for oxygenated and nitrogen-containing compounds such as methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile with deposition velocities close to the aerodynamic limit. This suggests that the canopy resistance (Rc) is very small and not the rate-limiting step for the nighttime deposition of many VOCs. Our measured mean dry deposition velocities of methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile were a factor 10–20 higher than estimated from traditional deposition models. If our measurements are generalized, this could have important implications for the redistribution of VOCs in atmospheric chemistry models. Our observations indicate that the current understanding of reactive carbon exchange can only be seen as a first-order approximation.

Isoprene fluxes measured by enclosure, relaxed eddy accumulation, surface layer gradient, mixed layer gradient, and mixed layer mass balance techniques

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

Estimates of regional natural volatile organic compound fluxes from enclosure and ambient measurements

Natural volatile organic compound (VOC) emissions were investigated at two forested sites in the southeastern United States. A variety of VOC compounds including methanol, 2-methyl-3-buten-2-ol, 6-methyl-5-hepten-2-one, isoprene and 15 monoterpenes were emitted from vegetation at these sites. Diurnal variations in VOC emissions were observed and related to light and temperature. Variations in isoprene emission from individual branches are well correlated with light intensity and leaf temperature while variations in monoterpene emissions can be explained by variations in leaf temperature alone. Isoprene emission rates for individual leaves tend to be about 75% higher than branch average emission rates due to shading on the lower leaves of a branch. Average daytime mixing ratios of 13.8 and 6.6 ppbv C isoprene and 5.0 and 4.5 ppbv C monoterpenes were observed at heights between 40 m and 1 km above ground level the two sites. Isoprene and monoterpenes account for 30% to 40% of the total carbon in the ambient non-methane VOC quantified in the mixed layer at these sites and over 90% of the VOC reactivity with OH. Ambient mixing ratios were used to estimate isoprene and monoterpene fluxes by applying box model and mixed-layer gradient techniques. Although the two techniques estimate fluxes averaged over different spatial scales, the average fluxes calculated by the two techniques agree within a factor of two. The ambient mixing ratios were used to evaluate a biogenic VOC emission model that uses field measurements of plant species composition, remotely sensed vegetation distributions, leaf level emission potentials determined from vegetation enclosures, and light and temperature dependent emission activity factors. Emissions estimated for a temperature of 30°C and above canopy photosynthetically active radiation flux of 1000 μmol m−2 s−1 are around 4 mg C m−2 h−1 of isoprene and 0.7 mg C m−2 h−1 of monoterpenes at the ROSE site in western Alabama and 3 mg C m−2 h−1 of isoprene and 0.5 mg C m−2 h−1 of monoterpenes at the SOS-M site in eastern Georgia. Isoprene and monoterpene emissions based on land characteristics data and emission enclosure measurements are within a factor of two of estimates based on ambient measurements in most cases. This represents reasonable agreement due to the large uncertainties associated with these models and because the observed differences are at least partially due to differences in the size and location of the source region (“flux footprint”) associated with each flux estimate.

WEATHER EFFECTS ON ISOPRENE EMISSION CAPACITY AND APPLICATIONS IN EMISSIONS ALGORITHMS

Many plants synthesize isoprene. Because it is volatile and reacts rapidly with hydroxyl radicals, it is emitted to the atmosphere and plays a critical role in atmospheric chemistry. Determining effective remediation efforts for ozone pollution requires accurate isoprene-emission inventories. Temperature and light effects on isoprene emission from plants over minutes to a few hours are fairly well known, but effects over a few days (i.e., influenced by weather) are also possible. We measured isoprene emission and photosynthesis under constant temperature and light (known as the basal emission rate, which reflects the capacity for isoprene emission) during eight field trips from 1994 to 1996. Measurements were made at the tops of oak trees at two sites between May and September. On six of the trips, the effect of short-term (minutes to hours) temperature changes was also investigated. The basal emission rate of isoprene was highly correlated with the average temperature of the previous two days. Including ...

Biogenic volatile organic compound emissions (BVOCs). I. Identifications from three continental sites in the U.S.

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).

Measurement and interpretation of isoprene fluxes and isoprene, methacrolein, and methyl vinyl ketone mixing ratios at the PROPHET site during the 1998 intensive

[1]xa0Mixing ratios of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) were determined continuously during an 8-day period in the summer of 1998 at a rural forested site located within the University of Michigan Biological Station (UMBS). The measurements were obtained as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport (PROPHET) study. Fluxes of isoprene were concurrently measured at a nearby tower (AmeriFlux, located 132 m north-northeast of the PROPHET tower). Following the study, 1-km-resolution emission estimates were derived for isoprene within a 60-km radius of the tower using forest density estimates (Biogenic Emissions Inventory System (BEIS3) model). Measured isoprene fluxes at the site compared well with modeled isoprene fluxes when using BEIS3 and a detailed leaf litter-fall data set by tree species from the UMBS site. Mean midday (1000–1400 LT) mixing ratios for isoprene, MACR, and MVK were 1.90 ± 0.43, 0.07 ± 0.01, and 0.14 ± 0.04 ppbv, respectively. Median midday mixing ratios of these compounds were 1.96 ± 0.26, 0.06 ± 0.02, and 0.10 ± 0.02 ppbv, respectively. Ratios of the isoprene oxidation products to isoprene are understood in the context of previous laboratory and field measurement studies of these compounds and a simple consecutive reaction scheme model. Results of the model indicate that the air masses studied represented relatively fresh emissions with a photochemical age of measured isoprene between 3.6 and 18 min, which is significantly less than the photochemical lifetime of isoprene (τ = 45 min at [OH] = 3.35 × 106 molecules cm−3). Thus a large portion of the isoprene that reaches the manifold has not had time to react completely with OH, yielding lower than expected ratios based on model calculations that do not explicitly take this into account. A rapid decrease in isoprene mixing ratios was observed soon after sunset, followed by a slower decay throughout the rest of the night. Emission maps were generated indicating that isoprene fluxes are highest in the immediate vicinity of the tower compared to the surrounding area of the site. Thus vertical diffusion and advection from the surrounding region are postulated to cause the observed initial rapid decrease in isoprene at the site. The second isoprene decay may be due to chemistry and/or dynamics, but the effects cannot be separated with the available data.

Isoprene emission capacity for US tree species

Isoprene emission capacity measurements are presented from 18 North American oak (Quercus) species and species from six other genera previously found to emit signicant quantities of isoprene. Sampling was conducted at physiographically diverse locations in North Carolina, Central California, and Northern Oregon. Emissions from several sun leaves of each species were measured at or near standard conditions (leaf temperature of 303C and photosynthetically active radiation of 1000mol m s) using environmentally controlled cuvette systems and gas chromatography with reduction gas detectors. Species mean emission capacity ranged from 39 to 158 gC g h (mean of 86), or 22 to 79 nmol m s (mean of 44). These rates are 2}28 times higher than those previously reported from the same species, which were summarized in a recent study where isoprene emission rates were assigned based on published data and taxonomy. These discrepancies were attributed to di!erences in leaf environment during development, measurement technique (branch or plant enclosure versus leaf enclosure), and lack of environmental measurements associated with some of the earlier branch enclosure measurements. Mass-based emission capacities for 15 of 18 oak species, sweetgum (Liquidambar styraciyua), and poplars (Populus trichocarpa and P. deltoides) were within ranges used in current biogenic volatile organic compound (BVOC) emission models, while measured rates for the remaining three oak species, Nyssa sylvatica, Platanus occidentalis, Robinia pseudoacacia, Salix nigra, and Populus hybrids (Populus trichocarpa P. deltoides) were considerably higher. In addition, mean specic leaf mass of the oak species was 30% higher than assumed in current emission models. Emission rates reported here and in other recent studies support recent conclusions that isoprene emission capacities for sun leaves of high emitting species may be better represented by a value of 100