Hal Westberg

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Vegetation provides a major source of reactive carbon entering the atmosphere. These compounds play an important role in (1) shaping global tropospheric chemistry, (2) regional photochemical oxidant formation, (3) balancing the global carbon cycle, and (4) production of organic acids which contribute to acidic deposition in rural areas. Present estimates place the total annual global emission of these compounds between approximately 500 and 825 Tg yr−1. The volatile olefinic compounds, such as isoprene and the monoterpenes, are thought to constitute the bulk of these emissions. However, it is becoming increasingly clear that a variety of partially oxidized hydrocarbons, principally alcohols, are also emitted. The available information concerning the terrestrial vegetation as sources of volatile organic compounds is reviewed. The biochemical processes associated with these emissions of the compounds and the atmospheric chemistry of the emitted compounds are discussed.

Measurement of methane emissions from ruminant livestock using a sulfur hexafluoride tracer technique.

The purpose of this paper is to describe a method for determining methane emission factors for cattle. The technique involves the direct measurement of methane emissions from livestock in their natural environment. A small permeation tube containing SF[sub 6] is placed in the cows rumen, and SF[sub 6] and CH[sub 4] concentrations are measured near the mouth and nostrils of the cow. The SF[sub 6] release provides a way to account for the dilution of gases near the animals mouth. The CH[sub 4] emission rate can be calculated from the known SF[sub 6] emission rate and the measured SF[sub 6] and CH[sub 4] concentrations. The tracer method described provides an easy means for acquiring a large methane emissions data base from domestic livestock. The low cost and simplicity should make it possible to monitor a large number of animals in countries throughout the world. An expanded data base of this type helps to reduce uncertainty in the ruminant contribution to the global methane budget. 18 refs., 3 figs., 3 tabs.

A biogenic hydrocarbon emission inventory for the U.S.A. using a simple forest canopy model

Abstract A biogenic hydrocarbon emission inventory system, developed for acid deposition and regional oxidant modeling, is described, and results for a U.S. emission inventory are presented. For deciduous and coniferous forests, scaling relationships are used to account for canopy effects upon solar radiation temperature, humidity and wind speed as a function of height through the canopy. Leaf temperature is calculated iteratively from a leaf energy balance as a function of height through the canopy. The predicted light and temperature levels are used with mean emprical emission rate factors and laboratory emission algorithms to predict hydrocarbon emission rates. For application to a U.S. inventory, diurnal emission fluxes of isoprene, α-pinene, other monoterpenes adn otehr hydrocarbons are predicted for eight land cover classes by state climatic division by month. The total U.S. emissions range from 22 to 50 Tg yr −1 depending upon the formulation of different emission rate factors. In the case where the forest canopy model is not used, the isoprene emissions increase by 50% and terpene emissions increase by 6%. In case study analyses, the predicted leaf temperatures were within 1–2°C of observed for a deciduous forest, and predicted emissions were within a factor of two of observations. Further evaluation of the inventory using field measurements is required to determine the overall accuracy of the emission estimates.

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.

Measurement of isoprene and its atmospheric oxidation products in a central Pennsylvania deciduous forest

Ambient concentrations of isoprene and several of its atmospheric oxidation productsmethacrolein, methylvinyl ketone, formaldehyde, formic acid, acetic acid, and pyruvic acid-were measured in a central Pennsylvania deciduous forest during the summer of 1988. Isoprene concentrations ranged from near zero at night to levels in excess of 30 ppbv during daylight hours. During fair weather periods, midday isoprene levels normally fell in the 5–10 ppbv range. Methacrolein and methylvinyl ketone levels ranged from less than 0.5 ppbv to greater than 3 ppbv with average midday concentrations in the 1 to 2 ppbv range. The diurnal behavior of formaldehyde paralleled that of isoprene with ambient concentrations lowest (∼1 ppbv) in the predawn hours and highest (>9.0 ppbv) during the afternoon. The organic acids peaked during the midday period with average ambient concentration of 2.5, 2.0, and 0.05 ppbv for formic, acetic, and pyruvic acid, respectively. These data indicate that oxygenated organics comprise a large fraction of the total volatile organic carbon containing species present in rural, forested regions of the eastern United States. Consequently, these compounds need to be included in photochemical models that attempt to simulate oxidant behavior and/or atmospheric acidity in these forested regions.

Simulation of summertime ozone over North America

The concentrations of O3 and its precursors over North America are simulated for three summer months with a three-dimensional, continental-scale photochemical model using meteorological input from the Goddard Institute for Space Studies (GISS) general circulation model (GCM). The model has 4°×5° grid resolution and represents non linear chemistry in urban and industrial plumes with a subgrid nested scheme. Simulated median afternoon O3 concentrations at rural U.S. sites are within 5 ppb of observations in most cases, except in the south central United States where concentrations are overpredicted by 15–20 ppb. The model captures successfully the development of regional high-O3 episodes over the northeastern United States on the back side of weak, warm, stagnant anticyclones. Simulated concentrations of CO and nonmethane hydrocarbons are generally in good agreement with observations, concentrations of NOx are underpredicted by 10–30%, and concentrations of peroxyacylnitrates (PANs) are overpredicted by a factor of 2 to 3. The overprediction of PANs is attributed to flaws in the photochemical mechanism, including excessive production from oxidation of isoprene, and may also reflect an underestimate of PANs deposition. Subgrid nonlinear chemistry as captured by the nested plumes scheme decreases the net O3 production computed in the United States boundary layer by 8% on average.

Nonmethane hydrocarbon composition of urban and rural atmospheres

Individual hydrocarbon species have been recorded in some 500 samples collected in both urban and rural areas. Rural nonmethane hydrocarbon levels are some five percent of those in urban regions. 16 refs.

Peroxy radicals in the ROSE experiment: Measurement and theory

The concentrations of the HO2-RO2 species measured during July 11, 1990, in the ROSE (Rural Oxidants in the Southern Environment) study in Alabama are compared to those expected in theory from calculations based upon detailed hourly measurements of a variety of trace gases including the hydrocarbons, NO, NO2, carbonyl compounds, CO, PAN (peroxyacetylnitrate) and calculated jO3 values. The measurements are also compared with the [HO2] + [RO2] as estimated from deviations from the NO2 + hv (+O2) ⇄ NO + O3 photostationary state. Within the error of the measurements all of the data appear to be in reasonable accord.

Peroxy radicals as measured in ROSE and estimated from photostationary state deviations

Ambient measurements of peroxy radical concentrations were made using the chemical amplifier (CA) and determined independently from photostationary state deviations (PSSD), NO2 + hv (+O2) ⇌ NO + O3, derived from simultaneous measurements of O3, NO, NO2 and jNO2. The data were collected in the Rural Oxidants in the Southern Environment experiment during 19 days of July 1990. A reasonably good correspondence between the two methods is observed for many of the days, although estimates from the PSSD method for some of the days are higher by as much as a factor of 2. Scatter observed between estimates probably results from several sources: uncertainties in the calibration of the RO2-HO2 instrument, rapid changes in the ozone background, rapid alterations in the solar flux induced by intermittent cloud cover, and imprecisions in making simultaneous measurements of [NO], [NO2], [O3], and jNO2 required for the PSSD method. Possible origins of bias in the two measurement techniques are discussed. Theoretical estimates of the peroxy radical concentrations were made using the measured suite of trace gas concentrations for 2 days, one for which the CA and PSSD estimates of peroxy radical concentrations differed significantly (July 14) and one for which they showed good agreement (July 11). Theoretical estimates for July 11 checked well with the results from both methods. Those for July 14 fell between the GA and PSSD estimates. These results suggest that the PSSD method may have a bias toward higher estimates on some days and/or that the CA method may have a bias for the lower estimates for reasons which are discussed.