C. N. Hewitt

Relative contribution of oxygenated hydrocarbons to the total biogenic VOC emissions of selected mid-European agricultural and natural plant species

Abstract Emission rates of more than 50 individual VOCs were determined for eight plant species and three different types of grass land typical for natural deciduous and agricultural vegetation in Austria. In addition to the emissions of isoprene and monoterpenes, 33 biogenic oxygenated volatile organic compounds (BOVOCs) were detected. Of these, 2-methyl-l-propanol, 1-butanal, 2-butanal, 1-pentanol, 3-pentanol, 1-hexanol, 6-methyl-5-hepten-2-one, butanal and ethylhexylacetate were observed for the first time as plant emissions. In terms of prevalence of one of the groups of emitted VOCs (isoprene, terpenes, BOVOCs) the grain plants wheat and rye, grape, oilseed rape and the decidous trees hombeam and birch could be classified as “BOVOC”-emitters. For the grass plots examined, BOVOCs and terpenes appear to be of equal importance. The emission rates of the total assigned organic plant emissions ranged from 0.01 μ g −1 h −1 for wheat to 0.8 μg g −1 h −1 for oak (based on dry leaf weight). Intercomparison with available data from other studies show that our emission rates are rather at the lower end of reported ranges. The influence of the stage of growth was examined for rye, rape (comparing emissions of blossoming and nonblossoming plants) and for grape (with and without fruit). Emission rate differences for different stages of growth varied from nondetectable for blossoming and nonblossoming rye to a factor of six for the grape with fruits vs grape without fruits (emission rate based on dry leaf weight). The major decidous tree in Austria (beech) is a terpene emitter, with the contribution of BOVOCs below 5% of the total assigned emissions of 0.2 μg g −1 h −1 for the investigations of 20°C.

Screening of 18 Mediterranean plant species for volatile organic compound emissions

Abstract Eighteen tree and shrub species were screened for emissions of isoprene and other volatile organic compounds (VOCs) at three locations at Castelporziano (Italy) using a bag-enclosure sampling method followed by GC analysis. Thirty emitted compounds were identified. Temperature sensitivity of emissions of monoterpenes varied between species. Strong temperature dependencies were found for isoprene emissions. For monoterpene-emitting plant species with greatest ground cover in the dunes and macchia habitats, α-pinene, β-pinene and sabinene appeared to be the most frequently and abundantly emitted compounds. Isoprene was the major emission from the shrub species screened in the forest. Emissions from four dominant plant species were scaled up to estimate total fluxes from the dunes and macchia over a daytime period. Species with greatest biomass but low emission rates made a substantial contribution to total emissions.

The application of proton transfer reaction-mass spectrometry (PTR-MS) to the monitoring and analysis of volatile organic compounds in the atmosphere

Proton transfer reaction-mass spectrometry (PTR-MS) is a new and emerging technique for the measurement and monitoring of volatile organic compounds (VOCs) at low concentrations in gaseous samples in more-or-less real time. Utilising chemical ionisation, it combines the desirable attributes of high sensitivity and short integration times with good precision and accuracy. Recently it has been exploited in applications related to atmospheric science. Here, the principles of operation of the PTR-MS are described, its advantages and disadvantages discussed, its inherent uncertainties highlighted, some of its uses in atmospheric sciences reviewed, and some suggestions made on its future application to atmospheric chemistry.

Measurement of monoterpenes and related compounds by proton transfer reaction-mass spectrometry (PTR-MS)

The reactions of monoterpenes and related C10 compounds with H3O+ in a proton transfer reaction-mass spectrometer (PTR-MS) were studied, with a view to better understanding the signal produced by this instrument when detecting these compounds. The monoterpenes α- and β-pinene, 3-carene and limonene produced fragment ions of masses 67, 81 and 95 as well as a protonated molecular ion of mass 137, while p-cymene (C10H14) produced ions of masses 41, 91, 93 and 119 in addition to mass 135. The fragmentation patterns were observed to vary as E/N was varied. Camphor (C10H16O) did not fragment within the E/N range 80–120 Td. The proton transfer reaction rate coefficients for these monoterpene species with H3O+ were found to be 2.2×10−9 to 2.5×10−9 cm3 s−1. For camphor the rate coefficient was 4.4×10−9 cm3 s−1. Water vapour pressure in the inlet air affected the fragmentation pattern for p-cymene, limonene and 3-carene. The uncertainties associated with the PTR-MS measurement of these compounds are discussed.

Nitrogen management is essential to prevent tropical oil palm plantations from causing ground-level ozone pollution

More than half the worlds rainforest has been lost to agriculture since the Industrial Revolution. Among the most widespread tropical crops is oil palm (Elaeis guineensis): global production now exceeds 35 million tonnes per year. In Malaysia, for example, 13% of land area is now oil palm plantation, compared with 1% in 1974. There are enormous pressures to increase palm oil production for food, domestic products, and, especially, biofuels. Greater use of palm oil for biofuel production is predicated on the assumption that palm oil is an “environmentally friendly” fuel feedstock. Here we show, using measurements and models, that oil palm plantations in Malaysia directly emit more oxides of nitrogen and volatile organic compounds than rainforest. These compounds lead to the production of ground-level ozone (O3), an air pollutant that damages human health, plants, and materials, reduces crop productivity, and has effects on the Earths climate. Our measurements show that, at present, O3 concentrations do not differ significantly over rainforest and adjacent oil palm plantation landscapes. However, our model calculations predict that if concentrations of oxides of nitrogen in Borneo are allowed to reach those currently seen over rural North America and Europe, ground-level O3 concentrations will reach 100 parts per billion (109) volume (ppbv) and exceed levels known to be harmful to human health. Our study provides an early warning of the urgent need to develop policies that manage nitrogen emissions if the detrimental effects of palm oil production on air quality and climate are to be avoided.

Effect of habitat and age on variations in volatile organic compound (VOC) emissions from Quercus ilex and Pinus pinea

A dynamic branch enclosure was used to measure emission rates of volatile organic compounds (VOCs) under field conditions from two common native Mediterranean species, Quercus ilex and Pinus pinea. In addition to α-pinene, β-pinene, sabinene, limonene and cineole, a suite of lesser known compounds were tentatively identified including cis- and trans-ocimene, cis- and trans-linalool oxide and sabinaketone. Emissions of isoprene from Quercus ilex were insignificant in comparison to those of the monoterpenes and were not detected from Pinus pinea. Variability in emission rates between two habitats, the forest and the dunes, were assessed for Quercus ilex. Temperature sensitivities of emissions and total summed emission rates from Quercus ilex were clearly related to environmental conditions. Emission rates from Pinus pinea showed great variability, but differences between normalised mean emission rates from mature forest and young plantation trees may be significant. Existing emission rate models were found to inadequately describe the observed data.

An overview of the Castelporziano experiments

This paper reviews the major outcomes of the measuring campaigns performed at the Castelporziano nature preserve near Rome, Italy, by 14 European laboratories as part of the BEMA (Biogenic Emissions in the Mediterranean Area)-project. Six campaigns of 1–4 weeks duration were carried out in different seasons of the years 1993–1994 at semi-continuously running test plots in the nature reserve, representing common Mediterranean vegetation types. The aim was to characterise, at the different test plots, the atmospheric chemical and meteorological situations, the plant biomass and physiology, the type, amount and controls of emissions from different plants by means of branch enclosures, and the BVOC emission fluxes from different ecosystems, by scaling up enclosure data from individual sources, and by measuring fluxes directly by use of micrometeorological methods. An important focus during the initial phase of the five year BEMA-project was the harmonisation and improvement of the analytical, physiological and micrometeorological methods used, and the development and testing of new methods for measuring BVOC fluxes.

The atmospheric chemistry of sulphur and nitrogen in power station plumes

Emissions of sulphur and nitrogen compounds from power stations represent a significant fraction of the total emissions of these elements to the atmosphere. Understanding their subsequent chemical reactions in the atmosphere is of fundamental importance as without it, a quantitative assessment of their contribution to local and regional scale air pollution is not possible. Here the atmospheric chemistry of sulphur dioxide and the oxides of nitrogen, and their resultant likely behaviour in the plumes of power stations are reviewed

Light dependency of VOC emissions from selected Mediterranean plant species

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

An integrated budget for selected pollutants for a major rural highway.

A comprehensive study has been made of the fluxes of selected pollutants emitted from a major rural highway in NW England. Lead, cadmium, copper, the organic compounds of lead and 8 PAH species have been studied and their fluxes measured in bulk deposition samples in transects away from the road in the road runoff waters and its associated sediments and in soil profiles. Data collected in detail over one year indicate that, in the case of lead, 8% of the emitted metal is removed in the drainage waters 6% is deposited in the first 50 m adjacent to the motorway and approximately 86% is dispersed in the atmosphere away from the immediate vicinity of the road. Uncertainties in the emission rates of the other metals prevent such budget calculations being made. The amount of PAH removed away from the road environment by the atmosphere varies from approximately 99% for the lowest molecular weight compounds to approximately 70% for the heavier compound.