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

More than half the world's 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 (O(3)), an air pollutant that damages human health, plants, and materials, reduces crop productivity, and has effects on the Earth's climate. Our measurements show that, at present, O(3) 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 O(3) concentrations will reach 100 parts per billion (10(9)) 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.

Defining hybrid poplar (Populus deltoides x Populus trichocarpa) tolerance to ozone: identifying key parameters.

This study examined whether two genotypes of hybrid poplar (Populus deltoides x Populus trichocarpa), previously classified as ozone tolerant and ozone sensitive, had differing physiological and biochemical responses when fumigated with 120 nL L(-1) ozone for 6 h per day for eight consecutive days. Isoprene emission rate, ozone uptake and a number of physiological and biochemical parameters were investigated before, during and after fumigation with ozone. Previous studies have shown that isoprene protects plants against oxidative stress. Therefore, it was hypothesized that these two genotypes would differ in either their basal isoprene emission rates or in the response of isoprene to fumigation by ozone. Our results showed that the basal emission rates of isoprene, physiological responses and ozone uptake rates were all similar. However, significant differences were found in visible damage, carotenoids, hydrogen peroxide (H(2)O(2)), thiobarbituric acid reactions (TBARS) and post-fumigation isoprene emission rates. It is shown that, although the classification of ozone tolerance or sensitivity had been previously clearly and carefully defined using one particular set of parameters, assessment of other key variables does not necessarily lead to the same conclusions. Thus, it may be necessary to reconsider the way in which plants are classified as ozone tolerant or sensitive.

The effect of ozone fumigation on the biogenic volatile organic compounds (BVOCs) emitted from Brassica napus above- and below-ground.

The emissions of BVOCs from oilseed rape (Brassica napus), both when the plant is exposed to clean air and when it is fumigated with ozone at environmentally-relevant mixing ratios (ca. 135 ppbv), were measured under controlled laboratory conditions. Emissions of BVOCs were recorded from combined leaf and root chambers using a recently developed Selective Reagent Ionisation-Time of Flight-Mass Spectrometer (SRI-ToF-MS) enabling BVOC detection with high time and mass resolution, together with the ability to identify certain molecular functionality. Emissions of BVOCs from below-ground were found to be dominated by sulfur compounds including methanethiol, dimethyl disulfide and dimethyl sulfide, and these emissions did not change following fumigation of the plant with ozone. Emissions from above-ground plant organs exposed to clean air were dominated by methanol, monoterpenes, 4-oxopentanal and methanethiol. Ozone fumigation of the plants caused a rapid decrease in monoterpene and sesquiterpene concentrations in the leaf chamber and increased concentrations of ca. 20 oxygenated species, almost doubling the total carbon lost by the plant leaves as volatiles. The drop in sesquiterpenes concentrations was attributed to ozonolysis occurring to a major extent on the leaf surface. The drop in monoterpene concentrations was attributed to gas phase reactions with OH radicals deriving from ozonolysis reactions. As plant-emitted terpenoids have been shown to play a role in plant-plant and plant-insect signalling, the rapid loss of these species in the air surrounding the plants during photochemical pollution episodes may have a significant impact on plant-plant and plant-insect communications.

Forests and Their Canopies: Achievements and Horizons in Canopy Science.

Forest canopies are dynamic interfaces between organisms and atmosphere, providing buffered microclimates and complex microhabitats. Canopies form vertically stratified ecosystems interconnected with other strata. Some forest biodiversity patterns and food webs have been documented and measurements of ecophysiology and biogeochemical cycling have allowed analyses of large-scale transfer of CO2, water, and trace gases between forests and the atmosphere. However, many knowledge gaps remain. With global research networks and databases, and new technologies and infrastructure, we envisage rapid advances in our understanding of the mechanisms that drive the spatial and temporal dynamics of forests and their canopies. Such understanding is vital for the successful management and conservation of global forests and the ecosystem services they provide to the world.

Atmospheric benzenoid emissions from plants rival those from fossil fuels.

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y(-1)), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

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.

Measurements of alkyllead compounds in the gas and aerosol phase in urban and rural atmospheres.

Alkyllead compounds in the gas and aerosol phase were determined simultaneously in urban and rural atmospheres using gas chromatography--atomic absorption spectroscopy and wet chemical (iodine monochloride) methods. The difference in results between the two methods suggests the presence of vapour-phase tri- (and/or di-)alkyllead in both urban and rural air. Concentrations of 0.06-1.6 and 16-205 ng Pb m-3 were found for vapour-phase organolead compounds other than tetraalkyllead in rural and kerbside urban air, respectively. Tetraalkyllead and trialkyllead compounds were identified in atmospheric aerosols at both sites, but these were found to be present at concentrations less than 1.2% of the total gas-phase alkyllead.

The environmental half-lives and mean residence times of contaminants in dust for an urban environment: Barrow-in-Furness.

Radiocaesium contamination of dusts from external (road and school yards) and internal (house) environments within Barrow-in-Furness was found to be derived from the primary input event of Chernobyl fallout. The specific activity of radiocaesium in the dust reservoirs studied, decreased exponentially, enabling environmental half-lives to be calculated (190-370 day). The broad similarity of these half-lives indicated that secondary contamination processes, such as atmospheric deposition of resuspended dust, cause all the internal and external reservoirs to be linked into a system encompassing much of Barrow-in-Furness. Mean residence times of external dust were derived from the calculated environmental half-lives and measurements of atmospheric deposition (150-250 day). These mean residence times are dependent on local processes and are thus site specific, whilst the environmental half-lives represent an integration of all the processes operating in Barrow-in-Furness.

Effects of reactive hydrocarbons and hydrogen peroxide on antioxidant activity in cherry leaves.

One-year-old cherry trees were fumigated with propene and gas-phase hydrogen peroxide, singly and in combination, in controlled-environment chambers for an 8-week period during the summer season. A UV light source was included with the combined propene and hydrogen peroxide regime to provide a source of hydroxyl radicals and ozone, and thus all the constituents of a photochemical smog. Measurements were made of soluble protein concentration and of glutathione reductase activity in leaf extracts from two or three leaf classes in plants from each treatment regime at the end of each fumigation period. Significant increases in soluble protein concentration with respect to the controls were found in plants fumigated with propene and hydrogen peroxide. The occurrence and extent of these differences depended on the leaf class and on the timing of the fumigation period over the summer with respect to bud break. The activity of glutathione reductase was found to be significantly increased in mature lower leaves of plants which had been fumigated with hydrogen peroxide. This effect was independent of the timing of fumigation with respect to bud break. Enzyme activity was also increased in propene and in propene plus hydrogen peroxide treatments, but only when plants were fumigated early in the growth season.

Spatially-varying surface roughness and ground-level air quality in an operational dispersion model.

Urban form controls the overall aerodynamic roughness of a city, and hence plays a significant role in how air flow interacts with the urban landscape. This paper reports improved model performance resulting from the introduction of variable surface roughness in the operational air-quality model ADMS-Urban (v3.1). We then assess to what extent pollutant concentrations can be reduced solely through local reductions in roughness. The model results suggest that reducing surface roughness in a city centre can increase ground-level pollutant concentrations, both locally in the area of reduced roughness and downwind of that area. The unexpected simulation of increased ground-level pollutant concentrations implies that this type of modelling should be used with caution for urban planning and design studies looking at ventilation of pollution. We expect the results from this study to be relevant for all atmospheric dispersion models with urban-surface parameterisations based on roughness.

The atmospheric chemistry of trace gases and particulate matter emitted by different land uses in Borneo.

We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.

The impact of local surface changes in Borneo on atmospheric composition at wider spatial scales: coastal processes, land-use change and air quality.

We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO(x) emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.

An exposure system for the calibration of passive samplers to volatile organic compounds at low (ppbv) concentrations.

A recycling exposure system, which has characteristics of dynamic and static systems, has been designed and constructed for calibrating passive sampling tubes. This system is very easy to set up and maintain. Organic vapors inside the system are generated by syringe injection, and homogeneous vapors are circulated by a metal-bellows pump. The concentrations of light hydrocarbons (e.g., isoprene) may decrease slightly after circulating for longer than 10 hours; however, this system is very stable for C5-C8 hydrocarbons for at least eight hours. The system has been used successfully to calibrate Perkin-Elmer diffusion tubes packed with Chromosorb 106 for collecting benzene vapor at low exposure doses (< 70 ppmv x min). The entire system can be easily and effectively cleaned by circulating through a U-tube packed with activated carbon.

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.

Hydroperoxides in plants exposed to ozone mediate air pollution damage to alkene emitters.

OZONE is phytotoxic: it is damaging to cell integrity and photosynthesis(1,2), causing leaf necrosis(3) and reducing crop yield(4). It has been implicated in forest decline(5), perhaps through interactions with stress ethene(6). Here we show that organic hydroperoxides (ROOH), which are products of ozone-alkene reactions(7-9), are present in the leaves of isoprene-emitting plants after exposure to ozone, but are not found in control plants grown in clean air. On the basis of earlier studies(6,7,10), we suggest that this reaction of ozone with biogenic alkenes to produce toxic ROOH could be one of the mechanisms by which damage to plants occurs. This could be particularly important in areas experiencing acidic deposition, where the stability of ROOH will be enhanced. This model may explain in part the die-back of tree species producing reactive alkenes, such as the red spruce, which emits isoprene(11-15) and monoterpenes(16), and the Norway spruce and silver fir, which are both prolific monoterpene emitters(17).